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Improving the functionality of carbon nanodots:

doping and surface functionalization
Published on 27 June 2016. Downloaded by McMaster University on 9/25/2024 3:03:36 PM.
Cite this: J. Mater. Chem. A, 2016, 4,

11582
Y. Park,†a J. Yoo,†a B. Lim,b W. Kwon*b and S.-W. Rhee*ab
Distinct from conventional carbon nanostructures, such as fullerene, graphene, and carbon nanotubes,
carbon nanodots (C-dots) exhibit unique properties such as strong fluorescence, high photostability,
chemical inertness, low toxicity, and biocompatibility. Various synthesis routes for C-dots have been
developed in the last few years, and now intense research efforts have been focused on improving their
functionality. In this aspect, doping and surface functionalization are two major ways to control the
chemical, optical, and electrical properties of C-dots. Doping introduces atomic impurities into C-dots
Received 8th June 2016
Accepted 27th June 2016
to modulate their electronic structure, and surface functionalization modifies the C-dot surface with
functional molecules or polymers. In this review, we summarize recent progress in doping and surface
DOI: 10.1039/c6ta04813g
functionalization of C-dots for improving their functionality, and offer insight into controlling the
www.rsc.org/MaterialsA properties of C-dots for a variety of applications ranging from biomedicine to optoelectronics to energy.
electrochemical oxidation, solvothermal carbonization, tem-

1. Introduction plated carbonization, and microwave irradiation. Furthermore,
Carbon nanodots (C-dots), uorescent carbon spheres with the excellent electron donating/accepting abilities, chemical
sizes of ca. 1–10 nm, have received tremendous attention due to inertness, biocompatibility, and strong uorescence make
their numerous outstanding properties.1–3 Since their discovery C-dots valuable in a variety of elds including biomedicine,
by Scrivens et al. via purication of single-walled carbon optoelectronics, sensing, photovoltaics, and photocatalysis.
nanotubes (SWNTs),1 a variety of synthesis methods have been Although C-dots have shown great potential in various
developed to improve the optical properties and functionality applications, their properties still need to be improved by
of C-dots,2,3 including arc discharge, laser ablation, tuning the chemical structure of their core and surface. For
instance, C-dots contain abundant carbonyl groups on their
a
Department of Chemical Engineering, Pohang University of Science and Technology surface, which not only impart high water solubility but also
(POSTECH), 77 Cheongam-ro, Nam-gu, Pohang, South Korea 37673. E-mail: srhee@ lead to aggregation. Furthermore, the light absorption range
postech.ac.kr; Fax: +82-54-279-8619; Tel: +82-54-279-2265 of C-dots is mainly conned to UV–blue wavelengths, and
b
Department of Chemical and Biological Engineering, Sookmyung Women's University, their photoluminescence (PL) is limited to a short-wavelength
100 Cheongpa-ro 47-gil, Seoul, South Korea 04310. E-mail: [email protected];
(blue–green) region. These facts are oen indicated as major
Fax: +82-2-2077-7399; Tel: +82-2-2077-7398
limitations of C-dots to compete with organic uorophores or
† These authors contributed equally to this work.
Yoonsang Park received his B.S. Jounghyun Yoo received his B.S.
in Chemical Engineering from in Chemical Engineering from
Pohang University of Science Pohang University of Science
and Technology (POSTECH) in and Technology (POSTECH). He
2014. He is currently pursuing is currently pursuing his Ph.D. in
his Ph.D. in Chemical Engi- Chemical Engineering at POST-
neering at POSTECH. His ECH. His research interests
research interests include focus on luminescent carbona-
synthesis of luminescent carbo- ceous and siliceous nano-
naceous nanomaterials (carbon materials and their application
nanodots, graphene quantum in optoelectronics, bioimaging,
dots, carbon nitrides, etc.) and and therapeutics.
their application in optoelec-
tronics and bioimaging.
11582 | J. Mater. Chem. A, 2016, 4, 11582–11603 This journal is © The Royal Society of Chemistry 2016
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Review Journal of Materials Chemistry A
inorganic nanocrystals that have been conventionally used in introduced. Section 4 covers surface functionalization of C-dots
the past few decades. for multiple purposes, ranging from characterization to appli-
Many research groups have made efforts to improve the cation. We hope that this review provides valuable information
functionality of C-dots, with doping and surface functionaliza- on methods for controlling the properties of C-dots and even-
tion being two major ways of controlling their chemical, optical, tually promotes the use of C-dots in a variety of science and
and electrical properties. Doping (incorporating atomic impu- engineering elds.
rities into carbon cores) creates n-type and p-type carriers,
changing the electronic structures of C-dots. Surface function-
alization (tuning the functional groups on the surface of C-dots) 2. Chemical and electronic structures
can create or change the surface states, as well as endow C-dots of C-dots
with a variety of functionalities by conjugation with functional

2.1. Theoretical models for chemical structures of C-dots
molecules or polymers, which can extend their application
range. So far, various models for visualizing the chemical structure of
In this review, we introduce doping and surface functional- C-dots have been proposed. C-Dots are commonly described in
ization methods that have so far been developed to improve the terms of a carbogenic core with surface functional groups.
functionality of C-dots for various applications. In Section 2, the Elemental analysis by X-ray photoelectron spectroscopy (XPS)
chemical and electronic structures of C-dots and the related commonly indicated high oxygen content due to the oxidized
optical properties are described. In Section 3, various doping core and/or surface functional groups. For instance, in the wet
methods for tuning the optical properties of C-dots are oxidation of candle soot, the chemical composition of puried
C-dots (36.8% C; 5.9% H; 9.6% N; 44.7% O) was vastly different
from that of raw candle soot (91.7% C; 1.8% H; 1.8% N; 4.4% O),
having a signicantly higher oxygen content, partly due to the
Boram Lim received her B.S. in
presence of carbonyl groups.3,4 Fourier transform infrared
Chemistry from Sookmyung
(FT-IR) spectroscopy of C-dots revealed the presence of
Women's University in 2016. She
carboxylic functional groups on their surface. For C-dots
is currently pursuing her M.S. in
prepared using the laser ablation/passivation method, the
Chemical and Biological Engi-
stretching vibrations of C]O bonds (1623 cm1) together with
neering at Sookmyung Women's
the asymmetric and symmetric stretching vibrations of C–O–C
University. Her research interests
moieties (around 1300 cm1 and 1200 cm1, respectively) were
focus on nanomaterials and
detected in the FT-IR spectra.5 Similarly, FT-IR spectra of C-dots
structures for sensors and
prepared via purication of SWNTs showed the presence of
transistors.
surface carboxyl functional groups.1 Recently, C-dots with
non-carboxyl functionalities have been synthesized, with their
chemical structure conrmed by FT-IR and nuclear magnetic
resonance (NMR).6–10
Woosung Kwon received his B.S. Shi-Woo Rhee received his Ph.D.
in Chemical Engineering with in Chemical Engineering from
a minor in Physics (2010) and Massachusetts Institute of
Ph.D. in Chemical Engineering Technology (MIT) in 1984. Aer
(2013) from Pohang University two years of postdoctoral
of Science and Technology research at MIT, he joined the
(POSTECH). Aer postdoctoral faculty of Pohang University of
research at Stanford University, Science and Technology (POST-
he joined the faculty of Sook- ECH) in 1986. He currently
myung Women's University, holds a joint appointment in the
where he is now serving as an Department of Chemical Engi-
assistant professor of chemical neering at POSTECH as
and biological engineering. His professor emeritus and in the
research interests include (1) development of functional, biocom- Department of Chemical and Biological Engineering at Sookmyung
patible nanomaterials for theragnostic and optoelectronic appli- Women's University as the chair professor. His current research
cations, (2) advancement of functionality of nanomaterials interests are carbon materials for electrode applications, uores-
through atomic doping and molecular conjugation, and (3) study cent carbon nanomaterials for optoelectronic devices, and mate-
of the effect of nanomaterials on physiological and biochemical rials for electronic and solar cell devices. He has published more
processes in living organisms to address nanotoxicological issues. than 200 peer-reviewed journal articles and edited two books in
the eld of materials engineering.
This journal is © The Royal Society of Chemistry 2016 J. Mater. Chem. A, 2016, 4, 11582–11603 | 11583
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Journal of Materials Chemistry A Review
Although the surface functional groups of C-dots have been

successfully identied, the precise structure of the carbogenic
core is still debatable. One reason for this is that various
synthesis routes for C-dots lead to intrinsically different C-dots,
depending on the types of reactants or reaction conditions,
making any qualitative comparison between such different
C-dots almost impossible. For example, the lattice fringes of
X-ray diffraction planes of diamond-like and graphitic carbon
lie very close to each other, rendering unambiguous assignment.2
Thus, many structural models of the C-dot core suggested the
following classication: diamond-like structure,5 graphite struc-

ture with sp3 defects,11–18 graphite oxide structure,19 amorphous
carbon structure,20–26 and graphitic cluster structure.6,7,27–29
2.1.1. Diamond-like structure. Hu et al. prepared two types
of C-dots (passivated/non-passivated by polymer (PEG200N))
using the laser ablation/passivation method.5 The transmission
electron microscopy (TEM) image showed that the C-dots have
the size of 2 nm and are well-dispersed (Fig. 1a). Both types of
C-dots showed the same selected area electron diffraction
(SAED) pattern. The ratio of the ring radius squares was Fig. 2 (a–c) TEM images of C-dots obtained at the applied potential of
0.5 V (denoted as [email protected]), 1.5 V (denoted as [email protected]), and
3 : 8:11 : 16 : 19, implying a diamond-like structure, and the
2.5 V (denoted as [email protected]), respectively. (d–f) HR-TEM images of
rings corresponded to the {111}, {220}, {311}, {400}, and {331} [email protected], [email protected], and [email protected], respectively. (g and h)
planes of the diamond structure. The high-resolution trans- C1s high-resolution XPS spectra of [email protected] and [email protected]–
mission electron microscopy (HR-TEM) image showed variable 2.5V, respectively, with identification of peaks by curve fitting.
lattice spacings within 0.2–0.23 nm (Fig. 1c). Reprinted with permission from ref. 11. Copyright 2011 John Wiley and
Sons.
2.1.2. Graphite structure. Bao et al. reported a lattice
spacing of ca. 0.325 nm for C-dots obtained by electrochemical
etching of carbon bers, which corresponds to the (002) facet of
gallate esters with different alkyl chain lengths (lauryl, propyl
graphite (Fig. 2d–f).11 The corresponding XPS C1s spectra
and methyl).13 In Raman spectroscopy, the intensity ratios of the
showed a peak centered at 284.5 eV, assigned to graphitic sp2
D and G bands (ID/IG) decreased in the order lauryl > propyl >
carbons (Fig. 2g and h). Hola et al. reported C-dots with
methyl. The authors suggested that this trend was most likely
controlled size and surface chemistry synthesized from three
due to the inuence of the alkyl chain length on the graphiti-
zation of the carbogenic core. In FT-IR spectra, typical C–H
stretching vibrations (2930 and 2840 cm1) were also observed,
attributable to the remaining sp3 defects.
2.1.3. Graphite oxide structure. Bourlinos et al. synthesized
C-dots by thermal decomposition of different ammonium
citrate salts, where the citrate part served as a source of carbon,
while ammonium provided the covalently attached surface
modier.19 Pyrolysis of neat citric acid in the absence of
ammonium salts resulted in a completely insoluble carbogenic
solid, which shared a common stoichiometry with graphite
oxide. In addition, the X-ray diffraction (XRD) pattern of C-dots
exhibited two superimposed broad reections: one at 0.49 nm,
consistent with disordered carbon, and another at 0.35 nm,
implying the presence of densely packed phenyls within the
polymeric corona. Based on those experiments, the authors
suggested that the cores consist of carbonized intermediates
with a highly defective structure of co-existing aromatic and
aliphatic regions, in analogy with graphite oxide or the inter-
Fig. 1 (a) TEM image of the PEG200N passivated C-dots and direct
related carbogenic networks of lignite, coal, and humic
photograph of the sample under a 365 nm UV lamp (the inset is the substances.
SAED pattern of the C-dots). (b) TEM image of the bare surface C-dots 2.1.4. Amorphous carbon structure. Recently, numerous
and direct photograph of the sample under a 365 nm UV lamp. (c) HR- studies have revealed that C-dots are mainly composed of
TEM image of the PEG200N passivated C-dots. (d) The size distribution amorphous carbon.20–26 Liu et al. fabricated polyethylenimine
of the PEG200N passivated C-dots. Reproduced from ref. 5 with
(PEI) functionalized C-dots by a one-step microwave-assisted
permission from The Royal Society of Chemistry.
View Article Online
pyrolysis.26 The XRD pattern of C-dots displayed a broad

diffraction peak at 2q ¼ 18.3 , suggesting an amorphous nature.
C-Dots fabricated by pyrolysis also showed similar results.24 The
Raman spectrum of C-dots showed only a weak G band at
1557 cm1, and the XRD pattern exhibited one broad reection
centered at 0.43 nm. Both results indicated the presence of
disordered carbon. Liu et al. synthesized C-dots using surfac-
tant-modied silica spheres.20 The absence of discernible lattice
structures in the corresponding HR-TEM image indicated that
the resultant C-dots are amorphous.
2.1.5. Amorphous carbon structure with graphitic clusters.

