Anni Guo‡
a,
Xingchun Wu‡a,
Syed Husnain Alia,
Huawei Shenc,
Ligong Chen*ab,
Yang Liab and
Bowei Wang*ab
aSchool of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, P. R. China. E-mail: lgchen@tju.edu.cn; bwwang@tju.edu.cn
bInstitute of Shaoxing, Tianjin University, Shaoxing 312300, Zhejiang, P. R. China
cShaoxing Xingxin New Materials Co., Ltd, Shaoxing 312300, Zhejiang, P. R. China
First published on 22nd March 2024
The development of efficient oxygen evolution reaction (OER) catalysts is of great significance because the water oxidation reaction at the photoanode is the rate-determining step in photoelectrocatalytic (PEC) water splitting. Herein, two hybrid photoanodes named BiVO4/COF-Azo and BiVO4/COF-Ben were prepared by in situ solvothermal growth on a modified BiVO4 photoanode. Characterization results revealed that the Azo and Ben COFs could match with BiVO4 well to form heterojunctions, which could effectively enhance the separation efficiency of photogenerated carriers. Also, the smaller impedance of the composite photoanodes and faster kinetics of the water oxidation reaction promoted the charge transmission and enhanced the reaction efficiency of the surface-reaching holes, respectively. As a result, the composite photoanodes exhibited a larger photocurrent and more negative onset potential compared to the pristine BiVO4. This work not only provides a new strategy to construct efficient hybrid photoanodes, but also expands the applications of COFs.
Covalent organic frameworks (COFs), a class of porous nanomaterials with periodically tunable structures, can be used as a functional material with promising applications in environmental regulation and energy utilization.17,18 For example, they always combine the advantages of large specific surface area and ordered pore structure, which can provide more active sites and facilitate the mass transfer.19 Also, their π-conjugated skeleton as 2D materials endows them with an excellent ability to harvest light and conduct electrons. More importantly, formed by the stacking of molecular layers, COFs typically have columnar π-arrays that are beneficial for electron delocalization, further promoting the separation and migration of photogenerated carriers.20–22 Moreover, strong covalent bond linkages endow them with good chemical and thermal stabilities, which enables them to have a long lifetime. However, the fast charge recombination of most pure COFs results in their low photo- or electro-catalytic efficiency. Hence, considering that the tunable band structure of COFs can match with many inorganic semiconductors to form a built-in electric field, which is conducive to the separation of photogenerated holes and electrons, the hybridization of organic COFs and inorganic semiconductors may be a feasible strategy to boost the OER activity of photoanodes.23
Among inorganic semiconductors, bismuth vanadate (BiVO4) is recognized as a highly promising photoanode.24 First, its appropriate band gap (∼2.4 eV) allows solar light absorption and so it has the potential as a photocatalyst driven by visible light. Second, its moderate valence band (2.4 V vs. the reversible hydrogen electrode, RHE) matches the thermodynamic oxygen evolution potential well. Besides, its conduction band (∼0.0 V vs. RHE) provides a more negative photocurrent onset. Nevertheless, the application of BiVO4 is still impeded on account of the low separation capacity and high electron–hole recombination rate as well as poor charge transport.25 In this context, many modified strategies have been proposed, such as tuning the morphology, doping,26,27 incorporating cocatalysts28–30 and constructing heterojunctions.31–33 Especially a heterojunction photoanode is considered as an efficient method to increase optical absorption, promote charge separation and prolong carrier lifetime. Accordingly, combining the COFs mentioned above with BiVO4 to build a heterojunction photoanode may also be an effective way to enhance OER activity. However, to our best knowledge, there have been few reports on the hybridization of COFs and BiVO4 as effective photoanodes for photoelectrocatalytic OER.
Herein, BiVO4/COF-Azo and BiVO4/COF-Ben hybrid photoanodes were successfully prepared by an in situ solvothermal growth method (Scheme 1). Their structures and morphology were characterized by Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The phase compositions and surface chemical states were studied by powder X-ray diffraction (PXRD) analysis and X-ray photoelectron spectroscopy (XPS), respectively. Due to the change of light absorption ability and energy band structures, the OER performances of two hybrid photoanodes were improved compared to that of pristine BiVO4 photoanode. Furthermore, the corresponding catalytic mechanism was proposed.
