Nano Energy 27 (2016) 320–329

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Nano Energy
journal homepage: www.elsevier.com/locate/nanoen

Photocatalytic CO2 conversion to methanol by Cu2O/graphene/TNA

heterostructure catalyst in a visible-light-driven dual-chamber reactor
Fei Li a, Li Zhang a,n, Jincheng Tong a, Yingliang Liu a, Shengang Xu a, Yan Cao b,
Shaokui Cao a,n
a
School of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450052, China
b
Institute for Combustion Science and Environmental Technology, Western Kentucky University, Bowling Green, KY 42101, USA

art ic l e i nf o a b s t r a c t

Article history: Efficient photocatalytic CO2 conversion to methanol under visible light irradiation (λ 4400 nm) was
Received 28 October 2015 achieved in a light-driven dual-chamber reactor using the monolithic two-side Cu2O/graphene/TiO2
Received in revised form nanotube array (TNA) heterostructure as separated oxidation and reduction catalyst, that was prepared
29 June 2016
with anodic TNA as the substrate following by sequential electrochemical deposition of graphene and
Accepted 29 June 2016
Available online 30 June 2016
Cu2O. The combined heterojunction in the ternary composite helps to improve the photocatalytic per-
formance by increasing light absorption, preventing electron–hole recombination and facilitating elec-
Keywords: tron transfer across the heterojunction interfaces, as revealed by photoelectrochemical measurements.
Cu2O Methanol generation rate of 45 μmol cm
2 h
1 was achieved, which is much higher than those obtained
Graphene
for existing TNA-based photocatalysts reported. Moreover, the quantum efficiency of 5.71% at 420 nm has
Heterostructure
been attained. The improved photocatalytic activity together with the proposed reaction mechanism
Dual-chamber reactor
CO2 photoreduction demonstrated the advantage of Cu2O/graphene/TNA heterostructure and effectiveness of the reaction
system, which can efficiently suppress charge recombination, improve interfacial charge transfer and
inhibit the backward reaction by separating the photocatalytic reaction sites.
& 2016 Elsevier Ltd. All rights reserved.

1. Introduction attracted much attention owing to its large surface area, superior
electron transport property and appropriate band-edge position
The increasing emission of CO2 associated with a massive [5,6]. But its wide band gap ( 3.2 eV) limits the optical response
consumption of fossil fuel has brought about environmental and only to UV light (about 5% of total sunlight). Many efforts have
energy threat [1,2]. Photocatalytic reduction of CO2 by artificial been made to improve the photocatalytic activity of TNA in visible
photosynthesis is a promising technical solution since it uses light region, such as doping with metal [7,8], non-metal [9,10] and
readily available sunlight to convert CO2 into hydrocarbon fuels in coupling with the second semiconductor [11–15]. Particularly,
a carbon friendly manner, and these renewable solar fuels promise coupling n-type TNA with a p-type narrow band gap semi-
an attractive remedy to the energy shortage issues [3]. To date, conductor such as Cu2O to form the heterojunction structure has
many semiconductor photocatalysts have been reported for CO2 shown promising potential for photocatalytic CO2 conversion [1].
reduction, however the obtained CO2 conversion efficiency is still Cu2O is an attractive p-type semiconductor with a band gap
very moderate. Generally, the fast recombination of charge car- ( 2.0 eV) that matches well with the relevant sunlight spectrum
riers, the mismatch between the band gap of photocatalyst and and a conduction band that is more negative than that of TiO2
solar radiation spectrum, and unsuitable band-edge position are [2,16]. Thus, when TNA is conjugated with Cu2O, the photoexcited
the key factors that limit the efficiency of artificial photosynthesis electrons would transfer from the conduction band of Cu2O to that
[1,3,4]. Therefore, the development of more effective photo- of TiO2 and subsequently initiate a photoreduction reaction. More
catalysts and reaction systems for CO2 photoreduction is a topic of recently, a Cu2O/TNA heterostructure has been reported for CO2
great interest with practical importance. photoreduction showing enhanced photocatalytic activity com-
Among various photocatalysts, TiO2 nanotube array (TNA) has pared to the pure TNA under the UV illumination [17]. Never-
theless, the photostability of this heterostructural catalyst and CO2
n conversion efficiency still need to be further improved.
Corresponding authors.
E-mail addresses: [email protected] (L. Zhang), Since photogenerated electrons play a key role in the photo-
[email protected] (S. Cao). reduction reaction, any improvement in electron transfer across

http://dx.doi.org/10.1016/j.nanoen.2016.06.056
2211-2855/& 2016 Elsevier Ltd. All rights reserved.