According to Oberlin's paper dealing with the dependence of
graphitization on temperature, a graphitic cluster model is Fig. 4 (a) A synthesis route of C-dots (represented as CDs in the
plausible.6,7,27–29 The paper showed that the temperature figure) using citric acid and ethylenediamine. (b) TEM (upper) and HR-
generally employed for C-dot synthesis is not high enough to TEM (lower) images of the C-dots. (c) XRD pattern of C-dots. Reprinted
with permission from ref. 28. Copyright 2013 John Wiley and Sons.
form a fully graphitized nanostructure, leading to the formation
of graphitic clusters with ca. 5–8 aromatic rings instead. In this
regard, Kwon et al. described C-dots as paracrystalline carbon, and N), their electronic transitions are closely related to those of
composed of angstrom-sized graphitic clusters surrounded by organic molecules. According to the orbital theory, electrons in
amorphous carbon frames.6 In their previous report, C-dots organic molecules occupy various molecular orbitals (MOs)
were synthesized by so-template carbonization27 and then created by chemical bonding. The MOs fall into three types:
subjected to structural analysis (Fig. 3a). The corresponding bonding, antibonding, and nonbonding. Bonding MOs have
HR-TEM images suggested that the C-dots are composed of lower energy than the parent atomic orbitals (AOs) due to
graphitic (sp2) clusters distributed in an amorphous (probably constructive interactions. In contrast, antibonding MOs have
oxygenic) carbon matrix (Fig. 3b). The Raman spectra showed higher energy than the parent AOs, due to destructive interac-
much more clear-cut D and G bands compared to amorphous tions. Nonbonding MOs have the same energy as the parent AOs
carbon, but possessed no 2D peak and exhibited a more due to symmetry-related lack of interaction. In organic mole-
prominent D band compared to graphite. Thus, it is likely that cules, orbitals are commonly further classied based on the
the C-dots fall into the category of multi-crystalline or amor- symmetry of rotation around the internuclear axis: s (symmet-
phous carbon, but contain a signicant amount of sp2 clusters. rical) and p (asymmetrical). In conclusion, ve MO types are
Zhu et al. came to a similar conclusion for hydrothermally ob- found in organic molecules: s, p, n (nonbonding), s*, and p*,
tained C-dots.28 Based on HR-TEM images, most particles where the asterisk superscript denotes antibonding orbitals.
consist of amorphous carbon without any lattices; very few The sum of all electron-lled orbitals in a molecule is called its
particles possess well-resolved lattice fringes (Fig. 4). The XRD electronic state. Since a molecule can have various electronic
patterns also displayed a broad peak centered at around 2q ¼ congurations, a variety of electronic states with different
25 (corresponding to the lattice spacing of 0.34 nm), attributed energy levels exists. Electronic transitions take place when an
to highly disordered carbon (Fig. 4c). The presence of sp2 electron is excited to a higher energy state by light absorption.
carbons was also inferred from the 1H NMR spectrum. In the For instance, an electronic transition can occur by transferring
13
C NMR spectrum, signals between 30 and 45 ppm, corre- an electron from the s bonding orbital to the s* antibonding
sponding to aliphatic (sp3) carbons, and signals between 100 orbital, denoted as s / s*. Likewise, the following electronic
and 185 ppm, indicative of sp2 carbons, were observed. transitions exist: s / p*, p / p*, n / p* and n / s*. Each
transition corresponds to a typical absorption range in
UV-vis spectroscopy: s / s* (125 nm), n / s* (150–250 nm),
2.2. Electronic structures of C-dots
p / p* (200–400 nm), n / p* (400–700 nm). The s / s*
2.2.1. Electronic structures of organic molecules. Since transition requires very high energy (absorption maximum
C-dots are mainly composed of organogenic elements (e.g., C, O, at 125 nm) and is not observed in typical UV-vis spectra. The
n / s* transition occurs in saturated compounds containing
lone pairs, but these transitions are also rarely observed due to
the high energy required. In most cases, the absorption spec-
troscopy of organic molecules is focused on detecting n / p*
and p / p* transitions, due to their easily accessible transition
energies. The molar absorptivities of the n / p* transitions are
Fig. 3 (a) Schematic of the soft-template synthesis of C-dots. (b) HR- usually relatively low (due to the low transition dipole
TEM image of as-obtained C-dots. The white solid lines and arrows moments), ranging from 10 to 100 L mol1 cm1. The p / p*
indicate the lattice plane distance. The dotted red and green circles
transitions generally have molar absorptivities between 1000
divide graphitic clusters and amorphous (or oxygenic) carbon
matrices, respectively. Reprinted with permission from ref. 27. Copy- and 10 000 L mol1 cm1, ca. 100 times higher than those of
right 2013 John Wiley and Sons. n / p* transitions.
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2.2.2. Electronic structures of C-dots. Similar to organic

molecules, C-dots exhibit s / s*, s / p*, p / p*, n / p*,
and n / s* transitions, closely related to the chemical struc-
tures of C-dots. The p-states of C-dots can be attributed to
aromatic sp2-hybridized carbons in their core. Some studies
have shown that the energy gap between p-states gradually
decreases as the number of aromatic carbons increases, just as
in the case of p-conjugation in organic molecules.30,31 The
n-states of C-dots can be attributed to functional groups con-
taining electron lone pairs, such as carbonyls, amines, amides,
and thiols. If the functional groups carrying lone pairs are

bonded to aromatic sp2-hybridized carbons, electron transi-
tions from the n-states of the functional groups to the p*-states
of the aromatic carbons can happen. The interaction between Fig. 5 (a) Typical sized C-dots optical images illuminated under white
(left: daylight lamp) and UV light (right: 365 nm). (b) PL spectra of
p- and n-states in C-dots can also be affected by the extent of typical sized C-dots: the red, black, green, and blue lines are the PL
orbital overlap and electron withdrawing/donating abilities of spectra for blue-, green-, yellow-, and red-emission C-dots, respec-
functional groups. The electronic structures of C-dots and the tively. Reprinted with permission from ref. 31. Copyright 2010 John
related electronic transitions are deeply linked to their optical Wiley and Sons.
properties, represented by light absorption and luminescence.
which agrees well with the visible light emission of C-dots,

2.3. Optical properties of C-dots having diameters of less than 3 nm. Thus, it was concluded that
2.3.1. Light absorption of C-dots. C-dots typically exhibit the strong emission of C-dots arises from the quantum-sized
strong light absorption in the UV region with a tail extending graphite structure itself, instead of the carbon–oxygen surface.
into the visible range.2 The maximum absorption peak at Furthermore, the as-synthesized C-dots were treated with
230 nm may correspond to a p / p* transition involving hydrogen plasma to remove the oxygen from the graphite
aromatic sp2 carbons, and the tail starting from 300 nm can surface, in order to conrm that the strong emission of C-dots is
be assigned to an n / p* transition involving functional due to the quantum-sized graphite fragment. A series of control
groups with electron lone pairs.32,33 Recently, several papers experiments showed no obvious change in the C-dot PL spectra
have reported that surface functional groups of aromatic before and aer hydrogen plasma treatment. The insensitivity
compounds can play a major role in determining the light of the Raman spectra to hydrogen plasma treatment also
absorption properties of C-dots.34 suggests that the graphite fragment of C-dots remained largely
2.3.2. PL of C-dots. One of the most attractive optical intact.
properties of C-dots is their PL. Although the chemical and 2.3.2.2 Defective state emission. Hu et al. reported that the
electronic structures of C-dots vary depending on the synthesis origin of luminescence was attributed to carboxylate ligands on
methods used, most of the C-dots exhibit a similar range of PL, the surface of C-dots,5 and performed surface passivation
which mainly covers the blue region (corresponding to wave-
lengths from 400 to 500 nm). The origin of PL is still debatable,
with several theories proposed to explain the generation and
recombination of electron–hole pairs. Here, we introduce two
important theories explaining the origin of C-dot PL: the
quantum connement effect and the defective state emission.
2.3.2.1 Quantum connement effect. Li et al. claimed that the
strong emission of C-dots originates from a quantum-sized
graphite fragment.31 The authors puried the as-synthesized
C-dots by simple column chromatography to obtain different-
sized particles with a narrow size distribution, which showed
different emission colors (Fig. 5).
Theoretical calculations were also performed to investigate
the relationship between luminescence and cluster size. Fig. 6
shows the dependence of the energy gap between the highest
occupied molecular orbital (HOMO) and lowest unoccupied
molecular orbital (LUMO) on the size of the graphene frag-
ments. As the fragment size increases, the gap gradually
Fig. 6 (a) Relationship between the C-dots size and the PL energies.
decreases, in agreement with a previous study.30 A gap energy (b) HOMO–LUMO gap dependence on the size of the graphitene
corresponding to transitions in the visible light range can be fragments. Reprinted with permission from ref. 31. Copyright 2010
assigned to graphene fragments with a diameter of 14–22 Å, John Wiley and Sons.
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quantum yield of C-dots. For these reasons, numerous research

efforts have been directed at searching for dopants and devel-
oping doping processes over the last decade.
3.1. Nitrogen doping

Nitrogen is a typical dopant due to its ve valence electrons and
an atomic size comparable to that of carbon. In C-dots, nitrogen
atoms serve as n-type impurities providing excess electrons,
which results in an upward shi of the Fermi level and a change
in optical properties.36–39 So far, various nitrogen-containing

compounds have been tried as precursors for nitrogen doping
of C-dots.38–128
Zhang et al. prepared N-doped C-dots via a one-pot sol-
vothermal route by using CCl4 and NaNH2 as starting mate-
rials.38 Experimental results showed that the emission
wavelength of C-dots could be efficiently tuned by adjusting the
Fig. 7 PL and PL excitation (PLE) spectra of sample A (the supernatant nitrogen doping concentration, and the authors claimed that
from the suspension of graphite in PEG200N), R1 (pure PEG200N
nitrogen doping dominates the optical properties of the C-dots,
irradiated by laser for 2 h) and R2 (a mixture of PEG200N and
perchloric acid heated to 120 C and held for 72 h), PL spectra were rather than the size effect. Xu et al. proposed a facile and
recorded under 350 nm light excitation, while PLE spectra were general carbonization and extraction procedure for preparing
acquired by exciting the samples with the strongest absorption a series of N-doped C-dots with different nitrogen contents,
wavelength in the PLE spectra. Reproduced from ref. 5 with permission using 3-(3,4-dihydroxyphenyl)-L-alanine (L-DOPA), L-histidine,
from The Royal Society of Chemistry.
and L-arginine as model precursors.40 They argued that nitrogen
bonding disorders the carbon hexagonal rings and creates
emissive energy traps. As a result, the PL intensity of N-doped
experiments with normal C-dots, using PEG200N and perchloric C-dots was dependent on the nitrogen content, and N-doped
acid as surface ligands. Weak uorescence was detected for C-dots showed brighter PL than non-doped C-dots and oxidized
both samples, but the peak shapes and positions were N-doped C-dots. Guo et al. synthesized highly luminescent
completely different from those of normal C-dots (Fig. 7). nitrogen-containing carbogenic polymer dots (NPDs) through
Furthermore, PL intensities of the two samples were much a microwave-assisted ethanol thermal approach using poly-
weaker than that of normal C-dots. Pure PEG200N and the bromopyrroles (PBPs) as the starting material.41 The NPDs
product of its reaction with perchloric acid hardly emit light emitted strong blue luminescence around 470 nm under exci-
when irradiated by a laser; therefore the authors believed that tation at 360 nm showing a high quantum yield of 24% aer
the surface state of the C-dots might play an important role in simple surface reduction by NaBH4.
the observed PL. Some researchers studied the availability of nitrogen-doped
Wang et al. used transient absorption spectroscopy and C-dots for a wide range of applications such as photocatalysis,
time-resolved PL spectroscopy to reveal the origin of the green biochemical sensing, bioprobes, bioimaging, optoelectronic
luminescence observed for C-dots.35 According to the change of devices, etc. Ma et al. synthesized water-soluble uorescent
surface functional groups during chemical reduction experi- N-doped C-dots by a facile one-pot ultrasonic reaction between
ments, the green luminescence emission centers emerging in glucose and ammonium hydroxide.42 In a study of their pho-
C-dots were unambiguously assigned to special edge states tocatalytic performance under visible light irradiation, the
consisting of several carbon atoms on the edge of a carbon N-doped C-dots showed higher catalytic activity for the photo-
backbone and C]O functional groups (carbonyl and carboxyl). degradation of methyl orange compared to the non-doped
It was suggested that competition between different emission C-dots, implying their considerable application potential in
centers and traps dominates the optical properties of C-dots. environmental protection (Fig. 8).
Chen et al. claimed that highly luminescent N-doped C-dots
3. Doping (quantum yield of 15.7%) could be synthesized by a facile one-
step hydrothermal treatment of folic acid.43 The N-doped C-dots
Doping is an effective method for modulating the intrinsic were found to be a highly efficient and sensitive chemosensor
properties of C-dots. By introducing atomic impurities (e.g., for selective Hg2+ detection, exhibiting a detection limit of
nitrogen, phosphorus, boron, etc.) into C-dots, their electronic 0.23 mM. The sensitive and selective Hg2+ detection by the pre-
structure can be changed, generating n-type or p-type carriers. sented “turn-off” uorescent sensor was achieved by uores-
Therefore, their electronic and optical properties, closely cence quenching (Fig. 9), which may be attributed to the
related to the HOMO–LUMO energy gaps, can be tuned by using surface/molecular states of the quantum dots and/or the Hg2+-
certain types and amounts of dopants. Furthermore, recent induced conversion of the special functional group (–CONH–)
research revealed that doping could greatly enhance the from a spirolactam to an open-ring amide structure.
View Article Online
Fig. 10 (a) Emission spectrum of a white LED using a CND-10000 film