Fig. 1 Zenithal SEM images of (a) BiVO4/COF-Azo, (b) BiVO4, (c) BiVO4/COF-Ben and cross-sectional SEM images of (d) BiVO4/COF-Azo, (e) BiVO4, (f) BiVO4/COF-Ben. |
Subsequently, the phase composition of the prepared photoanode was characterized by powder X-ray diffraction. There was a negligible difference between the XRD patterns of the two composite photoanodes and pure BiVO4 photoanode (Fig. S2†). They all displayed the diffraction peaks of FTO conductive glass and monoclinic scheelite of BiVO4, indicating that the composite of COF had no effect on the phase composition of the BiVO4 photoanode. However, compared with the standard PDF card (JCPDS No. 44-0081), there was no diffraction peak with 2θ of 30.5° in the XRD pattern of BiVO4, which corresponded to the (0 4 0) crystal plane. It implied that the growth of BiVO4 crystal in this direction was inhibited, which might also be the reason why BiVO4 crystal finally grew into nanosheets. In order to confirm the formation of crystalline COFs, the powders in Pyrex tube were collected by filtration and characterized by XRD (Fig. S3†). It was found that there was a main diffraction peak at 3.12° for COF-Azo and 2.72° for COF-Ben, respectively. In addition, the experimental PXRD patterns of the COFs were both highly consistent with the simulated stacking model. COFs with high crystallinity can improve the efficiency of mass transfer and make holes transfer to the surface of the photoanode quickly to participate in the OER. Furthermore, the structures of COF-Azo, COF-Ben and their corresponding composites with BiVO4 were confirmed by FT-IR spectroscopy (Fig. S4a†). It was shown that two new vibration peaks at 1618 cm−1 and 1577 cm−1 were observed in the spectra of COF-Azo and COF-Ben, which were attributed to CO and CC in the β-ketoamine linkages. Their appearance proved that both COF-Azo and COF-Ben were synthesized successfully. Compared with the spectrum of TP, the peaks at 1643 cm−1 and 2897 cm−1 corresponding to CO and C–H stretching of formyl totally disappeared in the spectra of COF-Azo and COF-Ben. Similarly, the N–H stretching bands (at 3300–3500 cm−1) presented in Azo and Ben also appeared to weaken obviously in the spectra of them. These results indicated the effective condensation between aldehyde groups of TP and amino groups of Azo and Ben. In addition, from Fig. S4b,† it was found that BiVO4/COF-Azo and BiVO4/COF-Ben obtained by in situ growth not only retained the characteristic peaks of COF-Azo and COF-Ben, but also displayed a wide peak at 700 cm−1 similar to that of BiVO4, which demonstrated the exact hybridization of COF and BiVO4. The surface chemical states before and after combining were measured by XPS. According to the full-spectra scan of BiVO4, BiVO4/COF-Azo and BiVO4/COF-Ben, they all exhibited C, O, V and Bi elements, while N 1s peak only appeared in two composites (Fig. 2a). These results were consistent with EDS mapping. It is worth noting that there was a peak corresponding to NN in addition to C–N in the N 1s spectrum of BiVO4/COF-Azo (Fig. 2d). Moreover, a CO peak appeared after combination from the high-resolution XPS spectrum of O 1s (Fig. 2e). Combined with the FT-IR spectrum, it was assigned to the CO functional group in COFs, while the peak at 399.96 eV in the N 1s spectrum corresponded to –C–N– bond from COFs or the connection bonds between COFs and aminated BiVO4 (Fig. 2d). The above phenomena further proved the successful synthesis of COFs and effective coating on BiVO4 surface.
Fig. 2 The full survey spectra, (b) V 2p, (c) Bi 4f, (d) N 1s and (e) O 1s high-resolution XPS spectra of BiVO4, BiVO4/COF-Azo and BiVO4/COF-Ben photoanodes. |
For photoelectrocatalysis, one of the important factors is the light absorption ability of photoelectric materials. Therefore, the UV-vis diffuse reflectance spectra of BiVO4/COF-Azo and BiVO4/COF-Ben before and after combining were collected (Fig. 3a). It was shown that the absorption wavelength ranges of COF-Azo and COF-Ben were both larger than that of pure BiVO4. Specifically, the absorption range of COF-Azo was 300–700 nm, revealing the strongest absorption ability among them. The maximum absorption edge of pristine BiVO4 photoanode was about 510 nm, while those of BiVO4/COF-Azo and BiVO4/COF-Ben became 650 nm and 600 nm, respectively. Additionally, a shoulder peak was observed in the spectrum of BiVO4/COF-Azo. These changes would greatly improve their absorption ability, thereby enhancing the utilization rate of visible light in a larger wavelength range. Transforming the above spectra by the Tauc plot method, the band gaps of three photoanodes were obtained. As shown in Fig. 3b, the band gap of BiVO4 is 2.53 eV, while that of BiVO4/COF-Azo and BiVO4/COF-Ben is 2.44 eV and 2.48 eV, respectively. The change of band gap indicated that there was interaction between BiVO4 and COFs, which would be beneficial to the conduction of photogenerated carriers so as to increase their photoelectrocatalytic performance. To explore the influence of the specific surface areas on the performance of the photoanode, the specific surface areas of COF-Azo and COF-Ben powders collected from the tube were calculated by nitrogen sorption isotherms at 77 K (Fig. 4). The Brunauer–Emmett–Teller (BET) specific surface areas of COF-Azo powders was calculated to be 151.48 m2 g−1, while that of COF-Ben is 61.61 m2 g−1. The larger BET specific surface area will be more conducive to mass transfer and increase the contact area between photoanode and electrolyte, thereby accelerating the progress of OER.