Please cite this article as: F. Li, et al., Photocatalytic CO2 conversion to methanol by Cu2O/graphene/TNA heterostructure catalyst in a
visible-light-driven dual-chamber reactor, Nano Energy (2016), http://dx.doi.org/10.1016/j.nanoen.2016.06.056i
 F. Li et al. / Nano Energy 27 (2016) 320–329 321

the heterojunction interface and the efficient utilization of sepa- at 60 V for 2 h and then the as-grown TiO2 nanotube layer was
rated photogenerated electrons is desirable for enhancing the ultrasonically removed in DW. The same Ti foil was then anodized
photocatalytic reduction of CO2 [7,18]. In this regard, graphene is secondly at 60 V for 20 min. After the two-step anodization, the
evaluated as the most efficient cocatalyst considering its excellent prepared TNA sample was cleaned with DW and dried in air, and
electron capture and transport properties that can enhance pho- then annealed in air at 500 °C for 2 h with a heating rate of
toinduced charge transfer and prolong the lifetime of photo- 5 °C min
1.
generated charge carriers [19,20]. The improved catalytic capacity
of graphene is also associated with its large specific surface area, 2.2. Fabrication of graphene/TNA
tunable band gap and excellent electron mobility [21–25]. There
has been a growing interest in the rational design of graphene- To prepare graphene/TNA, the synthesized TNA sample was
based semiconductor photocatalysts for solar fuel production in immersed in the 1.0 mg mL
1 aqueous dispersion of graphene
recent years. For example, Cu2O/reduced graphene oxide (rGO) oxide (GO) that was prepared from natural graphite powder by a
composites [26,27] were fabricated and applied for CO2 photo- modified Hummers' method [34]. The cyclic voltammetric reduc-
catalytic conversion, and the results showed that the presence of tion was performed in the GO dispersion with a three-electrode
rGO significantly promoted the photocatalytic activity and stability system (the annealed TNA/Ti as working electrode, Pt sheet as
of Cu2O, which was believed due to efficient charge separation and counter electrode and saturated calomel electrode (SCE) as re-
transfer from Cu2O to rGO. Incorporation of graphene with TNA to ference electrode) on a CHI 660D electrochemical workstation. The
obtain graphene/TNA hybrid photocatalyst was also reported by scan was from
1.5 to 1 V at a rate of 50 mV/s and operated with
Luo et al. [28], which led to the enhanced photodegradation of 20 cycles. After deposition, the obtained graphene/TNA sample
organic pollutants due to increased pollutant adsorption and was washed with DW and dried in air.
boosted charge transport and separation. However, there is little
reported about utilizing the ternary Cu2O/graphene/TNA compo-
2.3. Fabrication of Cu2O/graphene/TNA
site for photocatalytic CO2 conversion [29]. With a combination of
the potential advantages of each components, Cu2O/graphene/TNA
The ternary Cu2O/graphene/TNA heterostructure was fabri-
composite could be attractive as a visible-light-driven CO2 reduc-
cated by electrochemical deposition of Cu2O in a three-electrode
tion catalyst in which graphene may act as an electron conductor
system with graphene/TNA, SCE and Pt sheet as the working, re-
to accelerate the electron transfer from excited Cu2O to TNA, an
ference and counter electrodes, respectively. The electrolyte was
electron trapper to benefit charge separation, as well as a stabilizer
CuSO4 (0.4 M) in a 3 M lactic acid solution with pH adjusted to 10
to improve the stability of photocatalyst [26,30].
using 5 M NaOH solution. The electrodeposition was performed at
Herein, we report for the first time the construction of a ternary

0.4 V for 600 s and then washed with DW and dried in air. For
Cu2O/graphene/TNA heterostructure for photocatalytic reduction
comparison, Cu2O nanoparticles were directly deposited on the
of CO2 with water as a reductant. By using anodic TNA on a Ti foil
top of TNA under an identical deposition condition, and the ob-
(TNA/Ti) as the substrate, graphene film was electrodeposited on
tained sample is denoted as Cu2O/TNA.
the TNA/Ti and then Cu2O nanoparticles were decorated on the
graphene sheets by electrochemical method. Through these two
steps, a monolithic two-side Cu2O/graphene/TNA photocatalyst 2.4. Characterization
was obtained, and its photoelectrochemical properties were in-
vestigated under visible light irradiation. Furthermore, a novel Scanning electron micrographs (SEM) were taken on a JEOL
light-driven dual-chamber reactor, which was separated by the 6700 F field emission electron microscope operated at 20 kV. X-ray
two-side Cu2O/graphene/TNA photocatalyst and proton exchange diffraction (XRD) patterns were obtained by using D8 Advance
membrane, was developed to divide the photoinduced process (Bruker) X-ray diffractometer with Cu Kα radiation (λ ¼1.5418 Å).
into two physically distinct areas related to water oxidation (oc- Raman spectra were recorded on a RM 2000 Microscopic confocal
curs on the light irradiation side of photocatalyst) and CO2 re- Raman spectrometer (Renishaw PLC, England) using a 633 nm la-
duction (occurs on the unexposed side of photocatalyst). This ser beam. X-ray photoelectron microscopy (XPS) was performed
reaction system was able to limit the charge recombination, pre- on an ESCALAB 250 photoelectron spectrometer (ThermoFisher
vent the backward reactions, and consequently increase the effi- Scientific) with Al Kα (1486.6 eV) as the X-ray source set at 150 W
ciency of CO2 reduction reaction [31,32]. As expected, such a and a pass energy of 30 eV for high-resolution scan. UV/Vis diffuse
ternary Cu2O/graphene/TNA heterostructure exhibited excellent reflectance spectra were recorded on a U-3010 UV–visible spec-
photocatalytic activity, photostability, and selectivity toward CO2 trometer (Hitachi, Japan).
reduction to methanol under visible light irradiation owing to the
synergetic effect of all the components and heterojunctions in 2.5. Photoelectrochemical measurements
between.
All photoelectrochemical performance were measured using a
CHI 660D electrochemical workstation in a standard three-elec-
2. Experimental section trode system with the as-prepared samples, Pt sheet and SCE as
working, counter and reference electrodes, respectively. A 0.05 M
2.1. Fabrication of TiO2 nanotube array (TNA) Na2SO4 aqueous solution was used as the electrolyte. A 300 W Xe
arc lamp with a UV-cutoff filter (λ 4400 nm) was utilized as the
Highly ordered TNA was fabricated on 2 cm  1 cm Ti foils by a visible light source and the focused intensity was 100 mW cm
2.
two-step anodization approach [33]. Prior to anodization, Ti foil The transient photocurrent response was measured under a
(99.96% purity, 0.1 mm thickness) was ultrasonically cleaned in chopped light irritation (light on-off cycles: 50 s) at a bias poten-
acetone, alcohol and distilled water (DW) sequentially. Anodic tial of 0 V vs. SCE. The scan rate for the potentiodynamic scan was
oxidization was carried out using a two-electrode system with the 5 mV/s. The electrochemical impedance spectra (EIS) were re-
Ti foil as an anode and a Pt sheet as a cathode at room tempera- corded under an alternating current perturbation signal of 10 mV
ture. The electrolyte was ethylene glycol solution containing over the frequency range of 1 MHz to 10 mHz under illumination
0.5 wt% NH4F and 2 vol% DW. The first anodization was performed condition.

