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Titel: Semiconductor-Covalent Organic Framework Z-scheme

Heterojunctions for Artificial Photosynthesis

Autoren: Ya-Qian Lan, Mi Zhang, Meng Lu, Zhong-Ling Lang, Jiang

Liu, Ming Liu, Jia-Nan Chang, Le-Yan Li, Lin-Jie Shang, Min
Wang, and Shun-Li Li

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Zitierweise: Angew. Chem. Int. Ed. 10.1002/anie.202000929

Angew. Chem. 10.1002/ange.202000929

Link zur VoR: http://dx.doi.org/10.1002/anie.202000929

http://dx.doi.org/10.1002/ange.202000929
Angewandte Chemie 10.1002/ange.202000929

RESEARCH ARTICLE
Semiconductor-Covalent Organic Framework Z-scheme
Heterojunctions for Artificial Photosynthesis
Mi Zhang,[1+] Meng Lu,[1+] Zhong-Ling Lang, [2+] Jiang Liu,[1] Ming Liu,[1] Jia-Nan Chang,[1,2] Le-Yan Li, [1]
Lin-Jie Shang,[1] Min Wang,[1] Shun-Li Li,[1] and Ya-Qian Lan*[1]
Abstract: Here, we developed a versatile strategy to covalently many vital aspects are difficult to solve simultaneously in most
connect crystalline covalent organic frameworks (COFs) with all-inorganic Z-scheme system: i) efficient light absorption; ii)
semiconductors to create stable organic-inorganic Z-scheme fast CO2 adsorption and diffusion; iii) suitable redox sites and
heterojunctions for artificial photosynthesis. A series of COF- energy band structure for simultaneous CO2 reduction and H2O
semiconductor Z-scheme photocatalysts integrating water oxidation oxidation reaction; iv) fast separation and migration of photo-
semiconductors (TiO2, Bi2WO6 and α-Fe2O3) with CO2 reduction