as a color-converting phosphor and an InGaN blue (400 nm) LED as an
illuminant. (b) CIE (Commission Internationale d'É clairage) chroma-
ticity coordinates (x, y) calculated from the emission spectrum. (c)
Fig. 8 (a) The scheme for the formation process of the N-doped C- Photograph of an exemplary device under operation. Reprinted with
dots (represented as N-doped CQDs in the figure). (b) Relationship permission from ref. 48. Copyright 2013 American Chemical Society.
between methyl orange concentration and reaction time for different
catalysts (C-dots are represented as CDs in the figure). Reproduced
from ref. 42 with permission from The Royal Society of Chemistry.
phosphorus atom is larger than the carbon atom. Thus, it can
form substitutional defects in the carbon cluster and behave as
an n-type donor, thereby modifying the electronic and optical
properties.129 Several kinds of P-doped C-dots were produced
using phosphorus-containing precursors, such as phosphorous
tribromide,129 triphenylphosphine,106 monosodium phos-
phate,29 phosphoric acid,130 etc.
Zhou et al. synthesized P-doped C-dots by a solvothermal
method using phosphorous tribromide and hydroquinone as
precursors.129 The as-prepared P-doped C-dots exhibited strong
Fig. 9 (a) PL spectra of the N-doped C-dots in aqueous solution upon blue uorescence with a quantum yield of up to 25% (Table 1).
addition of various concentrations of Hg2+ (from top to bottom: 0, 5, It was suggested that the coexistence of defect sites and isolated
10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70 and 75 mM), excitation at sp2 carbon clusters could efficiently increase the band gap into
360 nm. (b) The dependence of PL intensity on the concentration of
UV-vis light regions and give rise to stronger visible uorescence
Hg2+ ions within the range of 0–75 mM, and the inset shows the linear
relationship between the PL intensity and Hg2+ concentration. than the single sp2 carbon clusters. The uorescence enhance-
Reprinted from ref. 43, Copyright 2014, with permission from Elsevier. ment may also originate from the isolated sp2 carbon clusters,
since the incorporation of phosphorus into C-dots creates more
isolated sp2 carbon clusters, with the number of these clusters
Wang et al. have synthesized N-doped C-dots of less than
increasing concomitantly with the phosphorus content. Toxicity
3 nm size via a facile one-pot route by reacting melamine and
and bioimaging experiments showed that P-doped C-dots have
glycerol in the presence of an acid catalyst.47 The N-doped
low cell toxicity and excellent biolabeling ability.
C-dots were used to sensitize TiO2 solar cells, showing compa-
Sarkar et al. demonstrated the effects of phosphorus doping
rable performance to CdSe and InAs quantum dots at their early
by comparing non-doped C-dots with phosphorus-doped
development stage. More signicantly, the C-dot sensitized
C-dots.29 Doping the non-doped C-dots with phosphorus caused
solar cell is responsive to near-IR irradiation, owing to the
a red shi of the maximum emission wavelength from 420 to
energy upconversion ability of the N-doped C-dots. Kwon et al.
470 nm and enhanced their uorescence intensity as well as
reported the preparation of nitrogen-rich C-dots by emulsion-
quantum yields by up to 10%.
templated carbonization of polyacrylamide.48 The authors
fabricated large-scale (20 20 cm) freestanding luminescent
C-dot lms based on a poly(methyl methacrylate) matrix. The
3.3. Boron dopings
obtained lms are low-cost, fully exible, easily scalable, ther-
mally stable, eco-friendly, and mechanically robust. Further- Boron has only three valence electrons, i.e., one less than
more, white LEDs using these lms as color-converting carbon. Thus, if a boron atom is introduced in a carbon cluster,
phosphors and InGaN blue LEDs as illuminators were demon-
strated. Fig. 10 shows the emission spectrum and CIE Table 1 The fluorescence quantum yields and lifetimes of C-dots and
(Commission Internationale d'É clairage) chromaticity coordi- P-doped C-dots. Reproduced from ref. 129 with permission from The
nates of the white LED. Such white LEDs exhibit no temporal Royal Society of Chemistry
degradation of their emission spectrum under practical opera-
Sample lex (nm) Ff a (%) sb (ns)
tion conditions.
C-Dots 368 3.4 8.4
P-Doped C-dots 372 25.1 5.0
3.2. Phosphorus doping
a
The uorescence quantum yields in ethanol at their respective
Phosphorus, which belongs to group 15 of the periodic table, excitation wavelength. b The average lifetimes.
can act as an n-type impurity in C-dots. Unlike nitrogen, the
View Article Online
p-type carriers are generated inside C-dots, changing their non-linear optical response compared to non-doped C-dots.
electronic structures and optical properties.106,131–134 This result is in line with previous studies, which reported
Shan et al. reported that uorescent B-doped carbon a similar effect on the non-linear optical properties of boron-
quantum dots were prepared by a facile one-pot solvothermal doped silicon nanocrystals.
route using BBr3 as the boron source and hydroquinone as the
carbon source131 (Fig. 11). B-Doped C-dots exhibit bright blue 3.4. Sulfur doping
uorescence with a maximum emission peak at 368 nm,
Recently, S-doped C-dots have received great attention, since
whereas non-doped C-dots show weak green emission with
sulfur atoms can provide energy or emissive trap states for
a maximum at 440 nm. The maximum uorescence quantum
photoexcited electron capture, which modies the electronic
yield of B-doped C-dots is 14.8%, which is considerably higher
structure of C-dots.135 Numerous studies reported the synthesis
than that of C-dots (3.4%). It was proposed that the large

of S-doped C-dots using sulfuric acid,136 sodium hydrosulde,87
emission blue shi of B-doped C-dots compared to non-doped
sodium thiosulfate,137 waste frying oil,138 dodecanethiol,106
C-dots might be attributed to the strong electron-withdrawing
ethane-sulfonic acid,57 and 2,20 -(ethylenedithio)diacetic acid91
character of boron, since it is a well-known electron-decient
as sulfur sources.
Lewis acid. Taking advantage of the effective uorescence
Chandra et al. developed a facile route for the rst-time
quenching effect of hydrogen peroxide, induced by charge
synthesis of isolated S-doped C-dots from thiomalic acid (TMA)
transfer between doped boron atoms and hydrogen peroxide,
via pyrolysis in the presence of conc. H2SO4 (98%) followed by
a sensitive uorescence analytical system for hydrogen peroxide
isolation and polymerization with excess NH4OH.136 The
was established based on B-doped C-dots. Sadhanala et al.
synthesized S-doped C-dots show excellent water dispersibility,
synthesized B-doped C-dots from sucrose as the carbon source
high photostability, and negligible toxicity, exhibiting a high
and boric acid as the boron source by using a simple hydro-
quantum yield of 11.8% at 340 nm excitation at pH 8. Due to the
thermal method at 180 C.132 It was shown that the C-dot size
presence of sulfur atoms in their interior, S-doped C-dots using
and boron doping level could be controlled by simply varying
phenyl-C60-butyric acid methyl ester (PCBM) as the electron
the reaction time; the quantum yield was found to increase
transporting layer exhibit a wide band gap of 4.43 eV with a high
from 0.5% to 2.7% aer boron doping. In contrast to the results
open circuit voltage (VOC) of 617 mV and a ll factor (FF) of as
of Shan et al., the PL peaks of B-doped C-dots are red-shied as
high as 37%. The J–V characteristics of this hybrid photovoltaic
the reaction time is increased, which suggests that the size
cell are presented in Fig. 12.
effect dominates over the inuence of boron concentration.
Yang et al. synthesized S-doped C-dots by a one-step hydro-
Another type of B-doped C-dots was produced by microwave
thermal reduction and in situ doping using oxidized C-dots and
heating of an aqueous solution of citric acid, boric acid, and
sodium hydrosulde.87 The excitation and emission wave-
urea by Bourlinos et al.133 They demonstrated for the rst time
lengths of these S-doped C-dots were red-shied to 418 and 539
that boron doping causes a signicant enhancement of the
nm compared to oxidized C-dots, which exhibit excitation and
emission wavelength of 397 and 482 nm, respectively. The
authors claimed that the emission wavelength of heavily doped
C-dots is related to the electronegativity of heteroatoms. Similar
to uorescent dyes, the uorescence spectrum of C-dots was
red-shied when they were doped by sulfur. This can be
attributed to the low electronegativity of sulfur, which can act
as an electron donor. Synthesis of S-doped C-dots via a simple
and straightforward hydrothermal reaction using sodium
citrate and sodium thiosulfate as precursors was suggested
by Xu et al.137 As the sulfur to carbon precursor ratio
Fig. 11 Schematic representation of the synthesis of B-doped C-dots Fig. 12 (a) J–V characteristics under dark and photo conditions of the
and glucose-sensing mechanisms based on B-doped C-dots and hybrid cell made by C-dots (donor) and PCBM (acceptor). (b) The
H2O2. Reproduced from ref. 131 with permission from The Royal corresponding plot of power density against voltage. Reproduced
Society of Chemistry. from ref. 136 with permission from The Royal Society of Chemistry.
View Article Online
increased, more sulfur was doped into the carbon dots,

increasing their quantum yield. The as-prepared S-doped
C-dots exhibit maximum uorescence at 440 nm with
a quantum yield of 67%, which is the highest value observed
for S-doped C-dots.
3.5. Co-doping
So far, single-element doping has shown great potential for
controlling the intrinsic properties of C-dots, but it also has
several limitations. For instance, one of the major limitations of

single-element-doped C-dots is that their light emission spectra
are conned to the blue–yellow range.139 Several researchers
suggested that such disadvantages of single-element doping
can be overcome by doping two or more atoms simultaneously,
which is called co-doping.39,106,135,139–160 The light absorption and
emission behavior of co-doped C-dots could be affected by the
synergistic effect of different elements.135 Fig. 13 Representation for the fluorescence mechanism of O-doped
3.5.1. Nitrogen/sulfur. Nitrogen and sulfur co-doped C-dots, N-doped C-dots, and N,S-doped C-dots. (1): electrons
excited from the ground state and trapped by the surface states. (2):
C-dots (N,S-doped C-dots) have been frequently investigated,
excited electrons return to the ground state via a non-radiative route.
since nitrogen has an atomic radius close to that of carbon, and (3): excited electrons return to the ground state via a radiative route.
sulfur has an electronegativity similar to that of carbon.140 Yu O-Doped C-dots, N-doped C-dots and N,S-doped C-dots are rep-
et al. synthesized N,S-doped C-dots via a one-step hydrothermal resented as O-CDs, N-CDs and N,S-CDs in the figure, respectively.
treatment using citric acid (CA) as a carbon precursor and Reprinted with permission from ref. 141. Copyright 2013 John Wiley
141 and Sons.
L-cysteine as a nitrogen and sulfur source. The introduced
sulfur atoms could enhance the effect of nitrogen atoms on the
properties of the doped carbon nanomaterials through a coop-
erative effect. For the N,S-doped C-dots, the introduced sulfur structural changes induced by doping with nitrogen and sulfur
atoms were able to eliminate the O-states (kind of surface states heteroatoms play a key role in regulating their PL properties.
caused by oxygen presence in C-dots) and enhance the N-state Wang et al. showed that introduction of nitrogen or sulfur
(new kind of surface states caused by nitrogen doping) (Fig. 13). atoms into graphite lattices could reduce the band gap of the
Therefore, the N,S-doped C-dots showed a high uorescence nanoscale graphene structure, while co-doping with nitrogen
quantum yield (73%) and excitation-independent emission. and sulfur could reduce the band gap more efficiently.145
The maximum excitation and emission wavelengths of the Experimental investigations conrmed that the N,S-doped
aqueous N,S-doped C-dot solution are 345 and 415 nm, C-dots can generate much higher photocurrents than the
respectively. C-dots, N-doped C-dots, and S-doped C-dots. The prepared
Sun et al. developed a simple method for a large-scale N,S-doped C-dots enhanced the photocurrent responses of TiO2
synthesis of N,S-doped C-dots using carbonization and etching nanotube arrays by 50%, indicating that the N,S-doped C-dots
of hair bers by sulfuric acid.142 Higher reaction temperature can be used as an excellent photosensitizer for solar radiation
favored the formation of N,S-doped C-dots with smaller size, collection and charge transport in the N,S-doped C-dots/TiO2
higher S content, and longer PL wavelength. The obtained hybrid devices.
N,S-doped C-dots exhibited good luminescence stability, 3.5.2. Boron/nitrogen. Jahan et al. demonstrated a facile
nanosecond lifetime, low toxicity, good biocompatibility, and hydrothermal oxidative synthesis route to highly uorescent
high water solubility. N,S-Doped C-dots with a quantum yield of boron/nitrogen co-doped C-dots (B,N-doped C-dots).157 During
54.4% were hydrothermally synthesized using a-lipoic acid and this process, N-(4-hydroxyphenyl)glycine served as a nitrogen
ethylenediamine by Ding et al.143 It was argued that the doped and carbon source, while boric acid (H3BO3) was used as an
nitrogen formed C]N and C–N bonds, which signicantly oxidizing agent under an atmosphere of N2. Upon excitation of
enhanced the uorescence efficiency, and the co-doped sulfur the aqueous solution of C-dots, bright green PL was observed,
was found to synergistically enhance the effect of nitrogen with the emission peak centered at 500 nm and a quantum
doping by providing more opportunities to form C]N bonds. yield of 11.44%. Han et al. synthesized B,N-doped C-dots by
Choi et al. reported the synthesis of N,S-doped C-dots by a combustion ame technique, using boric acid and pyrrole as
microwave-assisted pyrolysis of rice as a carbon source and precursors.106 The B,N-doped C-dots have a maximum emission
N-acetyl-L-cysteine (NAC) as a nitrogen and sulfur dopant.144 wavelength of 524 nm, and exhibit excitation-independent PL
High performance liquid chromatography (HPLC) was used to behavior. The as-prepared B,N-doped C-dots show high catalytic
separate the N,S-doped C-dots into fractions, which were activity in the oxygen reduction reaction (ORR), comparable to
collected and further characterized by mass spectrometry, that of commercial Pt/C.
UV-vis absorption, and PL spectroscopy, showing that the
View Article Online
3.5.3. Phosphorus/nitrogen. Han et al. also synthesized

phosphorus/nitrogen co-doped C-dots (P,N-doped C-dots) by
a combustion ame technique, using triphenylphosphine and
pyrrole as precursors.106 The P,N-doped C-dots exhibit
maximum emission intensity at 523 nm, while B,N-doped
C-dots exhibit an excitation-independent PL behavior. Similar
to B,N-doped C-dots, P,N-doped C-dots show excellent ORR
performance, compared with non-doped C-dots. P,N-doped
C-dots with a satisfactory quantum yield have been prepared via Fig. 14 Illustration of the formation process of Ge-doped C-dots by
carbonization and its further applications for Hg2+ detection. Repro-
one-step acidic oxidation of pumpkin by H3PO4 at low temper-
duced from ref. 162 with permission from The Royal Society of
ature (90 C) by Gong et al.158 The as-synthesized P,N-doped Chemistry.

C-dots exhibit uorescence around 550 nm with a quantum
yield of 9.42% without surface passivation, and have excitation
wavelength dependent PL behavior. It was observed that
P,N-doped C-dots are superior uorescent bioimaging agents of mercury(II) ions with excellent selectivity in a complex
due to their excellent solubility and ultralow toxicity. In addi- medium.
tion, P,N-doped C-dots display a notably large Stokes shi of Yang et al. reported that Se-doped C-dots were obtained by
125 nm with good reversibility and could effectively avoid the a one-step hydrothermal reduction of oxidized C-dots with
inuence of autouorescence in biological systems. Zhang et al. NaHSe. Se-doped C-dots have maximum emission intensity at
prepared nitrogen- and phosphorus-doped C-dots by hydro- 563 nm with a quantum yield of 19%, and exhibit yellow
thermal carbonization of adenosine-50 -triphosphate.159 The luminescence under UV irradiation.87 Just as in the case of
quantum yield of P,N-doped C-dots excited at 340 nm was as S-doped C-dots, the authors claimed that the red-shied emis-
high as 23.5%. The P,N-doped C-dots have remarkable advan- sion wavelength of Se-doped C-dots was related to the low
tages of high sensitivity, rapid response time, wide response electronegativity of selenium.
range, and high biocompatibility, making them suitable for in Some researchers fabricated gadolinium-doped C-dots for
vivo reactive oxygen species (ROS)/reactive nitrogen species medical applications, especially for magnetic resonance
(RNS) detection and biological imaging. imaging (MRI).163,164 In the study by Bourlinos et al.,
3.5.4. Nitrogen/sulfur/phosphorus. Zhuo et al. reported Gd-doped C-dots were synthesized via pyrolysis of a mixture
a simple and green approach to prepare water-soluble nitrogen/ of gadopentetic acid with tris(hydroxymethyl)aminomethane
sulfur/phosphorus co-doped carbon dots (N,S,P-doped C-dots) (Tris) and betaine hydrochloride in air at 250 C.163 The ob-
by a one-step hydrothermal treatment of cucumber juice.160 It tained Gd(III)-doped carbon dots have uniform particle size
was found that a higher reaction temperature favors the (3–4 nm) and exhibit bright uorescence, strong T1-weighted
formation of N,S,P-doped C-dots with smaller size and longer MRI contrast, and low cytotoxicity. Gong et al. reported that
PL wavelength. Gd-doped C-dots could be prepared by a one-step microwave-
assisted polyol method using sucrose and Gd2O3.164 The ob-
tained Gd-doped C-dots exhibited unique green PL with
3.6. Other atoms (Si, Ge, Se, Gd, and Tb) a quantum yield of 5.4%, and were an excellent T1 contrast
In addition to the previously mentioned elements, many other agent for magnetic resonance imaging (Fig. 15).
elements such as Si, Ge, Se, Gd, Tb, etc. have been used as Chen et al. claimed that Tb-doped C-dots were rst prepared
dopants to change the optical, electrochemical, and biological by simply heating a mixture of terbium(III) nitrate pentahydrate
properties of C-dots for their versatile application.87,161–166 and citric acid at 190 C.165 The as-prepared Tb-doped C-dots
Qian et al. developed a simple solvothermal method to exhibited excitation wavelength dependent emission (blue
synthesize Si-doped C-dots using SiCl4 and hydroquinone.161 uorescence), having high reproducibility and selectivity for
The as-prepared Si-doped C-dots have maximum uorescence detecting 2,4,6-trinitrophenol (TNP) in complex water samples.
at 382 nm with a quantum yield of up to 19.2%, owing to A summary of doped C-dots is presented in Table 2.
uorescence enhancement by the introduced silicon atoms.
The Si-doped CQDs exhibit excellent multifunctional sensing
performance in the determination of Fe(III), H2O2, and
melamine.
C-Dots doped with Ge were prepared for the rst time via
carbonation synthesis using citric acid and bis-(2-carbox-
yethylgermanium(IV)sesquioxide) (Ge-132) by Yuan et al.162
(Fig. 14). The as-prepared Ge-doped C-dots exhibited excitation-
independent PL, which could help to avoid autouorescence in
bioimaging applications. Additionally, Ge-doped C-dots have Fig. 15 T1-weighted magnetic resonance (MR) images of water and
low cell toxicity, good biocompatibility, high intracellular serial dilutions of Gd-doped C-dots. Reprinted with permission from
delivery efficiency, and stability and could be used for detection ref. 164. Copyright 2014 American Chemical Society.
View Article Online
106, 135 and 139–156