Please cite this article as: F. Li, et al., Photocatalytic CO2 conversion to methanol by Cu2O/graphene/TNA heterostructure catalyst in a
visible-light-driven dual-chamber reactor, Nano Energy (2016), http://dx.doi.org/10.1016/j.nanoen.2016.06.056i
322 F. Li et al. / Nano Energy 27 (2016) 320–329

2.6. Photocatalytic CO2 reduction chamber. For the isotope-tracer experiment, the same photo-
ctalytic procedure was performed using 13CO2 (99.0%, Sigma-Al-
The photocatalytic reduction of CO2 was performed in a 250 mL drich) as the feedstock and Cu2O/graphene/TNA as photocatalyst.
home-made Pyrex reactor at ambient temperature and atmo- After 2 h of visible-light irradiation, 10 μL liquid product taken
spheric pressure. The reactor had a two-chamber configuration from the reduction side solution was analyzed by GC-MS (HP6890/
separated by as-prepared two-side photocatalyst (with projected HP5973 system) with a Agilent DB-624 column. For evaluating the
area of 1 cm2) and proton exchange membrane. One chamber was quantum efficiency (QE) of methanol production, a 300 W Xe arc
for water oxidation at the light irradiation side of catalyst, and lamp with a band-pass filter (λ ¼420 nm) was used as the light
the other chamber for CO2 reduction at the unexposed side of source to trigger the photocatalytic reaction under similar condi-
catalyst. The latter chamber was covered with a black box to avoid tions. The light intensity and focused areas in the reactor were
light exposure. A 300 W Xe arc lamp with a UV-cutoff filter 60 mW cm
2 and 1 cm2, respectively. The QE values were calcu-
(λ 4400 nm) was used as the light source and the focused light lated according to the following Eq. (1):
intensity at the surface of the photocatalyst was 100 mW cm
2.
number of reacted electrons
Fig. 1 shows the schematic diagram of the reactor system. For a QE⎡⎣ %⎤⎦ = × 100
number of incident photons
typical photocatalytic experiment, the photocatalyst and proton
number of CH3OH molecules × 6
exchange membrane were fixed at the connection of two cham- = × 100
bers, and 100 mL of 1 M Na2SO4 and 1 M NaHCO3 aqueous solu- number of incident photons (1)
tions were respectively injected into the oxidation and reduction
chambers. Before irradiation, ultrapure N2 and CO2 were sepa-
rately bubbled through the solution in the oxidation and reduction 3. Results and discussion
chambers for at least 30 min to purge the air and saturate the
solution. During irradiation, ultrapure gases were continuously 3.1. Morphological and structural characterization
bubbled through the above solutions in the reactor, and 10 μL of
liquid sample was withdrawn from the reduction side solution at The overall fabrication procedure for the monolithic Cu2O/
regular intervals (1 h) for subsequent product analysis using a GC- graphene/TNA heterostructure is shown in Scheme 1. Firstly, the
FID of SRI-310 C equipped with a Porapak-Q column. Reaction framework of TiO2 nanotube array was fabricated via two-step
products were calibrated with a standard mixture and their anodization, by which disordered surface layer inherited from
identity was determined using the retention time (detailed ana- conventional one-step anodization technique were completely
lysis data are shown in Fig. S1). It is noted that only liquid product removed, thereby leading to highly ordered nanotube array [35].
will be detected with our setup and the gas-phase product will Subsequently, by using TNA/Ti as the electrode, the graphene film
remain undetected. Control experiments were conducted to en- was electrodeposited on the TNA via cyclic voltammetry and then
sure that the hydrocarbon production was due to the photo- Cu2O nanoparticles were decorated on the graphene sheets by
reduction of CO2, consisting of a light-illuminated reaction without cathodic current deposition. The morphology of as-prepared TNA,
introducing CO2 and a reaction in the dark. In the former control graphene/TNA, Cu2O/TNA and Cu2O/graphene/TNA samples was
experiment, N2 was used as the purging gas for the reduction examined by SEM. As shown in Fig. 2a, the anodic TNA framework
consists of a compact array of vertically aligned nanotubes with a
mesh-shaped surface layer [36] and the nanotubes are highly or-
dered and uniform manifesting an average tube diameter of 30 nm
and a tube length of ca. 500 nm. After 20 cycles of graphene
electrodeposition, the TNA surface was totally covered with a thin
and merged graphene film (Fig. 2b). From Fig. 2c, larger Cu2O
nanoparticles with a size of 400 nm were scattered on the top of
TNA by direct deposition on TNA. In contrast, smaller and uniform
Cu2O nanoparticles (  100 nm) were successfully deposited on the
surface of graphene/TNA (Fig. 2d and e) under an identical de-
position condition, suggesting that the presence of graphene can
significantly affect the deposition and formation process of Cu2O
nanoparticles. Moreover, the EDX spectrum (Fig. 2f) reveals that
as-prepared Cu2O/graphene/TNA composite is composed of Ti, C,
O, and Cu elements, also illustrating the combination of three
Fig. 1. Schematic diagram of the CO2 photoreduction reaction system. components.