Accepted Manuscript
generated electrons and holes to the adsorbed CO2 and H2O
COFs (COF-316/318) were synthesized and exhibited high molecules on active sites, respectively.[4] As a result, the
photocatalytic CO2-to-CO conversion efficiency (69.67/ 57.1/ 31.43 photocatalytic efficiency of CO2 reduction for all-inorganic Z-
μmol/g/h for COF-318-TiO2/-Bi2WO6/-α-Fe2O3), with H2O as electron scheme systems are still difficult to improve at present.
donor in the gas-solid CO2 reduction without additional Introduction of functionalized organic components to inorganic
photosensitizers and sacrificial agents. This is the first report of semiconductors is an effective way to improve these factors, but
covalent bonded COF-inorganic semiconductor Z-scheme applied the connectivity between them suffer from instability and
for artificial photosynthesis. Experiments and density functional ineffectiveness through physical adsorption or conjugate
theory confirmed the efficient electron transfer from semiconductors stacking force[4a, 5]. On the other hand, employing catalysts with
to COFs by covalent coupling, resulting in the electrons accumulated well-defined structures to further systematic study the reaction
in cyano/pyridine of COF for CO2 reduction and positive holes leave mechanisms are of great significance[6].
in semiconductor for H2O oxidation, thus mimicking the natural Crystalline covalent organic frameworks (COFs), in
photosynthesis. This work developed a new method to create possession of large surface areas and tunable structure, are
covalent bond linked organic-inorganic Z-scheme heterojunction and expected to provide an ideal scaffold for CO2 adsorption,
demonstrated a breakthrough on the field of artificial photosynthesis. diffusion, and activation.[7] With suitable building blocks and
functional organic groups, COFs have been shown to have high
visible light absorption capacity and fast charge carrier
Introduction mobility.[8] Furthermore, many COF-based photocatalysts have
been successfully used for light driven reduction of CO2[6a, 7c-e].
Excessive emission of carbon dioxide (CO2) produced from the Meanwhile, many inorganic semiconductors (SCs, such as TiO2,
fossil fuels burning to the atmosphere has caused energy and Bi2WO6, α-Fe2O3 et.al) have been demonstrated as outstanding
environmental issues that need to be resolved[1]. Inspired by photocatalysts that can achieve efficient H2O photooxidation[9].
natural photosynthesis, converting CO2 with H2O into On this basis, functionally integrating the water oxidizable
carbohydrate and O2 by solar energy is regarded as an ideal and inorganic semiconductor with CO2 reduction COFs to form Z-
green approach to solve this problem[2]. However, it is still the scheme heterogeneous system maybe a feasible strategy to
most challenging work to integrating the CO2 reduction reaction enhance the efficiency of artificial photosynthesis, that is,
(CO2RR) and H2O oxidation reaction into one photosynthetic simultaneously reduce CO2 and oxidize water. The key to
system and to further coupling effectively[2-3]. Traditional Z- achieve this integration is whether the charge carrier can be
scheme heterojunction assembled with two inorganic effectively transferred between semiconductors and the COFs.
semiconductors into a single-component with two separate The covalent bond connection between compositions is a good
functional sites has been considered as a photosynthetic tactic choice to address these problems, also provides high stability for
to satisfy the aforementioned criteria[3a]. This type of Z-scheme photocatalyst[10]. However, no practical method has been
system has been widely used in water splitting, while only a few appeared for effectively covalent connecting organic porous
studies have been conducted in the field of CO2RR because materials with inorganic semiconductors.
In this work, we present a versatile method for the fabrication
of stable covalent bond linked organic-inorganic Z-scheme
[1]
M. Zhang,[+] M. Lu,[+] Dr.J. Liu, M. Liu, J-N Chang, L-Y Li, L-J system between COFs and inorganic semiconductors for
Shang,M Wang ,Prof. S.-L. Li, Prof.Y. -Q. Lan* artificial photosynthesis (CO2RR with H2O). Polyarylether (PAE)-
Jiangsu Collaborative Innovation Centre of Biomedical Functional COFs are a class of designable COFs, which is condensed
Materials, School of Chemistry and Materials Science, Nanjing
Normal University. No. 1, Wenyuan Road, Nanjing, 210023 (China)
through aromatic nucleophilic substitution between the extended
E-mail: [email protected] o-difluoro benzene and catechol building units.[11] This type of
[2]
Dr. Z-L Lang[+] COFs can be rationally designed by selecting various o-difluoro
Key Laboratory of Polyoxometalate Science of the Ministry of benzene and catechol building units. Here we choose
Education, Faculty of Chemistry, Northeast Normal University,
Changchun, 130000, P. R. China.
2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) and
[+]
These authors contributed equally to this work. tetrafluorophthalonitrile (TFPN) or 2,3,5,6-tetrafluoro-4-
Supporting information and the ORCID identification number(s) for pyridinecarbonitrile (TFPC) as precursor to get two PAE-COFs,
the author(s) of this article can be found under: named COF-316 and COF-318, respectively. The strong
https://doi.org/10.1002/xxx.
electron withdrawing substituents on the TFPN and TFPC
building units make TFPN/TFPC prone to nucleophilic attack by

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Angewandte Chemie 10.1002/ange.202000929

RESEARCH ARTICLE
the hydroxyl functionalities.[12] It is well known that various covalent coupling, resulting in the electrons accumulated in
semiconductors can be functionalized by organic functional cyano/pyridine active sites of COF for CO2RR and positive holes
groups through covalent linkage, especially oxide- leave in semiconductor for H2O oxidation, thus mimicking the
semiconductors, which always contain hydroxyl functional group natural photosynthesis. From mechanism analysis, the
on the surface itself[13]. Through this feature, semiconductors coexistence of pyridine group and cyano reduces the overall
can be covalently connected to PAE-COFs. As a proof of activation energy barrier on the reduction of CO2. Our results
concept, a series of COFs-semiconductor heterojunctions (COF- provide a versatile route for the future construction of COF-
SCs: COF-TiO2, Bi2WO6, and α-Fe2O3) were designed and semiconductor heterojunction, and new possibilities for the
synthesized for photosynthetic gas-solid CO2 reduction reaction development of high-performance organic-inorganic Z-scheme
use H2O as electron donor, without the help of additional system applied for artificial photosynthetic overall reaction.
photosensitizers and sacrificial agents. As expected, the
covalent bond linked COF-318-TiO2 Z-scheme catalyst showed
the highest CO production rate of 69.67 μmol/g/h, 5.2 times Results and Discussion
higher than the pure COF-318 (13.3 μmol/g/h) and 6 times