4. Surface functionalization
29, 106, 129 and 130
39, 106, 158 and 159

57, 87, 91, 106 and
106 and 131–134
Surface functionalization with various molecules (e.g.,
106 and 157
163 and 164

organic/inorganic molecules, polymers, ions, metals, DNA,
proteins, etc.) is an effective pathway for tailoring the properties
136–138
38–128
of C-dots. Surface functionalization is a multipurpose method

Ref.
160
161
162
165
87
that has been used in various research elds, including energy
structure engineering, mechanical property engineering, sensor
applications, bioapplications, photocatalytic applications, etc.
yields (%)
Quantum
1.5–93.3
0.5–14.8
3.66–67
54.4–73
9.42–59
10–65
11.44
3.25
19.2
8.9
5.4
4.1. Electronic structure engineering
19
—
So far, many studies have shown that the optical properties of
C-dots are highly dependent on their surface states. These
Maximum emission
surface states, including emissive surface states and defect

wavelength (nm)
sites, are closely related to the energy structure of C-dots, which

determine excitation/emission wavelengths and quantum
yields. In this regard, many surface functionalization methods
445, 521
390–560
372–470
368–680
378–539
500–524
406–550
450–571
have been investigated for engineering the energy structures of

415
382
465
563
450
C-dots.
A bare C-dot surface contains many defect sites, such as
dangling bonds, non-radiative states, radicals, etc. These defect
(N, S), ethylenediamine (N),
sites make C-dots defenseless to external contaminants, which

may cause poor photostability and low quantum yields. Surface
Terbium(III) nitrate pentahydrate
Pyrrole (N), triphenylphosphine,
NaNH2, NH4OH, melamine, etc.
H2SO4, sodium thiosulfate, etc.
passivation is one of the surface functionalization methods

a-lipoic acid, H2SO4 (S), etc.
developed to enhance the optical properties of C-dots. By intro-

H3BO3 (B), C4H5N (N), etc.
Gadopentetic acid, Gd2O3
ducing a thin passivating layer on the C-dot surface, their photo-

stability and quantum yields are remarkably increased. Passivation
PBr3, NaH2PO4, etc.
of C-dots to improve their quantum efficiency was rst

BBr3, H3BO3, etc.
H3PO4 (P), etc.
conducted by the Sun group. In 2006, Sun et al. rst discovered

Doping agent
the benecial effect of C-dot surface passivation. They

L-Cysteine
Ge-132
synthesized surface-passivated C-dots with diamine-terminated

NaHSe
SiCl4
oligomeric poly(ethylene glycol) H2NCH2(CH2CH2O)nCH2CH2-

CH2NH2 (average n 35, PEG1500N).167 In a typical reaction,
PEG1500N was mixed with an acid-treated particle sample, and the
mixture was heated to 120 C for 72 h. Aer the reaction, the
CCl4, glucose, folic acid, glycerol, etc.
Pyrrole, adenosine triphosphate, etc.
Tris, betaine hydrochloride, sucrose

Thiomalic acid, sodium citrate, etc.
mixture was cooled to room temperature and dispersed in water,

N-(4-Hydroxyphenyl)glycine, etc.
followed by centrifuging for 30 min. The obtained colored but

Hydroquinone, citric acid, etc.
Hydroquinone, sucrose, etc.
homogeneous supernatant contained PEG1500N-passivated C-dots

Cucumber juice (N, S, P)
(Fig. 16). The resulting C-dots showed high photostability to

continuously repeated irradiation for several hours with high
quantum yields (from 4% to more than 10%). Wang et al.
Summary of representative doped C-dots
Citric acid, etc.
synthesized blue uorescent C-dots using citric acid as a carbon

Carbon source
Hydroquinone
Chinese ink
source and hyperbranched polyethylenimine (PEI) as a surface

Citric acid
Citric acid
passivation agent.168 The resultant C-dots showed strong blue

uorescence with a quantum yield of up to 24.3% and high photo-
and metal-stability, attributed to the protective surface passivation
layer formed by PEI.
Lu et al. generated ionic liquid (IL) passivated C-dots from
Nitrogen/sulfur/phosphorus
graphite electrodes using IL-assisted electrochemical exfolia-

tion.169 ILs improved the nanoparticle dispersion and dimin-
Phosphorus/nitrogen
ished the quenching effects due to interparticle interactions,

Doping element
resulting in a quantum yield of 2.8–5.2%. Inorganic shell

Nitrogen/sulfur
Boron/nitrogen
Germanium
passivation could also improve the quality of C-dots. Liu et al.

Gadolinium
Phosphorus
Selenium
Nitrogen
Terbium
reported a novel wet-chemistry-based route towards C-dots by

Table 2
Silicon
Boron
Sulfur
employing surfactant-modied silica spheres as carriers.20 The

resulting C-dots showed good biocompatibility and high
View Article Online

Fig. 17 Illustration of emission from C-dots along with the variation of

surface oxidation degree. Reprinted with permission from ref. 11.
Copyright 2011 John Wiley and Sons.
Fig. 16 Aqueous solution of the PEG1500N-attached C-dots (a) excited could introduce different emission sites, resulting in variable
at 400 nm and photographed through band-pass filters of different intensities of the emission spectra (Fig. 17). The same group
wavelengths as indicated, and (b) excited at the indicated wavelengths reported a series of C-dots exhibiting various emission wave-
and photographed directly. (c) The colored but homogeneous lengths ranging from 430 to 610 nm by varying the degree of
supernatant contained the C-dots with PEG1500N species attached to
surface oxidation or their size.12
the surface. Reprinted with permission from ref. 167. Copyright 2006
American Chemical Society. Hola et al. reported the synthesis of alkyl chain passivated
C-dots with controlled size and surface chemistry from simple
gallate molecular precursors.13 The alkyl chains on the C-dot
surface were readily converted to carboxylate groups via mild
quantum yields of 11–15% for a wide range of pH values from base hydrolysis and induced red-shied emission (from 402 to
5 to 9. Gao et al. found an interesting phenomenon that Ag+ 440 nm) due to COO surface states. Recently, Ding et al.
exhibited an enhancement effect on the photoluminescence of synthesized C-dots with tunable PL and a quantum yield of up
C-dots, which is a quite different way to the usual quenching to 35% in water using a hydrothermal method and silica
effects of metal ions on the uorescence of C-dots.170 Based on column chromatography.21 Although these samples had similar
their proposed mechanism, Ag+ ions could be reduced to Ag0 distributions of particle size and graphite structure in their
clusters on the surface of the C-dots, which can efficiently carbon cores, the surface states varied between the samples,
enhance the uorescence intensity of the C-dots. In 2010, the especially the degree of oxidation. Therefore, the red shi (440
Sun group synthesized PEG1500N-passivated C-dots for a more to 625 nm) observed for their emission peaks was ascribed to
rigorous control of the functionalization reaction conditions a gradual reduction of their band gaps with increasing incor-
and fractionated them on an aqueous gel column.171 The most poration of oxygen species into their surface structures. Intro-
uorescent fractions achieved quantum yields close to 60%, duction of new surface states using organic molecules was
comparable to those of the best commercial CdSe/ZnS QDs in conducted by Kwon et al.6 Surface functionalization with para-
solution and brighter at the individual dot level. Aer a year, substituted anilines endowed C-dots with new energy levels,
they reported C-dots surface-passivated by a combination of exhibiting long-wavelength (up to 650 nm) PL of very narrow
inorganic and organic moieties.172 In detail, doping the surface spectral widths with high quantum yields of ca. 20% (Fig. 18).
of the precursor C-dots with inorganic salts, such as ZnS or ZnO, Introduction of surface states also changes excitation-(in)
followed by functionalization with PEG1500N molecules led to dependent characteristics.7,14 Nie et al. prepared two types of
the formation of surface-doped carbon dots. Coupled with gel C-dots with either excitation-independent blue emission or
column fractionation, the most uorescent C-dots exhibited distinctive excitation-dependent full-color emission from chlo-
uorescence emission quantum yields of up to 78%. roform (CHCl3) and diethylamine (DEA) by varying the reaction
Surface functionalization can also change the excitation/ time.14 Diversied surface states obtained at longer reaction
emission characteristics by introducing new emissive surface times resulted in excitation-dependent behavior. The opposite
states on C-dots, which can interact with the intrinsic band gap phenomenon was observed by Li et al.7 They varied the passiv-
core via electron and/or energy transfer.6,7,11–14,21,173 The Pang ation degree of surface traps on C-dots by changing their
group prepared luminescent C-dots by electrochemical etching surface coverage with amino groups. Amino-poor C-dots had
of carbon bers and observed red-shied emission of the C-dots various surface states (terminated with various groups) and
with a high degree of surface oxidation.11 They speculated that exhibited excitation-dependent behavior, whereas C-dots with
surface oxidation would create emissive surface states, which surfaces rich in amino-groups exhibited excitation-independent
are considered responsible for C-dot PL. Different surface states behavior due to amino-passivated surface states (Fig. 19).
View Article Online
a rapid response towards Zn2+ (within 1 min), with a detection

limit as low as 6.4 nM. Although much research had been done
on C-dot-based sensors for heavy metal detection, the use of
similar systems for anion detection is relatively scarce. In 2013,
Liu et al. synthesized [Zr(H2O)2EDTA]-modulated luminescent
C-dots as uorescent probes for uoride detection.185 In 2015,
Baruah et al. reported sensitive and selective uoride ion
detectors based on C-dots functionalized with b-cyclodextrin
Fig. 18 Schematic of surface functionalization and molecular struc- and calix[4]arene-25,26,27,28-tetrol.186 The functionalized
tures of para-substituted anilines used in the functionalization of C- C-dots showed increased PL intensity exclusively in the pres-
ence of F, with a minimum detection limit of 6.6 M.
dots. Reproduced from ref. 6 with permission.

Recently, the detection range of C-dot-based sensors was
extended to various molecules.8,15,187–192 Shen et al. fabricated
4.2. Sensing uorescent C-dots modied with boronic acid for non-enzy-
Surface functionalization allows the synthesis of a variety of matic glucose sensing applications.8 The functionalized C-dots
C-dots for sensing applications by changing their surface were obtained by one-step hydrothermal carbonization of phe-
functional groups, which act as a receptor. Specically, surface nylboronic acid. The addition of glucose selectively led to the
functionalized C-dots are widely used for detecting ions in vivo assembly and uorescence quenching of the C-dots (Fig. 20),
and in vitro: Hg2+,174 Cu2+,175–177,183 Zn2+,178 Fe3+,25,179 Be2+,7 Pt4+,180 which could be used for quantifying glucose in the range of
Cr4+,181 Cd2+,182 etc. In 2010, Gonçalves et al. developed a Hg2+ 9–900 mM. Beyond that, various surface modication methods
biosensor based on functionalized C-dots.174 C-Dots were for C-dots were developed to detect specic molecules such as
synthesized by direct laser ablation of carbon targets and dipicolinic acid,15 methyl parathion,187 water,188 quercetin,189
functionalized with NH2–(polyethylene glycol) (PEG200) and nifedipine,190 ascorbic acid,191 m-phenylenediamine,192 etc.
N-acetyl-L-cysteine (NAC). Functionalization with PEG200 and Functionalized C-dots for nanoparticle detection were
NAC allowed the synthesis of a nanosensor sensitive to micro- developed by the Valcárcel group.9 They developed a simple
molar concentrations of Hg2+ and Cu2+ and the solution pH. In procedure involving amidation of passivated C-dots with
2012, Dong et al. developed a more selective sensor for cysteamine, which showed enhanced photoluminescent prop-
Cu2+ by synthesizing C-dots functionalized with branched erties and had thiol-terminated groups on their surface
poly(ethylenimine) (BPEI).183 BPEI is a well-known receptor (Fig. 21). The high affinity of thiol groups for gold atoms allowed
capable of selectively capturing traces of copper ions (Cu2+);184 development of a selective photoluminescent probe for gold
therefore, the BPEI-functionalized C-dots served as a good nanoparticles based on static quenching. A selective detection
uorescent probe for sensitive and selective sensing of Cu2+ method for citrated silver nanoparticles based on C-dots func-
ions.175 Zhang et al. developed an in vivo uorescent nanosensor tionalized with amine-terminated groups via an amidation
for Zn2+ based on C-dots functionalized with a quinoline reaction was also reported.193 C-Dot sensors for determination
derivative.178 The nanosensor demonstrated high selectivity and
Fig. 19 Surface-state engineering of C-dots with excitation depen-