Scheme 1. Fabrication steps for Cu2O/graphene/TNA heterostructure by sequential electrochemical method.

Please cite this article as: F. Li, et al., Photocatalytic CO2 conversion to methanol by Cu2O/graphene/TNA heterostructure catalyst in a
visible-light-driven dual-chamber reactor, Nano Energy (2016), http://dx.doi.org/10.1016/j.nanoen.2016.06.056i
 F. Li et al. / Nano Energy 27 (2016) 320–329 323

Fig. 2. SEM images of (a) TNA, (b) graphene/TNA, (c) Cu2O/TNA, and Cu2O/graphene/TNA at (d) low magnification and (e) high magnification; (f) EDX spectrum of Cu2O/
graphene/TNA in (e).

The phase structures of TNA and the composite samples were Fig. 4b displays the fitted Cu 2p core level spectrum, which assists
characterized by XRD and Raman spectroscopy. From the XRD pat- the determination of the oxidation states of Cu elements. The
terns in Fig. 3a, all the samples confirm the crystallization of TNA in peaks at binding energies of 932.5 and 952.3 eV correspond to Cu
the regular anatase phase (JCPDS file No. 21–1272) and metal Ti 2p3/2 and Cu 2p1/3 of Cu2O, and those at 934.0 and 954.2 eV are
phase (JCPDS file no. 44-1294) from Ti foil. For Cu2O/TNA and Cu2O/ ascribed to CuO [13,44]. The appearance of weak and broad sa-
graphene/TNA, the additional diffraction peaks at 36.5° and 40.3° tellite peaks around 943.0 eV also confirms the coexistence of a
were observed, which can be ascribed to the (111) and (200) crystal trace amount of CuO, although it was not detected in the XRD
planes of Cu2O (JCPDS file no. 34-1354). Note that the diffraction peak measurements [45]. This can be attributed to the relatively small
of (200) plane in Cu2O/graphene/TNA is much stronger than that of amount and the amorphous nature of CuO that might be formed
(111) plane, reflecting Cu2O grains electrodeposited on graphene by surface oxidation of Cu2O during the sample drying and
surface have a relatively high percentage of (200) facets [37]. No handling under normal ambient condition [46]. To confirm the
characteristic peaks of Cu and CuO phases were detected from these reduction of GO during the electrodeposition process, high re-
two samples. Meanwhile, the absence of diffraction peaks of carbon solution C 1 s XPS spectrum were collected from Cu2O/graphene/
species from the XRD patterns of graphene/TNA and Cu2O/graphene/ TNA sample (Fig. 4c), which can be deconvoluted into three peaks
TNA is due to the low amount and the relatively low diffraction in- at 284.2, 285.9 and 287.8 eV, corresponding to graphitic sp2 carbon
tensity of electrochemically reduced GO [38]. The existence of gra- (C ¼C/C–C), epoxy/hydroxyl (C–O) and carbonyl (C ¼ O) functional
phene can be determined by Raman spectra, as shown in Fig. 3b. The groups, respectively [38]. The much stronger peaks related to
Raman spectra of graphene/TNA and Cu2O/graphene/TNA contain graphitic sp2 carbon suggests considerable deoxygenation in the
two typical peaks at 1345 and 1580 cm
1, which are commonly at- electrochemical reduction, which leads to the formation of re-
tributed to the D (breathing mode of A1g) and G band (in-plane vi- duced GO in the composite, in accord with the Raman results.
bration of sp2 carbon atoms, E2g mode) of reduced GO [39,40]. For all
the samples, there are four apparent peaks at 141, 394, 511, 638 cm
1 3.2. Optical and photoelectrochemical performance
respectively corresponding to the Eg(1), B1g(1), A1g þ B1g(2) and Eg(2)
modes of anatase TiO2 [41,42], indicating that the electrodeposition The UV–vis diffuse reflectance spectra (DRS) of TNA and the
of graphene and Cu2O did not change the crystal structure of TNA. composite samples are displayed in Fig. 5a. Bare TNA exhibits the
From the inset of Fig. 3b, a weak peak at 218 cm
1 can be detected intrinsic band gap photo-response in the UV region with a wavelength
from Cu2O/TNA and Cu2O/graphene/TNA samples, which is indicative below 400 nm. The weak absorption of TNA in the visible region can
of the presence of Cu2O, and the other peaks associated with Cu2O be ascribed to the presence of structural defects in the nanotube array
are overlapped with the strong peaks of TiO2 [43]. [12,47]. In comparison with TNA, all the composite samples show the
To further determine the chemical composition of ternary red-shifted absorption band edges and the enhanced absorption in-
Cu2O/graphene/TNA composite, XPS analysis was performed, from tensities in the visible-light region from 400 to 800 nm, among which
which only Ti, O, C and Cu elements were observed (Fig. 4a). Cu2O/graphene/TNA exhibits the strongest absorption resulting from