Accepted Manuscript
higher than TiO2 (11.8 μmol/g/h), also much higher than the The COF-318/316-semiconductors (COF-318/316-SCs)
physical mixture state (29.3 μmol/g/h), which is one of the best composites were synthesized by condensation of HHTP, TFPC
performances of all the reported catalysts for overall CO2 /TFPN, and hydroxyl-containing oxide semiconductors (TiO2,
reduction with H2O to our knowledge. Moreover, COF-318-TiO2 Bi2WO6, and α-Fe2O3) (Scheme 1). The structures and
in which pyridine and cyano coexisted has higher performance successful preparation of COF-318 and COF-318-TiO2-1/2/3/4
than merely cyano content COF-316-TiO2 (57.16 μmol/g/h). (20%, 25%, 40%, 55% mass loading of TiO2, respectively.
From experiment and density functional theory (DFT) Abbreviated as COF-318-TiO2 for 40 wt.% content of TiO2, the
calculations combined with the accurate structure model, we same below) were confirmed by powder X-ray diffraction
illustrated the electron transfer direction and CO2 reduction (PXRD) patterns as shown in Fig 1a and Fig S1-2.
mechanisms. The photogenerated electrons driven by photo-
irradiation transfer effectively from semiconductors to COFs by

Scheme 1. Schematic representation of the preparation of COF-318-SCs via the condensation of COF-318 and semiconductor.

The presence of characteristic diffraction peaks at 4.38°, COF-318-TiO2 (Fig 1b and Fig S9-15). From the FTIR spectrum
7.53°, 8.82°, and 30.67° were attributed to the crystalline COF- (Fig 1c), the 1012 cm-1 can be assigned to symmetric stretching
318. The rest of peaks in the COF-318-TiO2 agreed with the of dioxin C-O bond of COF-318-TiO2, also existed in TFPC-TiO2.
simulated PXRD patterns of anatase TiO2 (PDF-21-1272). Proof The peak at 1243 cm-1 was denoted to C-O-C asymmetric
of the covalent bond connect was provided by X-ray stretching on COF-318 (b: Vas C-O-C in Fig 1c), while 1265 cm-
1
photoelectron (XPS) spectroscopy and Fourier-transform was from C-O-Ti asymmetric stretching (a: Vas C-O-Ti in Fig
infrared (FTIR) and DFT calculations. The XPS results showed 1c). All these evidences illustrated that TiO2 was successfully
C-O bond exists in the model compounds of TFPC-TiO2 and bonded to COF-318/TFPN through C-O covalent bond. The

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Angewandte Chemie 10.1002/ange.202000929

RESEARCH ARTICLE
structure of the as prepared COF-318-Bi2WO6 (40 wt.% of by COF-318, which indicated that there was a strong bonding
Bi2WO6, the same below) and COF-318-α-Fe2O3 (40 wt.% of α- interaction between TiO2 and COF. In high-resolution TEM (HR-
Fe2O3, the same below) were also confirmed by PXRD as shown TEM) image (Fig 1e) of COF-318-TiO2, the lattice fringe of 0.235
in Fig S3-4 and FTIR in Fig S7-8. The same, the structures and nm was attributed to the (001) face of TiO2, the outer covering
successful preparation of COF-316 and COF-316-TiO2 were with thickness of 5-10 nm was the COF shell. Fig 1f shows the
also confirmed by PXRD as shown in Fig S5-6. The porous high-angle annular dark field (HAADF) image and energy
structures and surface area of these samples were evaluated by dispersive X-ray spectroscopy (EDX) elemental mapping of the
N2 sorption measurements at 77 K (Fig S16-18). The surface COF-318-TiO2 samples, signifying that the Ti, N, and O are
area of COF-318-TiO2 was calculated to be 196.386 m2/g using evenly distributed within the COF-318-TiO2 nanostructure. The
the Brunauer–Emmett–Teller (BET) method, which is smaller morphology and elemental mapping of COF-318-Bi2WO6 and
than that of pure COF-318 (461.295 m2/g) due to the presence COF-318-α-Fe2O3 are shown in Fig S24-25. It can be clearly
of TiO2 with a low surface area (26.484 m2/g). The pore size of seen that Bi2WO6 and α-Fe2O3 are uniformly covered by COF-
COF-318 is distributing in ~1.6 nm and ~2.8 nm, which 318 as well. The morphology of COF-316-TiO2 was also
calculated from the N2 adsorption isotherms. This kind of pore conducted and shown in Fig S26. These results indicate that the