dent and excitation-independent luminescent properties. C-Dots
(represented as L-CDs in the figure) with various surface states
(terminated with various groups) emit excitation-dependent light. C- Fig. 20 (a) One-step “synthesis-modification integration” strategy for
Dots with surfaces rich in amino-groups exhibit excitation-indepen- fabrication of boronic acid functionalized C-dots. (b) Working principle
dent behavior because of passivated surface states. Reproduced from for glucose sensing. Reprinted with permission from ref. 8. Copyright
ref. 7 with permission. 2014 American Chemical Society.
View Article Online
of water-soluble C60 fullerenes have also been developed by the pyrolysis of anhydrous citric acid in N-(b-aminoethyl)-g-amino-
Valcárcel group.194 C-dots functionalized with carboxymethyl- propyl methyldimethoxysilane (AEAPMS) (Fig. 22). These surface
b-cyclodextrin showed uorescence quenching, owing to the methoxysilyl groups could be directly fabricated into a hybrid
non-covalent self-assembly of functionalized C-dots and C60, uorescent lm or monolith by simple heating in the absence of
making possible the quantication of the latter. any additional polymers or inorganic compounds. The change of
C-dot morphology was investigated by other researchers. Wang
et al. have created a exible, free-standing, and transparent
4.3. Enhancement of mechanical property
ionogel by the combination of a carboxyl-functionalized IL with
C-Dots without surface functionalization showed low dis- organosilane-functionalized C-dots.196 This C-dot ionogel exhibited
persibility and restricted solubility, which limit their potential thickness-dependent emission tunability at a single excitation
applications. Surface functionalization enables the high dis- wavelength, based on the combination of light reabsorption and
persibility of C-dots in various solvents, including organic the excitation-dependent PL of organosilane-functionalized C-dots
ones.19,24,195 Bourlinos et al. synthesized surface-functionalized dispersed in the ionogel at a high concentration (Fig. 23).
C-dots by thermal decomposition of either different ammonium
citrate salts or 4-aminoantipyrine.19 In the ammonium citrate 4.4. Bioapplication
route, the citrate unit served as the source of carbon, while the
Surface functionalization of C-dots introduces an effective
ammonium provided the covalently attached surface modier.
linkage to connect C-dots to biological systems. In addition,
Thus, carbonization of different ammonium citrates resulted in
biocompatibility and nontoxicity encourage the investigation
different C-dot properties, e.g., using octadecyl ammonium
of C-dot bioapplications, such as bioimaging, biosensing,
citrate resulted in organophilic nanoparticles, whereas
drug delivery, theranostics, etc. In vivo bioimaging and bio-
carbonization of the 2-(2-aminoethoxy)-ethanol salt resulted in
sensing based on functionalized C-dots was investigated by
hydrophilic nanoparticles. In the 4-aminoantipyrine route, the
various researchers.10,14,16,22,23,25,167,168,176,178,188,198–210 The rst
obtained particles also showed high dispersibility in solvents
work on C-dots for bioimaging applications was reported by
such as DMSO, DMF, and CF3CH(OH)CF3. The authors also
the Sun group.167 In this paper, the authors synthesized
developed a method for making functionalized C-dots highly
dispersible in water and photostable in the long term, using
thermal oxidation of a salt precursor prepared from the
acid–base reaction of tris(hydroxymethyl)aminomethane (Tris)
and betaine hydrochloride to form the corresponding ammo-
nium carboxylate complex.195 Superhydrophobic C-dots in
liquid and solid phases were presented by Wang et al., obtained
via surface functionalization of water-soluble C-dots with
amine-functionalized polyhedral oligomeric silsesquioxane
(POSS–NH2) by chemical bonding.24
Surface functionalization also allowed C-dots to form
Fig. 22 Schematic diagram for the preparation of photoluminescent
solid-state architectures.24,196,197 Wang et al. rst used an organo- C-dots (represented as CDs in the figure), flexible CDs film, and CDs/
silane as a coordinating solvent to synthesize highly luminescent silica particles. Reprinted with permission from ref. 24. Copyright 2011
C-dots (quantum yield ¼ 47%).24 The reaction proceeded through John Wiley and Sons.
Fig. 23 (a) Schematic illustration of the preparation of the C-dot-

ionogel using Si–C-dots through sol–gel processing in the presence
Fig. 21 Synthesis route for raw carbon dots (represented as r-CDs in of an IL [Carb-Bim]Br. (b) Photographs of the free-standing pellets of
the figure), their subsequent passivation with acetone and final func- the C-dot-ionogel, which are both transparent and flexible. Reprinted
tionalization with cysteamine. Reprinted from ref. 9, Copyright 2014, with permission from ref. 196. Copyright 2014 American Chemical
with permission from Elsevier. Society.
View Article Online
PEG1500N-passivated C-dots via laser ablation and passivation. CdSe/ZnS QDs to obtain a dual-emission uorophore
Confocal microscopy images of E. coli ATCC 25922 cells labeled (CdSe@C nanohybrid), in which CdSe/ZnS QDs embedded in
with the passivated C-dots were obtained (Fig. 24a–d). Shortly silica shells (CdSe@SiO2) were inert to Cu2+ ions and only
aerwards, they reported two-photon luminescence microscopy served as reference signals for providing built-in correction to
imaging of the C-dots internalized in human cancer cells.198 The avoid environmental effects. Meanwhile, AE-TPEA, acting as
C-dots were passivated with poly(propionylethylenimine-co-ethyl- a specic receptor for Cu2+ ions, was synthesized and conju-
enimine) (PPEI-EI) and exhibited strong luminescence based on gated with the responsive C-dot surface to form inorganic–
two-photon excitation in the near-infrared region. Finally the organic CdSe@C-TPEA probes. The blue-uorescent C-dots
two-photon luminescence microscopy imaging of the C-dots functionalized with AE-TPEA could selectively recognize Cu2+
internalized in human breast cancer MCF-7 cells using excitation ions, leading to blue uorescence quenching, whereas the red
by 800 nm laser pulses was demonstrated (Fig. 24e). uorescence of CdSe@SiO2 particles stayed constant. Conse-
The Tian group integrated an organic molecule specic quently, variation of the two uorescence intensities showed
for Cu2+ ions, N-(2-aminoethyl)-N,N,N0 -tris(pyridin-2-ylmethyl) a continuous change upon addition of Cu2+ ions, which could be
ethane-1,2-diamine (AE-TPEA), into a hybrid system composed successfully applied for imaging and biosensing of Cu2+ ions in
of C-dots and CdSe/ZnS quantum dots (Fig. 25).199 In detail, the living cells. In the same year, the group reported a C-dot-based
blue-uorescent C-dots were hybridized with red-uorescent inorganic–organic uorescent probe for two-photon biosensing of
physiological pH in living cells.200 The AE-TPY (40 -(amino-
methylphenyl)-2,20 :60 ,200 -terpyridine) molecules were bound to
C-dots functionalized with –COOH and/or –OH groups to form the
inorganic–organic nanosystem CD-TPY, using amidation catalysts
such as sulfo-NHS (N-hydroxysulfosuccinimide) and EDC (1-ethyl-
3-(3-dimethylaminopropyl)carbodiimide) (Fig. 26). The CD-TPY
probe has been successfully used in two-photon imaging and
biosensing of pH gradients in living cells and tissues.
Li et al. reported functionalized C-dots as nanoprobes for
targeting cancer cells in vitro.211 In this work, they synthesized
three passivated C-dot types with different polymer coatings:
polymer 1, poly(ethylene glycol), H2NCH2-(CH2CH2O)nCH2-
CH2CH2NH2 (average n 35, PEG1500N); polymer 2, a triblock
copolymer consisting of poly(ethylenimine)-b-poly(ethylene
glycol)-b-poly(ethylenimine) (PEI-PEG-PEI, 5k-5k-5k); and poly-
mer 3, a 4-arm, amine-terminated PEG (4-arm PEG, MW ¼ 10k).
The three C-dot types with the different polymer coatings were
named CD2 (CD-PEG1500N), CD3 (CD-PEI-PEG-PEI), and CD4
(CD-4 arm PEG). All three CDs were further functionalized with
human transferrin (Tf) through carbodiimide chemistry to
target HeLa cancer cells in vitro (Fig. 27).
Theranostic drug delivery systems, representing a combination
of medical therapy and bioimaging diagnostics, are paving the way
for personalized medicine. A C-dot-based theranostic gene delivery
system was reported by several researchers.17,26,212–216 Liu et al.
synthesized polyethylenimine-functionalized C-dots (CD-PEI) via
Fig. 24 Confocal microscopy images of E. coli ATCC 25922 cells

labeled with the C-dots: (a) lEX ¼ 458 nm, detected with a 475 nm long
pass filter; (b) lEX ¼ 477 nm, detected with a 505 nm long pass filter; (c)
lEX ¼ 488 nm, detected with a 530 nm long pass filter; and (d) lEX ¼ 514
nm, detected with a 560 nm long pass filter. Reprinted with permission
from ref. 167. Copyright 2006 American Chemical Society. (e)
Representative two-photon luminescence image (800 nm excitation)
of human breast cancer MCF-7 cells with internalized C-dots. Fig. 25 Dual-emission fluorescent sensing of Cu2+ ions based on
Reprinted with permission from ref. 198. Copyright 2007 American a CdSe@C-TPEA nanohybrid. Reprinted with permission from ref. 199.
Chemical Society. Copyright 2011 John Wiley and Sons.
View Article Online

Fig. 26 Schematic illustration of a CD-TPY nanoprobe for two-

photon pH imaging and biosensing. The receptor-AE-TPY binding
onto C-dots was achieved through the condensation reaction of
amino and carboxyl with NHS and EDC as catalysts. In the sensing
process, the photochemical cycle was regulated by the protonation Fig. 27 Targeting HeLa cells with transferrin conjugated C-dots.
and deprotonation of N atoms with pH value change in the nanoprobe Comparison of cells treated with (a) CD3 (top transmission and PL
solution. Reprinted with permission from ref. 200. Copyright 2012 images) versus CD3-Tf (middle transmission and PL images) versus
John Wiley and Sons. CD3-Tf incubated with cells pretreated with free Tf for 1 h (bottom
transmission and PL images) and cells nonpretreated with free Tf; (b)
CD4-Tf incubated with cells pretreated with free Tf for 1 h (top
transmission and PL images) and cells nonpretreated with free Tf
a one-step microwave-assisted pyrolysis of glycerol in the presence (bottom transmission and PL images). Reprinted with permission from
of branched PEI.26 The outer cationic polymer layer could mediate ref. 211. Copyright 2010 American Chemical Society.
plasmid DNA transfection, thus CD-PEI could mediate gene
transfection in COS-7 and HepG2 cells with high efficiency. In
addition, the multicolor uorescence of CD-PEI endowed CD-PEI multicolor imaging ability of C-dots. Wu et al. developed
with an intrinsic ability to combine the dual function of gene a theranostic nanoagent that can be simultaneously used in
delivery and bioimaging. Karthik et al. constructed a photo- lung cancer diagnosis and therapeutics.214 The synthesis route
responsive nanodrug delivery system (DDS) using C-dots and is briey demonstrated as follows (Fig. 28d). In the diagnostic
a quinolone-based phototrigger.212 In this paper, they described segment, C-dots were synthesized via microwave pyrolysis of
the synthesis of a phototrigger-conjugated anticancer drug. The glycerol and polyethylenimine (PEI). Free PEI molecules were
drug was covalently graed onto the surface of C-dots using then conjugated with PEI-Cdots using the environment-sensi-
potassium tert-butoxide in dry THF. The functionalized C-dots tive disulde linkage, forming reducible PEI-Cdots (rPEI-Cdots).
were readily internalized inside the HeLa cells and showed The positive charge on rPEI could electrostatically bind nega-
precisely controlled drug release, killing the cancer cells upon tively charged siRNA molecules. The disulde linkages between
irradiation by UV light (>365 nm). PEI molecules could be broken down by glutathione aer the
Tang et al. also reported a drug delivery system obtained by uptake of theranostic nanoagents by cancer cells, releasing
direct coupling17 of poly(ethylene glycol) (PEG) with the C-dot therapeutic siRNAs into the cytosol to accomplish the thera-
surface, followed by trapping the guest drug molecules (DOX) peutic purpose. Folate, serving as a tumor-targeting molecule,
within the PEG network and attaching them to the C-dot surface was conjugated with the rPEI-Cdots/siRNA complex to form
via p–p stacking (Fig. 28a and b). The efficient FRET between fc-rPEI-Cdots/siRNA multifunctional nanoagents.
C-dots and DOX showed emission peaks at 498 and 595 nm.
When DOX was released from the C-dot surface, the FRET signal 4.5. Other applications
(594 nm) between C-dots and DOX was reduced or quenched,
The surface functionalization strategy can be used in other
thus displaying an enhanced emission at 498 nm. This change
applications such as photocatalysis,217–221 electrocatalysis,222,223
in the FRET signal allowed C-dot DDS for real-time monitoring
optoelectronics,224 and electrochemiluminescence.225,226 Photo-
and tracking of the uorescent drug molecule release. Zheng
reduction of CO2 under homogeneous reaction conditions in
et al. integrated oxaliplatin with C-dots (CD-Oxa) to form
water using surface-functionalized C-dots was proposed by the
a theranostic system by means of a condensation reaction.213
Sun group.217 In this study, the C-dot surface was functionalized
The carboxyl group of Oxa(IV)–COOH was conjugated with CDs
with oligomeric poly(ethylene glycol)diamine (PEG1500N) and
to form a theranostic nanomedicine (Fig. 28c). CD-Oxa inte-
subsequently doped with gold or platinum, concentrating the
grated the optical properties of CDs and the anticancer function
photogenerated electrons to enable more efficient CO2 reduc-
of oxaliplatin into a single unit, and showed multiple functions:
tion (Fig. 29a). Hu et al. synthesized C-dots by heating
(i) endocytosis-based drug carrier; (ii) controlled drug release by
various carbon sources in HNO3 solution at reux, with the
the intrinsically reducing environment of cancer cells; (iii)
oxygen-containing surface groups of the as-prepared C-dots
View Article Online

Fig. 29 (a) Aqueous soluble PEG-functionalized C-dots before (left,

fluorescent) and after (right, photocatalytic for CO2 reduction in
aqueous solution) coating with metal. Reprinted with permission from
ref. 217. Copyright 2011 American Chemical Society. (b) Illustration of
the fabrication of a label-free electrochemiluminescent cytosensor.
Reproduced from ref. 225 with permission from The Royal Society of
Chemistry.
cancer cells by using a poly(allylamine hydrochloride) (PAH)

functionalized graphene-modied glassy carbon (GC) elec-
trode (Fig. 29b).225 Wang et al. also showed the enhanced ECL
of the nanoAg–C-dot composite and its application for
sensitive detection of sulde (S2) ions.226
Fig. 28 (a) A schematic representation of the surface coupling