Please cite this article as: F. Li, et al., Photocatalytic CO2 conversion to methanol by Cu2O/graphene/TNA heterostructure catalyst in a
visible-light-driven dual-chamber reactor, Nano Energy (2016), http://dx.doi.org/10.1016/j.nanoen.2016.06.056i
324 F. Li et al. / Nano Energy 27 (2016) 320–329

Fig. 3. (a) XRD patterns and (b) Raman spectra of TNA (I), graphene/TNA (II), Cu2O/
TNA (III) and Cu2O/graphene/TNA (IV) samples. The inset in (b) shows the magni-
fied Raman spectra curves ranged from 100 to 325 cm
1, and the character D and G
denote the D band and G band resulted from the reduced GO respectively.

the combination of broad background absorption from graphene and

characteristic absorption of Cu2O centered around 410 nm [24,26].
The enhanced visible light absorption is favorable to use sunlight ef-
fectively and therefore the improved photon conversion efficiency of
Cu2O/graphene/TNA under visible light irradiation can be expected.
In order to determine the band gaps of samples, the DRS measure-
ment were transformed using the Kubelka-Munk function and plotted
against the energy of light (Fig. 5b), from which the band gaps are
estimated to be 3.25 eV for TNA, 2.90 eV for graphene/TNA, 2.19 eV for
Cu2O/TNA, and 2.14 eV for Cu2O/graphene/TNA, indicating that the
introduction of graphene and/or Cu2O can extend the photo-response
of composites into the visible-light region, which is a prerequisite for
the utilization of visible light for photocatalysis.
In order to provide evidence for the variations of photoelectric
response of these composites, the photoelectrochemical measure- Fig. 4. (a) XPS survey spectrum of Cu2O/graphene/TNA; the corresponding high
ments were performed under visible light irradiation. Fig. 6a displays resolution XPS spectra of (b) Cu 2p and (c) C 1 s.
the photocurrent density-time curves of TNA and the composite
samples over several on-off irradiation cycles at 0 V bias vs. SCE. No
significant photocurrent was observed in the dark for all samples. indicative of n-type photoelectrode properties [48]. For bare TNA
Upon being irradiated with visible light (λ 4400 nm), all electrodes electrode, the detectable photocurrent response is likely due to the
exhibited promptly increased anodic photocurrents, which is fact that the stopband limit (λs ¼ 340 nm) of the 400 nm filter still

Please cite this article as: F. Li, et al., Photocatalytic CO2 conversion to methanol by Cu2O/graphene/TNA heterostructure catalyst in a
visible-light-driven dual-chamber reactor, Nano Energy (2016), http://dx.doi.org/10.1016/j.nanoen.2016.06.056i
 F. Li et al. / Nano Energy 27 (2016) 320–329 325

Fig. 6. (a) Transient photocurrent responses of TNA, graphene/TNA, Cu2O/TNA and

Cu2O/graphene/TNA at a bias potential of 0 V vs. SCE with 50 s visible light on-off
Fig. 5. (a) UV–Vis DRS of TNA, graphene/TNA, Cu2O/TNA and Cu2O/graphene/TNA cycles (λ4 400 nm); (b) EIS Nyquist plots of TNA, graphene/TNA, Cu2O/TNA and
samples; (b) the plots of transformed Kubelka-Munk function of these four samples Cu2O/graphene/TNA under visible light illumination (λ 4400 nm).
versus the energy of light.