Accepted Manuscript
also exist in COF-318-TiO2 due to the introduced non porous selected semiconductors are all encapsulated uniformly by the
feature of TiO2. The TiO2 mass content of COF-318-TiO2 was selected COFs, proving the versatility of this approach.
calculated from thermogravimetric analysis (TGA) (Fig S20). Previous studies have confirmed that a high CO2 adsorption
capability is favorable to the improvement of the photocatalytic
performance.[5b, 14] The CO2 capacity measurement was
performed for the synthesized hybrid materials COF-318-TiO2
and pure COF and TiO2 (Fig 2a and Fig S19). These results
shows that COF-318-TiO2 have high CO2 uptakes of 27.5 and
19.0 cm3/g at 273K and 298K, respectively, this large absorption
ability is kinetically advantaged for CO2 reduction.[15] The UV-vis
optical absorption measurement was performed, followed by a
Tauc plot to estimate the bandgap for the as-prepared COF-318
and TiO2 (Fig 2b), also for Bi2WO6 and α-Fe2O3 (Fig S27-28).
Mott–Schottky (MS) measurements were conducted to
determine the electronic band positions of the as-prepared
materials (Fig 2c and Fig S29-32). The conduction band
position is -0.55 and -0.75 eV (vs. NHE) for COF-318 and TiO2.
Combined with the bandgap of COF-318 and TiO2 from UV-vis
absorption data, the valence band position of them is 0.86, 2.62
eV, respectively.
The electron transfer direction between the COF-318 and
TiO2 and whether a Z-scheme or a type II heterojunction was
formed will be discussed in detail below. We took the view that
the covalent bond linking existed in the COF-318-TiO2
heterojunction owns superior photo-induced electron
separation/transport efficiency compared to conventional
heterojunctions. As a proof of concept, transient photocurrent
response and photoluminescence (PL) were conducted to
investigate the charge transfer behaviors (Fig 2d). As expected,
the strength of transient photocurrent response intensity of COF-
318-TiO2 showed 3 times and 1.5 times higher than the pure
TiO2 and COF-318, respectively. The transient photocurrent
response intensity of COF-318-Bi2WO6 and COF-318-α-Fe2O3
were also much higher than COF-318, Bi2WO6 and α-Fe2O3 as
shown in Fig S33-34. The PL of COF-318-TiO2 showed the
Fig 1. The characterization and morphology of the COF-318-TiO2. (a) weakest intensity of them (Fig 2e), most importantly, much lower
Experimental and simulated PXRD patterns of COF-318-TiO2 (40 wt.% for
than that the physical mixture composite COF-318/TiO2. All
TiO2); (b) High resolution O 1s XPS spectra of model compound TFPC-TiO2;
(c) FTIR spectrum of COF-318-TiO2 (the particulars are highlighted in the these results illustrate that the covalently linked heterojunction
inset); (d) TEM image of COF-318-TiO2; (e) HRTEM image and the lattice structure can effectively enhance the electron-hole separation
fringes (the lattice fringe of 0.235 nm is attributed to the (001) face of TiO2) and prevent electron-hole recombination which is attributed to
and (f) High-angle annular dark field element mapping of COF-318-TiO2.
efficient electron transfer through covalent bond. At the same
The morphology of COF-318-SCs were investigated by time, the electronic conductivity of COF-SCs were also found to
transmission electron microscopy (TEM) and scanning electron be better than that of the semiconductors from electrochemical
microscopy (SEM). Fig S21-22 showed SEM and TEM images impedance spectroscopy (EIS) measurements, as indicated by
of pure COF-318 and TiO2. It reveals that the bulk COF-318 own the radius of the preceding semicircle (Fig S35-37), suggesting
graphene like layered assembly by thin nanosheet. The that the covalent linkage of COF and semiconductor can
synthesized TiO2 shown anatase type and the average diameter obviously enhance the charge transfer.
is ca. 50 nm. Significantly, from the TEM images of COF-318-
TiO2 (Fig 1d and Fig S23), all the TiO2 was completely covered