5. Summary and outlook
chemistry for FRET-C-dot-DDS. (b) Proposed mechanism of the
C-Dots, as a type of uorescent carbon nanoparticles, have
FRET-C-dot-DDS for drug delivery. Reprinted with permission from
ref. 17. Copyright 2013 John Wiley and Sons. (c) Synthesis scheme for recently enjoyed considerable attention due to their interesting
CD-Oxa and its applications in bioimaging and theranostics. Reprinted properties, distinguishing them from conventional uorescent
with permission from ref. 213. Copyright 2014 John Wiley and Sons. (d) materials such as organic uorophores or inorganic nano-
Synthesis route of fc-rPEI-C-dots/siRNA multifunctional nanoagents. crystals. The major advantages of C-dots such as strong lumi-
Reproduced from ref. 214 with permission.
nescence, non-toxicity, and biocompatibility make them
promising materials for biomedicine, optoelectronics, sensing,
photovoltaics, and photocatalysis. So far, many synthesis
subsequently selectively reduced by NaBH4, leading to new methods have been developed to improve the functionality of
surface states.218 The authors claimed that the photocatalytic C-dots for various applications, with doping and surface func-
activity of C-dots was determined by surface states alone, tionalization considered to be two main methods for control-
more specically by C]O and COOH groups, and was not ling the chemical, optical, and electrical properties of C-dots.
related to their size. Choi et al. developed efficient polymer With the help of doping and surface functionalization, the
optoelectronic devices by using C-dot-supported silver electronic structures of C-dots related to their light absorption
nanoparticles as plasmonic materials.224 The poly(ethylene and luminescence become tunable, extending the application
glycol)-functionalized C-dots were photoexcited with ultra- range of C-dots.
violet irradiation in the presence of AgNO3 for reducing the Although many research groups have made efforts to
Ag+ ions to form silver nanoparticles on the surface of the improve the functionality of C-dots, several limitations still
carbon dots. Wu et al. developed C-dot@Ag core–shell hybrid exist, hampering the use of C-dots in certain research elds. For
nanoparticles as an electrochemiluminescence (ECL) signal bio-imaging, it would be very useful if C-dots exhibited light
reporter for label-free sensitive and selective detection of absorption and PL in a near-infrared region to avoid the
View Article Online
auto-uorescence of cells and tissues. Optoelectronic applica- 19 A. B. Bourlinos, A. Stassinopoulos, D. Anglos, R. Zboril,
tions have required C-dots to exhibit high color-purity (narrow M. Karakassides and E. P. Giannelis, Small, 2008, 4, 455–
linewidth) luminescence and warm colors, such as amber and 458.
red, by tuning of their electronic structures. Recently, progress 20 R. Liu, D. Wu, S. Liu, K. Koynov, W. Knoll and Q. Li, Angew.
has been made to li the aforementioned limitations of C-dots, Chem., Int. Ed., 2009, 121, 4668–4671.
achieving a certain level of success to prove the potential of 21 H. Ding, S.-B. Yu, J.-S. Wei and H.-M. Xiong, ACS Nano,
C-dots in a variety of research areas. There is no doubt that 2016, 10, 484–491.
C-dots will complement the weak points of organic uo- 22 L. Yang, W. Jiang, L. Qiu, X. Jiang, D. Zuo, D. Wang and
rophores and inorganic nanocrystals, guaranteeing themselves L. Yang, Nanoscale, 2015, 7, 6104–6113.
a bright future. 23 I. P.-J. Lai, S. G. Harroun, S.-Y. Chena, B. Unnikrishnana,
Y.-J. Li and C.-C. Huang, Sens. Actuators, B, 2016, 228,