separate and transfer photogenerated electron–hole pairs more effi-

allows small amount of stray UV light to directly excite the band gap of ciently through its ternary heterostructure [51]. Fig. 6b presents EIS
TNA ( 380 nm). Among all the electrodes, the ternary Cu2O/gra- Nyquist plots of TNA and the composite samples under visible light
phene/TNA electrode shows the best photocurrent response, sug- illumination. It is known that the semicircle in a Nyquist plot at high
gesting an enhanced generation and separation of photoinduced frequencies conveys information of the charge transfer process and the
electron–hole pairs at Cu2O/graphene/TNA heterojunction interfaces: diameter of the semicircle is equal to charge transfer resistance [52].
photogenerated electrons from Cu2O are effectively transported to TNA Apparently, the Nyquist plot of Cu2O/graphene/TNA electrode exhibits
and Ti substrate via the graphene interlayer, while holes in Cu2O are the smallest semicircle among all the measured electrodes, which is an
taken by the hole acceptor in the electrolyte [49,50]. It is also noted indication of the fastest interfacial charge transfer. This is presumably
that Cu2O/TNA electrode suffers a gradually decrease of photocurrent due to the excellent conductivity of graphene which facilitates electron
density within six light cycles due to its poor photostability, while transfer through Cu2O/graphene/TNA ternary system and thus lower
Cu2O/graphene/TNA ternary electrode shows the stable and re- the resistance and charge recombination. Additionally, the semicircle
producible photocurrent response, signifying that the presence of of Cu2O/TNA electrode is much smaller than that of graphene/TNA
graphene interlayer can alleviate the occurrence of photocorrosion. electrode, which could be due to an enhanced visible light absorption
The effect of bias potential on the photocurrent response was also and photoinduced charge generation occurred on Cu2O/TNA hete-
investigated by potentiodynamic scans on these electrodes (Fig. S3). rojunction.
The photocurrent increase with the applied bias potential was ob-
served before the photocurrent finally levelled-off, and the photo- 3.3. Photocatalytic activity and mechanism
current increase for Cu2O/graphene/TNA was much more pronounced
than that for other electrodes, reaching a saturated photocurrent The photocatalytic activity for CO2 reduction using various
density of 9.6 mA/cm2 at 0.8 V vs. SCE. Besides, the Cu2O/graphene/ samples as photocatalysts was evaluated in a dual-chamber re-
TNA electrode showed the most negative zero-current potential actor under visible light irradiation (as illustrated in Fig. 1). For all
(
0.36 V) as compared to other electrodes (
0.25,
0.17, and catalysts, methanol was observed as an exclusive liquid photo-

0.07 V for Cu2O/TNA, graphene/TNA and TNA, respectively). These reduction product by GC analysis. Control experiments with
results again imply that the Cu2O/graphene/TNA electrode can identical condition but in the absence of either CO2 or.

Please cite this article as: F. Li, et al., Photocatalytic CO2 conversion to methanol by Cu2O/graphene/TNA heterostructure catalyst in a
visible-light-driven dual-chamber reactor, Nano Energy (2016), http://dx.doi.org/10.1016/j.nanoen.2016.06.056i
326 F. Li et al. / Nano Energy 27 (2016) 320–329

Fig. 8. Photocatalytic methanol evolution over 6 h time course for TNA, graphene-
TNA, Cu2O/TNA and Cu2O/graphene/TNA catalysts under visible light irradiation
(λ 4400 nm) (b) the recyclability of Cu2O/graphene/TNA catalysts in this reaction
Fig. 7. GC-MS results of methanol produced by photocatalytic reduction of 12CO2 system.
(a) and 13CO2 (b) with Cu2O/graphene/TNA photocatalyst under irradiation of
visible light (λ4 400 nm). Of which the corresponding results of MS are shown in
the inset of (a) and (b).
suggesting that the efficient photoinduced charge generation
and separation are the main factors responsible for improved
irradiation shows no appearance of hydrocarbon compound photocatalytic activity. The highest methanol generation rate of
(Fig. S2), suggesting that the methanol production is due to the 45 μmol cm
2 h
1 was obtained with the ternary Cu2O/graphene/
photocatalytic reduction of CO2. To further clarify the origin of TNA catalyst. This rate exceeds those obtained on binary graphene/
the methanol generated during the reaction, the photoreduction of TNA and Cu2O/TNA catalysts by more than 5 and 2 times respec-
13
C-labeled CO2 was conducted by using the Cu2O/graphene/TNA tively, and is even much higher than the production rate values
photocatalyst, and the resulting liquid product was analyzed by of previously reported TNA-based composite photocatalysts under
GC-MS. As displayed in Fig. 7, when 12CO2 was replaced by 13CO2, full spectrum or UV illumination (less than 10 μmol cm
2 h
1)
the dominant 13CH3OH (m/z ¼ 33) along with negligible 12CH3OH [7,17,31,53]. Moreover, the apparent quantum efficiency (QE)
(m/z ¼ 32) was detected, and the 13CH3OH accounted for around of Cu2O/graphene/TNA under visible-light irradiation was de-
99% of the total amount of methanol product according to the MS termined to be 5.7%, which is significantly higher than the
analysis, which is consistent with the content of 13CO2 in the methanol QE (about 1.73%) using Cu2O/TNA catalyst under UV ir-
feedstock gas. This result clearly indicates that the produced me- radiation reported by Wang et al. [17]. These results demonstrate
thanol originates entirely from the photoreduction of CO2 rather the advantage of the ternary heterostructure and effectiveness of
than the photoconversion of the carbon-containing catalyst or any the reaction system in our case.
other carbon source in the reaction system. Fig. 8a shows the It has been well-established that Cu2O generally suffers from
evolution of methanol over 6 h irradiation time in the presence of photocorrosion since its reduction and oxidation potentials lie
bare TNA, graphene/TNA, Cu2O/TNA and Cu2O/graphene/TNA. The within the band gap [16,52], hence it is of prime importance to
photocatalytic activity of catalysts can be denoted by the average probe the photostability and reusability of the ternary hetero-
production rate of methanol that is defined as the total amount of structure in this reaction system. To this end, cyclic CO2 pho-
evolved methanol divided by the reaction time. It can be seen that toreduction, XRD and XPS were combined to access the eva-
the average production rate of methanol follows the order: Cu2O/ luation. Fig. 8b displays ten cycling experiments of Cu2O/gra-
graphene/TNA 4 Cu2O/TNA 4graphene/TNA 4 TNA, which is in phene/TNA catalyst for CO2 photoreduction under visible-light
line with the order of photocurrent density (as shown in Fig. 6a), irradiation. The rate of methanol production in each run