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Angewandte Chemie 10.1002/ange.202000929

RESEARCH ARTICLE
heterojunctions, COF-318-Bi2WO6 and COF-318-α-Fe2O3 (Fig
3b and Fig S39). After forming heterojunction with COF-318 and
COF-316, all the CO2 reduction activity greatly improved
compared to its bulk component. More importantly, the
covalently connected COF-318-TiO2 also much higher than that
of physical mixture COF-318/TiO2 (117.2 µmol g−1, 40 wt.%
content of TiO2), showing the superior of covalent bond link of
heterojunction. This is one of the best performances of reported
the overall CO2 reduction with H2O to our knowledge as shown
in Table S1. The CO2 reduction performance of composites with
different TiO2 content shows volcanic shape, and the
performance is the highest at 40 wt.% content, which most likely
due to the more active site exposure and more efficient electron
transfer of the composites with appropriate proportion.

Accepted Manuscript
Fig 2. CO2 absorption and Optical properties of COF-SCs. (a) CO2
adsorption curves of COF-318, TiO2 and COF-318-TiO2 measured at 273 K;
(b) Solid-state UV-vis absorption spectra of COF-318, TiO2, and COF-318-
TiO2 and inset Tauc plot. (c) Mott–Schottky plot for COF-318 and TiO2; (d)
Transient photocurrent response of COF-318-TiO2, TiO2, and COF-318-TiO2;
(e) PL of COF-318, TiO2, and COF-318-TiO2; (f) Band structure diagram for
COF-318, TiO2, Bi2WO6, and α-Fe2O3.
Fig 3. Photocatalytic CO2RR performance of COF-SCs. (a) Photocatalytic
Theoretically, a photocatalyst needs a more negative CO2 to CO performances of COF-318-TiO2 for gas-solid CO2 reduction
conduction band minimum (CBM) potential than the theoretical compared with COF-318, TiO2 and COF-318/TiO2; (b) Photocatalytic
performances of various COF-318-SCs and bulk COF-318, TiO2, Bi2WO6 and
CO2 reduction potential to complete the CO2RR. As for H2O α-Fe2O3; (c) Durability measurements of COF-318-TiO2; (d) mass
oxidation reaction, a more positive valence band maximum spectroscopy of 13CO (m/z = 29) produced from the photocatalytic reduction of
(VBM) potential is needed to catalyze the H2O/O2 conversion.[6a]
13
CO2.
The optical band structure diagram for COF-318, TiO2, Bi2WO6,
During the photoreduction process, this catalyst can
and α-Fe2O3 are displayed in Fig 2f. These results showed that
simultaneously achieve the reaction of H2O oxidation into O2,
COF-318 is capable of reducing CO2 to many reductive carbon-
which confirmed by isotope labeling experiments through mass
based products (such as CO, CH4, HCOOH, et al.) and these
spectrometry. The stability of COF-318-TiO2 hybrid was
semiconductors are capable of oxidizing H2O to O2. Based on
investigated by five consecutive runs with each run of 4 hours
this, the efficient bonding between COF-318 and semiconductor
under light irradiation, where the performance showed negligible
has great potential to complete the overall reaction (i.e. CO2RR
drops (Fig 3c). We then performed isotope labeling experiments
with H2O as electron donor).
to ascertain the carbon and oxygen sources of the result
The photocatalytic CO2 reduction performance was
products. As showed in mass spectrometry spectrum in Fig 3d,
investigated with gas-solid method under simulated sunlight 13
CO (m/z = 29) was detected when using 13CO2 as substrates.
irradiation (λ = 380-800 nm), without additional photosensitizer,
Moreover, when H2O was replaced by H218O, 18O2 (m/z = 36)
sacrifice agent or co-catalyst. Detailed descriptions of the
and 18O16O (m/z = 34) were detected after the reaction (Fig S40-
photocatalytic CO2 reduction measurement are presented in the
41), affirming the generated 18O2/O2 is derived from the oxidation
Supporting information S3. Before gas-solid photocatalytic
of H218O/ H2O. The crystallinity and structural integrity of COF-
reaction measurement, these COF-SCs were soak washed with
318-SCs were retained after the reaction, as confirmed by
60 oC N,N-Dimethylformamide (DMF) and H2O for 12h, then
PXRD (Fig S42-44).
transferred to a Soxhlet extractor and washed with
To investigate the connection mode between COF-318 and
tetrahydrofuran for 24 h. Finally, the product was evacuated at
semiconductor TiO2, we constructed the adsorption of COF-
150 oC under dynamic vacuum overnight to yield activated
318(010) on the Titania (001) and (101) facets respectively from
sample. As shown in Fig 3a and Fig S38, the COF-318-TiO2
theoretical view. Both adsorptions are thermodynamically
displays an optimal CO formation rate of 278.7 µmol g−1, greatly
allowed through the CCOF-OTiO2-Ti5c bonds (dTi5c-O=2.04-2.10 Å),
higher than the 53.2 µmol g−1 for bulk COF-318 and 47.2 µmol
while the adsorption on TiO2(001) is more stable than on (101)
g−1 for bulk TiO2, revealing the function of heterostructure.
as labeled in Fig S45-46 (-0.80 vs. -072 eV). A more careful
Besides, we also tested the performance of the other two