Acknowledgements 465–470.
24 F. Wang, Z. Xie, H. Zhang, C. Liu and Y. Zhang, Adv. Funct.
This work is supported by the Basic Science Research Mater., 2011, 21, 1027–1031.
Program of the National Research Foundation of Korea 25 Q. Yang, L. Wei, X. Zheng and L. Xiao, Sci. Rep., 2015, 5,
(NRF-2016R1C1B1011830) and the Sookmyung Women's 17727.
University Research Grant (1-1603-2041). 26 C. Liu, P. Zhang, X. Zhai, F. Tian, W. Li, J. Yang, Y. Liu,
H. Wang, W. Wang and W. Liu, Biomaterials, 2012, 33,
Notes and references 3604–3613.
27 W. Kwon, G. Lee, S. Do, T. Joo and S.-W. Rhee, Small, 2014,
1 X. Xu, R. Ray, Y. Gu, H. J. Ploehn, L. Gearheart, K. Raker and 10, 506–513.
W. A. Scrivens, J. Am. Chem. Soc., 2004, 126, 12736–12737. 28 S. Zhu, Q. Meng, L. Wang, J. Zhang, Y. Song, H. Jin,
2 S. N. Baker and G. A. Baker, Angew. Chem., Int. Ed., 2010, 49, K. Zhang, H. Sun, H. Wang and B. Yang, Angew. Chem.,
6726–6744. Int. Ed., 2013, 52, 3953–3957.
3 H. Li, Z. Kang, Y. Liu and S.-T. Lee, J. Mater. Chem., 2012, 22, 29 S. Sarkar, K. Das, M. Ghosh and P. K. Das, RSC Adv., 2015, 5,
24230–24253. 65913–65921.
4 H. Liu, T. Ye and C. Mao, Angew. Chem., Int. Ed., 2007, 46, 30 R. Q. Zhang, E. Bertran and S.-T. Lee, Diamond Relat. Mater.,
6473–6475. 1998, 7, 1663–1668.
5 S.-L. Hu, K.-Y. Niu, J. Sun, J. Yang, N.-Q. Zhao and X.-W. Du, 31 H. Li, X. He, Z. Kang, H. Huang, Y. Liu, J. Liu, S. Lian,
J. Mater. Chem., 2009, 19, 484–488. C. H. A. Tsang, X. Yang and S.-T. Lee, Angew. Chem., Int.
6 W. Kwon, S. Do, J.-H. Kim, M. S. Jeong and S.-W. Rhee, Sci. Ed., 2010, 49, 4430–4434.
Rep., 2015, 5, 12604. 32 Z. Luo, Y. Lu, L. A. Somers and A. T. C. Johnson, J. Am.
7 X. Li, S. Zhang, S. A. Kulinich, Y. Liu and H. Zeng, Sci. Rep., Chem. Soc., 2009, 131, 898–899.
2014, 4, 4976. 33 S. Zhu, Y. Song, X. Zhao, J. Shao, J. Zhang and B. Yang, Nano
8 P. Shen and Y. Xia, Anal. Chem., 2014, 86, 5323–5329. Res., 2015, 8, 355–381.
9 A. Cayuela, M. L. Soriano, M. C. Carrión and M. Valcárcel, 34 P. Roy, P.-C. Chen, A. P. Periasamy, Y.-N. Chen and
Anal. Chim. Acta, 2014, 820, 133–138. H.-T. Chang, Mater. Today, 2015, 18, 447–458.
10 S. Liu, N. Zhao, Z. Cheng and H. Liu, Nanoscale, 2015, 7, 35 L. Wang, S.-J. Zhu, H.-Y. Wang, S.-N. Qu, Y.-L. Zhang,
6836–6842. J.-H. Zhang, Q.-D. Chen, H.-L. Xu, W. Han, B. Yang and
11 L. Bao, Z.-L. Zhang, Z.-Q. Tian, L. Zhang, C. Liu, Y. Lin, B. Qi H.-B. Sun, ACS Nano, 2014, 8, 2541–2547.
and D.-W. Pang, Adv. Mater., 2011, 23, 5801–5806. 36 P. Ayala, R. Arenal, A. Loiseau, A. Rubio and T. Pichler, Rev.
12 L. Bao, C. Liu, Z.-L. Zhang and D.-W. Pang, Adv. Mater., Mod. Phys., 2010, 82, 1843–1885.
2015, 27, 1663–1667. 37 Y. Wang and A. Hu, J. Mater. Chem. C, 2014, 2, 6921–6939.
13 K. Hola, A. B. Bourlinos, O. Kozak, K. Berka, K. M. Siskova, 38 Y.-Q. Zhang, D.-K. Ma, Y. Zhuang, X. Zhang, W. Chen,
M. Havrdova, J. Tucek, K. Safarova, M. Otyepka, L.-L. Hong, Q.-X. Yan, K. Yu and S.-M. Huang, J. Mater.
E. P. Giannelis and R. Zbori, Carbon, 2014, 70, 279–286. Chem., 2012, 22, 16714–16718.
14 H. Nie, M. Li, Q. Li, S. Liang, Y. Tan, L. Sheng, W. Shi and 39 S. Chandra, D. Laha, A. Pramanik, A. R. Chowdhuri,
S. X.-A. Zhang, Chem. Mater., 2014, 26, 3104–3112. P. Karmakar and S. K. Sahu, Luminescence, 2016, 31, 81–87.
15 H. Chen, Y. Xie, A. M. Kirillov, L. Liu, M. Yu, W. Liu and 40 Y. Xu, M. Wu, Y. Liu, X.-Z. Feng, X.-B. Yin, X.-W. He and
Y. Tang, Chem. Commun., 2015, 51, 5036–5039. Y.-K. Zhang, Chem.–Eur. J., 2013, 19, 2276–2283.
16 E. J. Goh, K. S. Kim, Y. R. Kim, H. S. Jung, S. Beack, 41 Z. Guo, L. Gai, J. Zhou, H. Jiang and Y. Tian, Sens. Actuators,
W. H. Kong, G. Scarcelli, S. H. Yun and S. K. Hahn, B, 2016, 232, 722–731.
Biomacromolecules, 2012, 13, 2554–2561. 42 Z. Ma, H. Ming, H. Huang, Y. Liu and Z. Kang, New J. Chem.,
17 J. Tang, B. Kong, H. Wu, M. Xu, Y. Wang, Y. Wang, D. Zhao 2012, 36, 861–864.
and G. Zheng, Adv. Mater., 2013, 25, 6569–6574. 43 R. Zhang and W. Chen, Biosens. Bioelectron., 2014, 55, 83–
18 L. Tian, D. Ghosh, W. Chen, S. Pradhan, X. Chang and 90.
S. Chen, Chem. Mater., 2009, 21, 2803–2809. 44 J. Ju and W. Chen, Biosens. Bioelectron., 2014, 58, 219–225.
View Article Online
45 J. Ju, R. Zhang, S. He and W. Chen, RSC Adv., 2014, 4, 72 H. Li, W. Kong, J. Liu, N. Liu, H. Huang, Y. Liu and Z. Kang,
52583–52589. Carbon, 2015, 91, 66–75.
46 J. Ju, R. Zhang and W. Chen, Sens. Actuators, B, 2016, 228, 73 F. Messina, L. Sciortino, R. Popescu, A. M. Venezia,
66–73. A. Sciortino, G. Buscarino, S. Agnello, R. Schneider,
47 C. Wang, X. Wu, X. Li, W. Wang, L. Wang, M. Gu and Q. Li, D. Gerthsen, M. Cannasa and F. M. Gelardia, J. Mater.
J. Mater. Chem., 2012, 22, 15522–15525. Chem. C, 2016, 4, 2598–2605.
48 W. Kwon, S. Do, J. Lee, S. Hwang, J. K. Kim and S.-W. Rhee, 74 Y. Zhang, P. Cui, F. Zhang, X. Feng, Y. Wang, Y. Yang and
Chem. Mater., 2013, 25, 1893–1899. X. Liu, Talanta, 2016, 152, 288–300.
49 Y. Jiang, Q. Han, C. Jin, J. Zhang and B. Wang, Mater. Lett., 75 J. Feng, W.-J. Wang, X. Hai, Y.-L. Yu and J.-H. Wang,
2015, 141, 366–368. J. Mater. Chem. B, 2016, 4, 387–393.
50 M. Xu, G. He, Z. Li, F. He, F. Gao, Y. Su, L. Zhang, Z. Yang 76 L. Wang and H. S. Zhou, Anal. Chem., 2014, 86, 8902–8905.
and Y. Zhang, Nanoscale, 2014, 6, 10307–10315. 77 X. Teng, C. Ma, C. Ge, M. Yan, J. Yang, Y. Zhang,
51 S. Gao, Y. Chen, H. Fan, X. Wei, C. Hu, L. Wang and L. Qu, P. C. Moraiscd and H. Bi, J. Mater. Chem. B, 2014, 2,
J. Mater. Chem. A, 2014, 2, 6320–6325. 4631–4639.
52 Z. Li, Y. Ni and S. Kokot, Biosens. Bioelectron., 2015, 74, 91– 78 Z. Zhang, S. Xu and P. Wu, Part. Part. Syst. Charact., 2015,
97. 32, 176–181.
53 J. Zhou, T. Han, H. Ma, T. Yan, X. Pang, Y. Li and Q. Wei, 79 J. Wang, P. Zhang, C. Huang, G. Liu, K. C.-F. Leung and
Anal. Chim. Acta, 2015, 889, 82–89. Y. X. J. Wáng, Langmuir, 2015, 31, 8063–8073.
54 T. H. Kim, H. W. Ho, C. L. Brown, S. L. Cresswell and Q. Li, 80 Z. Qian, J. Ma, X. Shan, H. Feng, L. Shao and J. Chen,
Anal. Methods, 2015, 7, 6869–6876. Chem.–Eur. J., 2014, 20, 2254–2263.
55 B. Wang, Y. Chen, Y. Wu, B. Weng, Y. Liu, Z. Lu, C. M. Li 81 Z. Li, H. Yu, T. Bian, Y. Zhao, C. Zhou, L. Shang, Y. Liu,
and C. Yu, Biosens. Bioelectron., 2016, 78, 23–30. L.-Z. Wu, C.-H. Tung and T. Zhang, J. Mater. Chem. C,
56 L. Wang, Y. Yin, A. Jain and H. S. Zhou, Langmuir, 2014, 30, 2015, 3, 1922–1928.
14270–14275. 82 Z.-Q. Xu, J.-Y. Lan, J.-C. Jin, P. Dong, F.-L. Jiang and Y. Liu,
57 W. Lu, X. Gong, M. Nan, Y. Liu, S. Shuang and C. Dong, ACS Appl. Mater. Interfaces, 2015, 7, 28346–28352.
Anal. Chim. Acta, 2015, 898, 116–127. 83 Q.-Q. Shi, Y.-H. Li, Y. Xu, Y. Wang, X.-B. Yin, X.-W. He and
58 H. Zhang, Y. Li, X. Liu, P. Liu, Y. Wang, T. An, H. Yang, Y.-K. Zhangac, RSC Adv., 2014, 4, 1563–1566.
D. Jing and H. Zhao, Environ. Sci. Technol. Lett., 2014, 1, 84 H. Yuan, J. Yu, S. Feng and Y. Gonga, RSC Adv., 2016, 6,
87–91. 15192–15200.
59 Y. Wang, Y. Meng, S. Wang, C. Li, W. Shi, J. Chen, J. Wang 85 H. Huang, C. Li, S. Zhu, H. Wang, C. Chen, Z. Wang, T. Bai,
and R. Huang, Small, 2015, 11, 3575–3581. Z. Shi and S. Feng, Langmuir, 2014, 30, 13542–13548.
60 X. Feng, Y. Jiang, J. Zhao, M. Miao, S. Cao, J. Fang and 86 M. Xu, S. Xu, Z. Yang, M. Shu, G. He, D. Huang, L. Zhang,
L. Shi, RSC Adv., 2015, 5, 31250–31254. L. Li, D. Cui and Y. Zhang, Nanoscale, 2015, 7, 15915–15923.
61 T. Han, T. Yan, Y. Li, W. Cao, X. Pang, Q. Huang and Q. Wei, 87 S. Yang, J. Sun, X. Li, W. Zhou, Z. Wang, P. He, G. Ding,
Carbon, 2015, 91, 144–152. X. Xie, Z. Kang and M. Jiang, J. Mater. Chem. A, 2014, 2,
62 S. Tiwari, A. Ghosh, A. Santra, T. Das and S. Ghosh, Journal 8660–8667.
of Material Science and Mechanical Engineering, 2015, 2, 58– 88 J. Tan, R. Zou, J. Zhang, W. Li, L. Zhang and D. Yue,
60. Nanoscale, 2016, 8, 4742–4747.
63 Q. Xu, J. Zhao, Y. Liu, P. Pu, X. Wang, Y. Chen, C. Gao, 89 Y. Jiang, B. Wang, F. Meng, Y. Cheng and C. Zhu, J. Colloid
J. Chen and H. Zhou, J. Mater. Sci., 2015, 50, 2571–2576. Interface Sci., 2015, 452, 199–202.
64 W.-J. Niu, Y. Li, R.-H. Zhu, D. Shan, Y.-R. Fan and 90 P. Yang, J. Zhao, J. Wang, H. Cui, L. Li and Z. Zhu,
X.-J. Zhang, Sens. Actuators, B, 2015, 218, 229–236. ChemPhysChem, 2015, 16, 3058–3063.
65 H. Ding and H.-M. Xiong, RSC Adv., 2015, 5, 66528–66533. 91 S. Do, W. Kwon, Y.-H. Kim, S. R. Kang, T. Lee, T.-W. Lee and
66 J. Niu, H. Gao, L. Wang, S. Xin, G. Y. Zhang, Q. Wang, S.-W. Rhee, Adv. Opt. Mater., 2016, 4, 276–284.
L. Guo, W. Liu, X. Gao and Y. Wang, New J. Chem., 2014, 92 J. Deng, Q. Lu, Y. Hou, M. Liu, H. Li, Y. Zhang and S. Yao,
38, 1522–1527. Anal. Chem., 2015, 87, 2195–2203.
67 X. Gong, W. Lu, M. C. Paau, Q. Hub, X. Wu, S. Shuang, 93 Y. Jiang, Y. Wang, F. Meng, B. Wang, Y. Cheng and C. Zhu,
C. Dong and M. M. F. Choi, Anal. Chim. Acta, 2015, 861, New J. Chem., 2015, 39, 3357–3360.
74–84. 94 Y.-Q. Zhang, D.-K. Ma, Y.-G. Zhang, W. Chen and
68 Z. Lei, S. Xu, J. Wan and P. Wu, Nanoscale, 2016, 8, 2219– S.-M. Huang, Nano Energy, 2013, 2, 545–552.
2226. 95 S. Dey, P. Chithaiah, S. Belawadi, K. Biswas and
69 W. Wang, Y.-C. Lu, H. Huang, J.-J. Feng, J.-R. Chen and C. N. R. Rao, J. Mater. Res., 2014, 29, 383–391.
A.-J. Wang, Analyst, 2014, 139, 1692–1696. 96 F. Du, X. Jin, J. Chen, Y. Hua, M. Cao, L. Zhang, J. Li,
70 J. Yu, C. Xu, Z. Tian, Y. Lin and Z. Shi, New J. Chem., 2016, L. Zhang, J. Jin, C. Wu, A. Gong, W. Xu, Q. Shao and
40, 2083–2088. M. Zhang, J. Nanopart. Res., 2014, 16, 2720.
71 X. Dong, Y. Su, H. Geng, Z. Li, C. Yang, X. Li and Y. Zhang, 97 H. Ding, P. Zhang, T.-Y. Wang, J.-L. Kong and H.-M. Xiong,
J. Mater. Chem. C, 2014, 2, 7477–7481. Nanotechnology, 2014, 25, 205604.
View Article Online
98 H. Wang, P. Sun, S. Cong, J. Wu, L. Gao, Y. Wang, X. Dai, 126 H. Peng, Y. Li, C. Jiang, C. Luo, R. Qi, R. Huang, C.-G. Duan
Q. Yi and G. Zou, Nanoscale Res. Lett., 2016, 11, 27. and J. Travas-Sejdic, Carbon, 2016, 100, 386–394.
99 F. Du, J. Yuan, M. Zhang, J. Li, Z. zhou, Z. Li, M. Cao, 127 X.-M. Wei, Y. Xu, Y.-H. Li, X.-B. Yin and X.-W. He, RSC Adv.,
J. Chen, L. Zhang, X. Liu, A. Gong, W. Xu and Q. Shao, 2014, 4, 44504–44508.
RSC Adv., 2014, 4, 37536–37541. 128 Y. Ke, B. Garg and Y.-C. Ling, RSC Adv., 2014, 4, 58329–
100 H. Zhang, J. Chen, Y. Li, P. Liu, Y. Wang, T. An and H. Zhao, 58336.
Electrochim. Acta, 2015, 165, 7–13. 129 J. Zhou, X. Shan, J. Ma, Y. Gu, Z. Qian, J. Chen and H. Feng,
101 X. Zhu, T. Zhao, Z. Nie, Z. Miao, Y. Liu and S. Yao, RSC Adv., 2014, 4, 5465–5468.
Nanoscale, 2016, 8, 2205–2211. 130 S. Chandra, P. Das, S. Bag, D. Laha and P. Pramanik,
102 Y. Dong, H. Pang, H. Yang, J. Jiang, Y. Chi and T. Yu, RSC Nanoscale, 2011, 3, 1533–1540.
Adv., 2014, 4, 32791–32795. 131 X. Shan, L. Chai, J. Ma, Z. Qian, J. Chen and H. Feng,
103 J. Hou, J. Li, J. Sun, S. Ai and M. Wang, RSC Adv., 2014, 4, Analyst, 2014, 139, 2322–2325.
37342–37348. 132 H. K. Sadhanala and K. K. Nanda, Carbon, 2016, 96, 166–
104 Z. Yang, M. Xu, Y. Liu, F. He, F. Gao, Y. Su, H. Wei and 173.
Y. Zhang, Nanoscale, 2014, 6, 1890–1895. 133 A. B. Bourlinos, G. Trivizas, M. A. Karakassides,
105 W. Wei, C. Xu, L. Wu, J. Wang, J. Ren and X. Qu, Sci. Rep., M. Baikousi, A. Kouloumpis, D. Gournis, A. Bakandritsos,
2014, 4, 3564. K. Hola, O. Kozak, R. Zboril, I. Papagiannouli, P. Aloukos
106 Y. Han, D. Tang, Y. Yang, C. Li, W. Kong, H. Huang, Y. Liu and S. Couris, Carbon, 2015, 83, 173–179.
and Z. Kang, Nanoscale, 2015, 7, 5955–5962. 134 F. Wang, Q. Hao, Y. Zhang, Y. Xu and W. Lei, Microchim.
107 C. Zheng, X. An and J. Gong, RSC Adv., 2015, 5, 32319– Acta, 2016, 183, 273–279.
32322. 135 Y. Sun, C. Shen, J. Wang and Y. Lu, RSC Adv., 2015, 5,
108 T.-R. Kuo, S.-Y. Sung, C.-W. Hsu, C.-J. Chang, T.-C. Chiu 16368–16375.
and C.-C. Hu, Anal. Bioanal. Chem., 2016, 408, 77–82. 136 S. Chandra, P. Patra, S. H. Pathan, S. Roy, S. Mitra, A. Layek,
109 H. Huang, J.-J. Lv, D.-L. Zhou, N. Bao, Y. Xu, A.-J. Wang and R. Bhar, P. Pramanik and A. Goswami, J. Mater. Chem. B,
J.-J. Feng, RSC Adv., 2013, 3, 21691–21696. 2013, 1, 2375–2382.
110 Z. L. Wu, P. Zhang, M. X. Gao, C. F. Liu, W. Wang, F. Leng 137 Q. Xu, P. Pu, J. Zhao, C. Dong, C. Gao, Y. Chen, J. Chen,
and C. Z. Huang, J. Mater. Chem. B, 2013, 1, 2868–2873. Y. Liu and H. Zhou, J. Mater. Chem. A, 2015, 3, 542–546.
111 B.-X. Zhang, G.-Y. Zhang, H. Gao, S.-H. Wu, J.-H. Chen and 138 Y. Hu, J. Yang, J. Tian, L. Jia and J.-S. Yu, Carbon, 2014, 77,
X.-L. Li, RSC Adv., 2015, 5, 7395–7400. 775–782.
112 J. Liu, X. Liu, H. Luo and Y. Gao, RSC Adv., 2014, 4, 7648– 139 Y. Guo, L. Yang, W. Li, X. Wang, Y. Shang and B. Li,
7654. Microchim. Acta, 2016, 183, 1409–1416.
113 A. Cayuela, C. Carrillo-Carrión, M. L. Soriano, W. J. Parak 140 Y. Wang, Q. Zhuang and Y. Ni, Chem.–Eur. J., 2015, 21,
and M. Valcárcel, Anal. Chem., 2016, 88, 3178–3185. 13004–13011.
114 Y. Hu, J. Yang, J. Tian, L. Jia and J.-S. Yu, RSC Adv., 2015, 5, 141 Y. Dong, H. Pang, H. B. Yang, C. Guo, J. Shao, Y. Chi,
15366–15373. C. M. Li and T. Yu, Angew. Chem., Int. Ed., 2013, 52, 7800–
115 M. K. Barman, B. Jana, S. Bhattacharyya and A. Patra, J. 7804.
Phys. Chem. C, 2014, 118, 20034–20041. 142 D. Sun, R. Ban, P.-H. Zhang, G.-H. Wu, J.-R. Zhang and
116 G. Jiang, T. Jiang, H. Zhou, J. Yao and X. Kong, RSC Adv., J.-J. Zhu, Carbon, 2013, 64, 424–434.
2015, 5, 9064–9068. 143 H. Ding, J.-S. Wei and H.-M. Xiong, Nanoscale, 2014, 6,
117 J. Zhang, Y. Yuan, G. Liang and S.-H. Yu, Adv. Sci., 2015, 2, 13817–13823.
1500002. 144 Q. Hu, M. C. Paau, Y. Zhang, X. Gong, L. Zhang, D. Lu,
118 W. Li, Z. Zhang, B. Kong, S. Feng, J. Wang, L. Wang, J. Yang, Y. Liu, Q. Liu, J. Yao and M. M. F. Choi, RSC Adv., 2014,
F. Zhang, P. Wu and D. Zhao, Angew. Chem., Int. Ed., 2013, 4, 18065–18073.
52, 8151–8155. 145 H.-X. Wang, J. Xiao, Z. Yang, H. Tang, Z.-T. Zhu, M. Zhao,
119 S. Do, W. Kwon and S.-W. Rhee, J. Mater. Chem. C, 2014, 2, Y. Liu, C. Zhang and H.-L. Zhang, J. Mater. Chem. A, 2015,
4221–4226. 3, 11287–11293.
120 H. Zhang, Y. Chen, M. Liang, L. Xu, S. Qi, H. Chen and 146 Z. Fu, M. Yao, X. Niu and F. Cui, Sens. Actuators, B, 2016,
X. Chen, Anal. Chem., 2014, 86, 9846–9852. 226, 486–494.
121 J. Niu and H. Gao, J. Lumin., 2014, 149, 159–162. 147 Y. Chen, Y. Wu, B. Weng, B. Wang and C. Li, Sens. Actuators,
122 A. Barati, M. Shamsipur, E. Arkan, L. Hosseinzadeh and B, 2016, 223, 689–696.
H. Abdollahi, Mater. Sci. Eng., C, 2015, 47, 325–332. 148 Y. Zhang and J. He, Phys. Chem. Chem. Phys., 2015, 17,
123 S. L. D'souza, B. Deshmukh, J. R. Bhamore, K. A. Rawat, 20154–20159.
N. Lenka and S. K. Kailasa, RSC Adv., 2016, 6, 12169–12179. 149 Y.-W. Zeng, D.-K. Ma, W. Wang, J.-J. Chen, L. Zhou,
124 Y. H. Yuan, Z. X. Liu, R. S. Li, H. Y. Zou, M. Lin, H. Liu and Y.-Z. Zheng, K. Yu and S.-M. Huang, Appl. Surf. Sci., 2015,
C. Z. Huang, Nanoscale, 2016, 8, 6770–6776. 342, 136–143.
125 F. Arcudi, L. ĐorCević and M. Prato, Angew. Chem., 2016, 150 M. Xue, L. Zhang, M. Zou, C. Lan, Z. Zhan and S. Zhao, Sens.
128, 2147–2152. Actuators, B, 2015, 219, 50–56.
View Article Online
151 L. Li, B. Yu and T. You, Biosens. Bioelectron., 2015, 74, 263– 175 Y. Dong, R. Wang, G. Li, C. Chen, Y. Chi and G. Chen, Anal.
269. Chem., 2012, 84, 6220–6224.
152 W. Wang, Y.-C. Lu, H. Huang, A.-J. Wang, J.-R. Chen and 176 J. Chena, Y. Li, K. Lv, W. Zhong, H. Wang, Z. Wu, P. Yi and
J.-J. Feng, Sens. Actuators, B, 2014, 202, 741–747. J. Jiang, Sens. Actuators, B, 2016, 224, 298–306.
153 M. Xue, L. Zhang, Z. Zhan, M. Zou, Y. Huang and S. Zhao, 177 Y. Lin, C. Wang, L. Li, H. Wang, K. Liu, K. Wang and B. Li,
Talanta, 2016, 150, 324–330. ACS Appl. Mater. Interfaces, 2015, 7, 27262–27270.
154 Z. Liu, J. Xiao, X. Wu, L. Lin, S. Weng, M. Chen, X. Cai and 178 Z. Zhang, Y. Shi, Y. Pan, X. Cheng, L. Zhang, J. Chen,
X. Lin, Sens. Actuators, B, 2016, 229, 217–224. M.-J. Lib and C. Yi, J. Mater. Chem. B, 2014, 2, 5020–5027.
155 C. Sun, Y. Zhang, P. Wang, Y. Yang, Y. Wang, J. Xu, Y. Wang 179 D. Wang, J. Liu, J.-F. Chen and L. Dai, Adv. Mater. Interfaces,
and W. W. Yu, Nanoscale Res. Lett., 2016, 11, 110. 2016, 3, 1500439.
156 J. Chen, H. Zhang, P. Liu, Y. Li, G. Li, T. An and H. Zhao, 180 B. B. Campos, M. M. Oliva, R. Contreras-Cáceres,
Carbon, 2015, 92, 339–347. E. Rodriguez-Castellón, J. Jiménez-Jiménez,
157 S. Jahan, F. Mansoor, S. Naz, J. Lei and S. Kanwal, Anal. J. C. G. Esteves da Silva and M. Algarra, J. Colloid Interface
Chem., 2013, 85, 10232–10239. Sci., 2016, 465, 165–173.
158 X. Gong, W. Lu, Y. Liu, Z. Li, S. Shuang, C. Dong and 181 Y. Liu, J. Hu, Y. Li, H.-P. Wei, X.-S. Li, X.-H. Zhang,
M. M. F. Choi, J. Mater. Chem. B, 2015, 3, 6813–6819. S.-M. Chen and X.-Q. Chen, Talanta, 2015, 134, 16–23.
159 Y. Gong, B. Yu, W. Yang and X. Zhang, Biosens. Bioelectron., 182 T. Yang, Y.-K. Li, M.-L. Chen and J.-H. Wang, Chin. Chem.
2016, 79, 822–828. Lett., 2015, 26, 1496–1501.
160 C. Wang, D. Sun, K. Zhuo, H. Zhang and J. Wang, RSC Adv., 183 Y. Dong, R. Wang, H. Li, J. Shao, Y. Chi, X. Lin and G. Chen,
2014, 4, 54060–54065. Carbon, 2010, 50, 2810–2815.
161 Z. Qian, X. Shan, L. Chai, J. Ma, J. Chen and H. Feng, ACS 184 I. Y. Goon, C. C. Zhang, M. Lim, J. J. Gooding and R. Amal,
Appl. Mater. Interfaces, 2014, 6, 6797–6805. Langmuir, 2010, 26, 12247–12252.
162 Y. H. Yuan, R. S. Li, Q. Wang, Z. L. Wu, J. Wang, H. Liu and 185 J.-M. Liu, L. Lin, X.-X. Wang, L. Jiao, M.-L. Cui, S.-L. Jiang,
C. Z. Huang, Nanoscale, 2015, 7, 16841–16847. W.-L. Cai, L.-H. Zhang and Z.-Y. Zheng, Analyst, 2013,
163 A. B. Bourlinos, A. Bakandritsos, A. Kouloumpis, 138, 278–283.
D. Gournis, M. Krysmann, E. P. Giannelis, K. Polakova, 186 U. Baruah, N. Gogoi, G. Majumdar and D. Chowdhury,
K. Safarova, K. Hola and R. Zboril, J. Mater. Chem., 2012, Carbohydr. Polym., 2015, 117, 377–383.
22, 23327–23330. 187 J. Hou, J. Dong, H. Zhu, X. Teng, S. Ai and M. Mang, Biosens.
164 N. Gong, H. Wang, S. Li, Y. Deng, X. Chen, L. Ye and W. Gu, Bioelectron., 2015, 68, 20–26.
Langmuir, 2014, 30, 10933–10939. 188 X. Wang, D. Wang, Y. Guo, C. Yang, A. Iqbal, W. Liu,
165 B. B. Chen, Z. X. Liu, H. Y. Zou and C. Z. Huang, Analyst, W. Qin, D. Yan and H. Guo, Dalton Trans., 2015, 44,
2016, 141, 2676–2681. 5547–5554.
166 F. Li, C. Liu, J. Yang, Z. Wang, W. Liu and F. Tian, RSC Adv., 189 Y. Zou, F. Yan, T. Zheng, D. Shi, F. Sun, N. Yang and
2014, 4, 3201–3205. L. Chen, Talanta, 2015, 135, 145–148.
167 Y.-P. Sun, B. Zhou, Y. Lin, W. Wang, K. A. S. Fernando, 190 R. Jalili and M. Amjadi, RSC Adv., 2015, 5, 74084–74090.
P. Pathak, M. J. Meziani, B. A. Harruff, X. Wang, 191 L. Li, C. Wang, J. Luo, Q. Guo, K. Liu, K. Liu, W. Zhao and
H. Wang, P. G. Luo, H. Yang, M. E. Kose, B. Chen, Y. Lin, Talanta, 2015, 144, 1301–1307.
L. M. Veca and S.-Y. Xie, J. Am. Chem. Soc., 2006, 128, 192 Z. Yan, Y. Yu and J. Chen, Anal. Methods, 2015, 7, 1133–
7756–7757. 1139.
168 C. Wang, Z. Xu and C. Zhang, ChemNanoMat, 2015, 1, 122– 193 A. Cayuela, M. L. Soriano and M. Valcárcel, Anal. Chim. Acta,
127. 2015, 872, 70–76.
169 J. Lu, J.-X. Yang, J. Wang, A. Lim, S. Wang and K. P. Loh, 194 A. Cayuela, M. L. Soriano and M. Valcárcel, Analyst, 2016,
ACS Nano, 2009, 3, 2367–2375. 141, 2682–2687.
170 X. Gao, Y. Lu, R. Zhang, S. He, J. Ju, M. Liu, L. Li and 195 A. B. Bourlinos, R. Zboril, J. Petr, A. Bakandritsos,
W. Chen, J. Mater. Chem. C, 2015, 3, 2302–2309. M. Krysmann and E. P. Giannelis, Chem. Mater., 2012, 24,
171 X. Wang, L. Cao, S.-T. Yang, F. Lu, M. J. Meziani, L. Tian, 6–8.
K. W. Sun, M. A. Bloodgood and Y.-P. Sun, Angew. Chem., 196 Y. Wang, S. Kalytchuk, Y. Zhang, H. Shi, S. V. Kershaw and
Int. Ed., 2010, 49, 5310–5314. A. L. Rogach, J. Phys. Chem. Lett., 2014, 5, 1412–1420.
172 P. Anilkumar, X. Wang, L. Cao, S. Sahu, J.-H. Liu, P. Wang, 197 L. Chen, C. Zhang, Z. Du, H. Li, L. Zhang and W. Zou, J.
K. Korch, K. N. Tackett II, A. Parenzan and Y.-P. Sun, Appl. Polym. Sci., 2015, 132, 42667.
Nanoscale, 2011, 3, 2023–2027. 198 L. Cao, X. Wang, M. J. Meziani, F. Lu, H. Wang, P. G. Luo,
173 S. Chandra, S. H. Pathan, S. Mitra, B. H. Modha, Y. Lin, B. a. A. Harruff, L. M. Veca, D. Murray, S.-Y. Xie and
A. Goswamic and P. Pramanik, RSC Adv., 2012, 2, 3602– Y.-P. Sun, J. Am. Chem. Soc., 2007, 129, 11318–11319.
3606. 199 A. Zhu, Q. Qu, X. Shao, B. Kong and Y. Tian, Angew. Chem.,
174 H. Gonçalves, P. A. S. Jorge, J. R. A. Fernandes and 2012, 124, 7297–7301.
J. C. G. Esteves da Silva, Sens. Actuators, B, 2010, 145, 702– 200 B. Kong, A. Zhu, C. Ding, X. Zhao, B. Li and Y. Tian, Adv.
707. Mater., 2012, 24, 5844–5848.
View Article Online
201 A. S. Krishna, C. Radhakumary and K. Sreenivasan, Anal. 215 H. Ding, F. Du, P. Liu, Z. Chen and J. Shen, ACS Appl. Mater.
Methods, 2015, 7, 9482–9488. Interfaces, 2015, 7, 6889–6897.
202 W.-J. Wang, X. Hai, Q.-X. Mao, M.-L. Chen and J.-H. Wang, 216 M. S. Khan, S. Pandey, A. Talib, M. L. Bhaisare and
ACS Appl. Mater. Interfaces, 2015, 7, 16609–16616. H.-F. Wu, Colloids Surf., B, 2015, 134, 140–146.
203 Z. Zhou, Q. Wang, J. Wang and C. C. Zhang, Carbon, 2015, 217 L. Cao, S. Sahu, P. Anilkumar, C. E. Bunker, J. Xu,
93, 671–680. K. A. S. Fernando, P. Wang, E. A. Guliants, K. N. Tackett
204 W. Dong, S. Zhou, Y. Dong, J. Wang, X. Ge and L. Sui, II and Y.-P. Sun, J. Am. Chem. Soc., 2011, 133, 4754–4757.
Luminescence, 2015, 30, 867–871. 218 S. Hu, R. Tian, L. Wu, Q. Zhao, J. Yang, J. Liu and S. Cao,
205 Y. K. Jung, E. Shin and B.-S. Kim, Sci. Rep., 2015, 5, 18807. Chem.–Asian J., 2013, 8, 1035–1041.
206 Q. Liu, S. Xu, C. Niu, M. Li, D. He, Z. Lu, L. Ma, N. Na, 219 S. Hu, Y. Ding, Q. Chang, J. Yang and K. Lin, Appl. Surf. Sci.,
F. Huang, H. Jiang and J. Ouyang, Biosens. Bioelectron., 2015, 355, 774–777.