Please cite this article as: F. Li, et al., Photocatalytic CO2 conversion to methanol by Cu2O/graphene/TNA heterostructure catalyst in a
visible-light-driven dual-chamber reactor, Nano Energy (2016), http://dx.doi.org/10.1016/j.nanoen.2016.06.056i
 F. Li et al. / Nano Energy 27 (2016) 320–329 327

gradually decreased and became stable after eight cycles, with a leading to the spatial separation of the photoinduced holes and
totally decrease by 18%, indicating a relatively stable photo- electrons. According to the values of energy band, this electron
catalytic activity. In the XRD patterns of the ternary catalyst transfer process is thermodynamically permissible. With elec-
after ten photocatalytic cycles (Fig. S4a), a new Cu peak at trons accumulating on graphene, the Fermi level of graphene
around 43.5° is observed in the unexposed side of catalyst, but (
0.08 V vs. NHE) would shift upward and close to the CB of TNA
no peak corresponding to Cu is detected for the irradiation side (
0.5 V vs. NHE) due to the metallic behavior of graphene, such
of the catalyst. This difference suggest that the photogenerated that it would be energetically favorable for the reduction of CO2
electrons from the irradiation side of the catalyst can sponta- to methanol on the surface of graphene [58,59]. Moreover, the
neously transfer to the unexposed side to reduce both CO2 and enriched electron density on graphene facilitates the multi-
concomitant Cu2O (unexposed side), and consequently self- electron interaction for methanol production selectively. In ad-
photoreduction of Cu2O (irradiation side) was inhibited. Gen- dition, CO2, the primary reactant in this reaction system, can be
erally, Cu2O (unexposed side) reduction is highly competitive adsorbed and activated on the surface of graphene and the loa-
with CO2 reduction because the reduction potential for Cu/Cu2O ded Cu2O nanoparticles, respectively, which is beneficial for en-
(0.05 V vs. NHE) is less negative than that for CH3OH/CO2 hancing the photocatalytic reduction efficiency of CO2 [49,60].
(
0.38 V vs. NHE) [3,46]. However, from XRD patterns (Fig. S4b) Simultaneously, the hole perching in the VB of Cu2O in irradia-
of the unexposed side at different reaction time, it is found that tion side can be quenched by the oxidation of H2O since the Cu2O
partial reduction of Cu2O only occurred in the early photo- VB level (which is estimated to be 1.04 V vs. NHE with its con-
catalytic reaction period, and after 6 h photocatalytic reaction, duction band potential and optical band gap [16,44]) is slightly
no significant XRD pattern change was observed, indicating no higher than the potential of H2O/O2 (0.82 V vs. NHE) (Fig. S7). The
more Cu2O was reduced into Cu afterwards. These observations following equations summarize the major reaction steps in this
imply that the CO2 photoreduction mainly occurs on the gra- mechanism under visible light irradiation:
phene surface rather than outmost Cu2O particles and Cu2O
hυ
(unexposed side) reduction only affects initial methanol for- Cu2O/graphene/TNA/graphene → (h+)
mation. On the other hand, the XPS spectra (Fig. S5b) of the ir-
Cu2O/graphene/TNA/graphene(e−) (2)
radiation side of ternary catalyst after ten photocatalytic cycles
show the increased peak intensities that corresponds to CuO in
comparison with the pristine sample before photocatalytic re-
Cu2O(2h+) + H2 O → Cu2O + 2H+ + 1/2O2 (3)
action (Fig. S5 a), revealing that partial oxidation of Cu2O into
CuO occurs during light irradiation, although which cannot be
identified easily by XRD. As a narrow-band-gap semiconductor,
CuO always shows poor photocatalytic efficiency due to the graphene(6e−) + CO2 + 6H+ → graphene + CH3OH + H2 O (4)
serious recombination and the weak redox ability [46]. There-
In consistence with the photocatalytic performance data, our
fore, the slight degradation in photocatalytic activity of ternary
hypothetical mechanism for CO2 reduction further declare the
catalyst is most likely due to the photo-oxidation of Cu2O on the
advantage of the ternary Cu2O/graphene/TiO2 heterostructure
irradiation side. Thus, a variety of hole scavengers which have a
and
suitable oxidation potential are currently being examined in the
effectiveness of the reaction system, which can efficiently sup-
oxidation chamber to improve the stability and reusability of
press charge recombination, improve interfacial charge transfer,
this ternary catalyst.
inhibit the backward reaction by separating the photocatalytic
In order to further prove the impact of graphene on the sta-
reaction sites, and consequently enhance the photocatalytic ac-
bility and activity of photocatalyst, both the pristine and ten-cycle
tivity for methanol generation (Fig. 9).
reused Cu2O/TNA catalyst (irradiation side) were applied to XPS
measurements, as shown in Fig. S5c and Fig. S5d respectively. Also,
the overall XPS peak intensity ratio of S(Cu þ )/S(Cu2 þ ) was calcu-
4. Conclusions
lated to denote the relative amount of Cu þ and Cu2 þ species. By
comparing S(Cu þ )/S(Cu2 þ ) of pristine samples with used samples,
In summary, efficient photocatalytic conversion CO2 to me-
it is clear that more Cu2O has been oxidized to CuO in Cu2O/TNA
thanol under visible light irradiation is achieved using the
than in Cu2O/graphene/TNA. The enhanced photostability of Cu2O/
monolithic Cu2O/graphene/TNA composite, which was prepared
graphene/TNA may be attributed to the presence of graphene
layer, which can provide an effective protection against Cu2O
photocorrosion as reported previously [26,54]. Meanwhile, as an
excellent electron collector and transporter, the graphene inter-
layer can promote the charge separation and electron transfer
from Cu2O (irradiation side) to the unexposed side of catalyst,
thereby, improving the photocatalytic activity of Cu2O/graphene/
TNA as compared to Cu2O/TNA (Fig. S6).
On the basis of the above results and discussion, a tentative
CO2 photoreduction mechanism of Cu2O/graphene/TNA was
proposed according to energy band alignment and schematically
displayed in Fig. 8. Under visible light irradiation, the Cu2O na-
noparticles in irradiation side are excited to generate electrons
and holes in its conduction band (CB) and valence band (VB),
respectively. Owing to the ability of graphene to store and shuttle
electrons [30,55,56], the photogenerated electrons from Cu2O
can be quickly and efficiently transferred to the CB of TNA
through the graphene interlayer, and migrated along TNA [6,57] Fig. 9. Illustration of proposed photocatalytic CO2 reduction mechanism on the
and then trapped by the graphene layer in unexposed side, ternary Cu2O/graphene/TNA catalyst under visible light irradiation.