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Angewandte Chemie 10.1002/ange.202000929

RESEARCH ARTICLE
comparison of the density of states (DOSs) for the bare coupled electron-transfer step (*COOH → *CO) serves as the
component (TiO2(001) and COF) and their advanced COF- potential-determining step (PDS). To identify the specific active
318(010)-TiO2(001) composite shows interesting electronic sites for CO2 reduction in COF, two possible reactive sites: N
characters (Fig 4a and Fig S47). New valence band (VB) and atoms in pyridine (site-N) and cyano group (site-CN) were
conduction band (CB) was formed by inserting of C(2p) and calculated toward the reduction. The required free energy
N(2p) bands between the well-established O(2p) and Ti(3d) change for the PDS is calculated to 1.59 and 0.93 eV on site-N
bands in pure TiO2(001) with band gap of only 0.35 eV, and site-CN, respectively, suggesting a lower required
indicating a photonic sensitization of the TiO2 substrate by the overpotential via site-CN. Therefore, we proposed that the cyano
COF layer. The Fermi level of the COF-318(010)-TiO2(001) group could be a promising catalyst site for CO2 photoreduction.
enter inside the valence band by increasing the O(2p) and Ti(3d) From another point of view, the cyano group plays a role of
states. On the other hand, the lowest unoccupied Ti(3d) states electron acceptors.[17] It is noticeable that the capture for CO2
was elevated to 1.5 eV due to the adsorption of COF-318. are almost equivalent on both sites, whilst the CO2 activation to
Consequently, the photo-electron would potentially transfer from *COOH is more favorable on site-N. This may lead to the
TiO2 to the COF-318 layer. pathway on pyridine N is also possible, lowering the difference

Accepted Manuscript
between site-N and site-CN. Hence, the photogenerated
electrons tend to aggregate on the cyano group, which is more
conducive to the reduction of CO2. As the second electron and
proton inject into the -C≡N-*COOH unit, the *COOH finally turns
into CO molecules and desorbs into the environment. For the
H2O oxidation process react in hole-doped TiO2 has been
extensively studied and unanimously recognized. Overall, we
get conclude that pyridine group is beneficial to the first step of
CO2 activation to *COOH, and cyano group is favorable for the
second proton coupled electron-transfer step (*COOH → *CO).
Therefore, the pyridine group and cyano coexist reduces the
overall activation energy barrier on the reduction of CO2. As a
result, compared with sole cyano active sites in COF-316-TiO2,
the combination of pyridine group and cyano (COF-318-TiO2)
attribute to higher CO2 reduction activity.