2015, 64, 119–125. 220 H. Li, S. Guo, C. Li, H. Huang, Y. Liu and Z. Kang, ACS Appl.
207 S. Kiran and R. D. K. Misra, J. Biomed. Mater. Res., Part A, Mater. Interfaces, 2015, 7, 10004–10012.
2015, 103, 2888–2897. 221 J. Xu, S. Sahu, L. Cao, C. E. Bunker, G. Peng, Y. Liu,
208 Y. Ding, J. Ling, H. Wang, J. Zou, K. Wang, X. Xiao and K. A. S. Fernando, P. Wang, E. A. Guliants, M. J. Meziani,
M. Yang, Anal. Methods, 2015, 7, 7792–7798. H. Qian and Y.-P. Sun, Langmuir, 2012, 28, 16141–16147.
209 D. Liu, F. Qu, X. Zhao and J. You, J. Phys. Chem. C, 2015, 119, 222 W. Wei and W. Chen, J. Power Sources, 2012, 204, 85–88.
17979–17987. 223 M. Liu and W. Chen, Nanoscale, 2013, 5, 12558–12564.
210 J. Ju and W. Chen, Anal. Chem., 2015, 87, 1903–1910. 224 H. Choi, S.-J. Ko, Y. Choi, P. Joo, T. Kim, B. R. Lee,
211 Q. Li, T. Y. Ohulchanskyy, R. Liu, K. Koynov, D. Wu, A. Best, J.-W. Jung, H. J. Choi, M. Cha, J.-R. Jeong, I.-W. Hwang,
R. Kumar, A. Bonoiu and P. N. Prasad, J. Phys. Chem. C, M. H. Song, B.-S. Kim and J. Y. Kim, Nat. Photonics, 2013,
2010, 114, 12062–12068. 7, 732–738.
212 S. Karthik, B. Saha, S. K. Ghosh and N. D. P. Singh, Chem. 225 L. Wu, J. Wang, J. Ren, W. Li and X. Qu, Chem. Commun.,
Commun., 2013, 49, 10471–10473. 2013, 49, 5675–5677.
213 M. Zheng, S. Liu, J. Li, D. Qu, H. Zhao, X. Guan, X. Hu, 226 Z.-X. Wang, C.-L. Zheng, Q.-L. Li and S.-N. Ding, Analyst,
Z. Xie, X. Jing and Z. Sun, Adv. Mater., 2014, 26, 3554–3560. 2014, 139, 1751–1755.
214 Y.-F. Wu, H.-C. Wu, C.-H. Kuan, C.-J. Lin, L.-W. Wang,
C.-W. Chang and T.-W. Wang, Sci. Rep., 2016, 6, 21170.

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Journal of

Improving the functionality of carbon nanodots:

Cite this: J. Mater. Chem. A, 2016, 4,

electrochemical oxidation, solvothermal carbonization, tem-

Review Journal of Materials Chemistry A

with a variety of functionalities by conjugation with functional

Journal of Materials Chemistry A Review

Although the surface functional groups of C-dots have been

following classication: diamond-like structure,5 graphite struc-

Review Journal of Materials Chemistry A

pyrolysis.26 The XRD pattern of C-dots displayed a broad

2.1.5. Amorphous carbon structure with graphitic clusters.

Journal of Materials Chemistry A Review

2.2.2. Electronic structures of C-dots. Similar to organic

and thiols. If the functional groups carrying lone pairs are

which agrees well with the visible light emission of C-dots,

Review Journal of Materials Chemistry A

quantum yield of C-dots. For these reasons, numerous research

3.1. Nitrogen doping

in optical properties.36–39 So far, various nitrogen-containing

Journal of Materials Chemistry A Review

Fig. 10 (a) Emission spectrum of a white LED using a CND-10000 ﬁlm

Review Journal of Materials Chemistry A

than that of C-dots (3.4%). It was proposed that the large

Journal of Materials Chemistry A Review

increased, more sulfur was doped into the carbon dots,

several limitations. For instance, one of the major limitations of

Review Journal of Materials Chemistry A

3.5.3. Phosphorus/nitrogen. Han et al. also synthesized

ature (90 C) by Gong et al.158 The as-synthesized P,N-doped Chemistry.

Journal of Materials Chemistry A Review

106, 135 and 139–156

29, 106, 129 and 130

39, 106, 158 and 159

106 and 157

163 and 164

of C-dots. Surface functionalization is a multipurpose method

surface states, including emissive surface states and defect

sites, are closely related to the energy structure of C-dots, which

have been investigated for engineering the energy structures of

sites make C-dots defenseless to external contaminants, which

H2SO4, sodium thiosulfate, etc.

passivation is one of the surface functionalization methods

developed to enhance the optical properties of C-dots. By intro-

Gadopentetic acid, Gd2O3

ducing a thin passivating layer on the C-dot surface, their photo-

of C-dots to improve their quantum eﬃciency was rst

H3PO4 (P), etc.

conducted by the Sun group. In 2006, Sun et al. rst discovered

the benecial eﬀect of C-dot surface passivation. They

synthesized surface-passivated C-dots with diamine-terminated

oligomeric poly(ethylene glycol) H2NCH2(CH2CH2O)nCH2CH2-

Pyrrole, adenosine triphosphate, etc.

Tris, betaine hydrochloride, sucrose

mixture was cooled to room temperature and dispersed in water,

followed by centrifuging for 30 min. The obtained colored but

homogeneous supernatant contained PEG1500N-passivated C-dots

(Fig. 16). The resulting C-dots showed high photostability to

Citric acid, etc.