Please cite this article as: F. Li, et al., Photocatalytic CO2 conversion to methanol by Cu2O/graphene/TNA heterostructure catalyst in a
visible-light-driven dual-chamber reactor, Nano Energy (2016), http://dx.doi.org/10.1016/j.nanoen.2016.06.056i
328 F. Li et al. / Nano Energy 27 (2016) 320–329

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Please cite this article as: F. Li, et al., Photocatalytic CO2 conversion to methanol by Cu2O/graphene/TNA heterostructure catalyst in a
visible-light-driven dual-chamber reactor, Nano Energy (2016), http://dx.doi.org/10.1016/j.nanoen.2016.06.056i
 F. Li et al. / Nano Energy 27 (2016) 320–329 329

Li Zhang received her B.S. degree from Beijing University Shengang Xu received his Ph.D. degree in Polymer
of Chemical Technology (1993), M.S. (1999) and Ph.D. Chemistry and Physics from Zhejiang University, China,
(2006) degrees from Zhengzhou University respectively. in 2003. Currently, he is a professor of Material Science
She worked at Institute of Multidisciplinary Research for at Zhengzhou University. His research interests focus
Advanced Materials, Tohoku University, Japan as a visiting on design and synthesis of opto-electronic functional
researcher during 2007-2008, and joined Department of polymers such as photorefractive polymers, electro-
Chemistry, Tsinghua University, China as a postdoctoral luminescent polymers, organic photovoltaics polymers,
researcher in 2009. Now, she is an Associated Professor at and photocatalysts for water splitting.
School of Material Science and Engineering, Zhengzhou
University, China. Her research focuses on the organic
optoelectronic and electronic functional materials, the
functionalization and application of graphene, and pho-
tocatalysts for energy conversion.

Yan Cao is a professor of the Chemistry Department,

Jincheng Tong received his B.S. (2014) and M.S. degrees Western Kentucky University. He is an expert in energy
(2016) from Zhengzhou University, China. Now, he just conversions. His previous research experiences cover
joined Prof. Cinzia Casiraghi’s group at University of chemical engineering, mechanical engineering, mate-
Manchester,UK as a Ph.D. candidate. His research in- rial chemistry, analytical chemistry and environmental
terests include the design, preparation and application chemistry. His current research focus is advanced clean
of 2D nanomaterials and porous nanomaterials for energy conversion processes with high efficiency, such
Photoelectrochemical catalysis. as CO2 capture, chemical looping combustion and ga-
sification, renewable solar energy conversions and en-
gineering. He has been PIs and Co-PIs of many research
projects on energy conversion and environmental
protection projects.

Shaokui Cao received his B.S. degree from Hebei Uni-

Yingliang Liu completed his B.S. (2000), M.S. (2003) versity (1982), M.S. degree from Changchun Institute of
and Ph.D. (2007) degrees from Zhengzhou University. Applied Chemistry, Chinese Academy of Sciences
From 2006 to 2008, He worked at Peking University as (1984), Ph.D. degree from Institute of Chemistry, Chi-
a postdoctoral fellow during 2006-2008, and then nese Academy of Sciences (1988). He has been a re-
moved to Tokyo University as a JSPS fellow until 2010. search associate at Tohoku University from 1991 to
He joined Cao’s group at Zhengzhou University and was 1994, and then he joined to Zhengzhou University in
appointed as an aAssociate Professor from 2010. His 1994 as a full professor. His current research interests
research interests include organic/polymer functional focus on organic/polymer photorefractive and photo-
materials, organic optoelectronic devices and semi- voltaic materials, photocatalysts for energy and en-
conductor photocatalysts for water splitting. vironment and so on.

Please cite this article as: F. Li, et al., Photocatalytic CO2 conversion to methanol by Cu2O/graphene/TNA heterostructure catalyst in a
visible-light-driven dual-chamber reactor, Nano Energy (2016), http://dx.doi.org/10.1016/j.nanoen.2016.06.056i