Conclusion

In summary, we developed a versatile strategy that

fabricated COFs with inorganic semiconductors through stable
Fig 4. Mechanism and DFT calculations. (a) Plots of the atom-projected
covalent bond to form organic-inorganic Z-scheme
density of states for COF-318(010)-TiO2(001). (b) High-resolution in-situ XPS
for Ti 2p of COF-318-TiO2 in the dark and under 365 nm LED irradiation; (c) heterojunctions for artificial photosynthesis. Three types of
Schematic illustration of the charge transfer process under light irradiation with semiconductors (TiO2, Bi2WO6, and α-Fe2O3) and two types of
Z-scheme model; d) CO2RR process on COF-318-TiO2 based on DFT COFs (COF-316 and COF-318) were selected to integrate COF-
calculations.
semiconductor heterojunctions and used for photosynthetic gas-
To clarify the electron transfer direction between COF-318 solid CO2RR using H2O as electron donor, without additional
and TiO2 experimentally and whether it complies with the Z- photosensitizers, sacrificial agents and co-catalysts. The
scheme or type-II heterojunction pathway, high resolution in-situ covalent bond linked COF-318-TiO2 Z-scheme heterojunction
XPS test for Ti 2p of COF-318-TiO2 were conducted (Fig 4b). show the highest CO production rate of 69.67 μmol/g/h, which is
The positive shift binding energy of Ti 2p under UV-light about six times higher than the pure COF-318 and TiO2 also
irradiation was due to the electron density reduction of Ti[16]. much higher than the physical mixture composites. These
These results showed that the photogenerated electrons results demonstrate the versatility of this method. Through
migration direction from TiO2 to COF-318, which is precisely in comprehensive characterization and DFT calculation results, we
line with the theoretical results. The proposed photogenerated confirmed that the effective covalent coupling between organic
electrons transfer path is shown in Fig 4c with red arrows. In framework and semiconductor enables the photo-generated
detail, by irradiation with UV-vis light, both COF-318 and TiO2 in electrons to transfer efficiently between organic functional group
COF-318-TiO2 can be excited to generate electrons and holes, and semiconductor counterpart. This feature result in that the
while the excited electrons of TiO2 tend to transfer to COF-318 photoexcited electrons and holes accumulated in COF and TiO2
and finally accumulated at the pyridine/cyano sites. can be efficiently used for CO2 reduction and H2O oxidation
Simultaneously, the remaining positive holes accumulate at the reactions, respectively, thus simulated the artificial
VB of TiO2. The entire electron transfer path formed a Z-scheme photosynthesis. Experiment and DFT calculations combined with
model. Importantly, the Z-scheme model of COF-318-TiO2 takes the clear structure model suggests the superiority of coexistence
advantage of the high photoreduction potential of COF-318 and of pyridine and cyano active sites in our COFs photocatalyst for
the powerful photooxidation ability of TiO2. The CO2 reduction CO2 reduction. This strategy represents a new insight for the
pathway was investigated via computational hydrogen electrode future rational design of Z-scheme organic-inorganic
mode with DFT method. Referring to the primitive steps for CO2 heterojunctions for artificial photosynthesis.
reduction to CO as presented in Fig 4d, the second proton

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Angewandte Chemie 10.1002/ange.202000929

RESEARCH ARTICLE
Acknowledgements Sci. 2020, 11, 543-550; f) N. Huang, P. Wang, D. Jiang, Nat.
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Angewandte Chemie 10.1002/ange.202000929

RESEARCH ARTICLE
RESEARCH ARTICLE
Text for Table of Contents Mi Zhang, Meng Lu, Zhong-Ling Lang,
Jiang Liu, Ming Liu, Jia-Nan Chang, Le-
A versatile strategy to covalently
Yan Li, Lin-Jie Shang, Min Wang, Shun-
connect crystalline covalent organic
Li Li, and Ya-Qian Lan*
frameworks with semiconductors to
create organic-inorganic Z-scheme Page No. – Page No.
heterojunctions was development and
applied for CO2 photoreduction with Semiconductor-Covalent Organic
H2O. This work represents a new Framework Z-scheme Heterojunctions
insight for the future rational design of for Artificial Photosynthesis
Z-scheme organic-inorganic
heterojunctions for artificial

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photosynthesis.

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