Fig. 3 (a) UV-vis diffuse reflectance spectra of BiVO4, COF-Azo, COF-Ben, BiVO4/COF-Azo and BiVO4/COF-Ben photoanodes; (b) Tauc curves of BiVO4, BiVO4/COF-Azo and BiVO4/COF-Ben photoanodes. |
Fig. 5 (a) LSV curves and OER curves without illumination; (b) I–t curves of BiVO4, BiVO4/COF-Azo and BiVO4/COF-Ben photoanodes. |
In addition, a series of measurements were conducted to explore the exact mechanism. Generally, sulfite oxidation reaction has faster kinetics than OER, so the surface-reaching holes can quickly participate in the oxidation reaction with nearly 100% efficiency. Based on this fact, the ratio of the water oxidation current to sulfite oxidation current can be used to reflect the reaction efficiency of surface-reaching holes.36 As shown in Fig. 6a, it was clear that the BiVO4/COF-Azo and BiVO4/COF-Ben hybrid photoanodes exhibited a higher oxidation current than the pristine one in the presence of Na2SO3, which was speculated that COF could promote the conduction of photogenerated holes to the surface of photoanodes to participate in OER. Compared to BiVO4/COF-Ben, the oxidation current of BiVO4/COF-Azo was higher, indicatingCOF-Azo can accelerate the above conduction process. By calculating the Jwater/Jsurface ratio that was considered as the yield of holes that participate in the water oxidation reaction at the electrolyte/semiconductor interface (ηsurface), the reaction efficiency of the surface-reaching holes was obtained. From Fig. 6b, the composite photoanodes BiVO4/COF-Azo and BiVO4/COF-Ben both showed a much higher reaction efficiency than that of pristine BiVO4 photoanode. It indicated that the surface-reaching holes tended to react with water more quickly and efficiently after the modification with COFs, which further confirmed that the integrated COFs can improve interface properties and boost the water oxidation reaction. The electrochemical impedance spectra (EIS) were also recorded to figure out the transfer of carriers in the PEC system. As presented in Fig. 6c, three curves all exhibited a typical resistance arc, but the smaller radius for the modified photoanode was compared with that for the pure BiVO4 photoanode, which meant that the former possessed a better ability to transfer the carrier. Among them, the resistance arc radius of BiVO4/COF-Azo was the smallest, revealing its minimal charge transfer impedance in the reaction and the best ability to transfer carriers. Thus, it was easiest for BiVO4/COF-Azo to transfer photogenerated holes to the surface of the photoanode, thereby showing the most outstanding OER performance. Considering that the intrinsic properties of the photoanode were unlikely to be changed just by the modification of COFs, the OER curves of two BiVO4/COF and original BiVO4 photoanodes in the absence of illumination were recorded as well, which verified the change of electrocatalytic OER performance after combining COFs (Fig. 6d). It was found that the photocurrent density of BiVO4/COF-Azo and BiVO4/COF-Ben photoanodes was much higher than that of the pristine BiVO4 when voltage was more than 2.0 V (vs. RHE) without illumination. Higher photocurrent density and lower overpotential meant better electrocatalytic performance. Therefore, the two composite photoanodes had higher water oxidation activity and more negative initial potential of oxygen evolution, which made their water oxidation reaction kinetics faster and could make use of the holes reaching the surface of the photoanodes more effectively. At the same time, the curves of BiVO4/COF-Azo and BiVO4/COF-Ben basically coincided, proving that the main difference of their photoelectrocatalytic OER performance came from the influence of light rather than electricity.
Finally, the interaction between BiVO4 and COF was further explored by testing the band structure of photoanodes before and after combination (Fig. 7). It can be inferred from Tauc and M–S diagrams that both COF-Azo and COF-Ben belong to N-type semiconductors with band gaps of 2.02 eV and 2.39 eV, respectively. Concretely, the conduction band position of COF-Azo is about 0.22 V (vs. RHE), so the valence band position is about 2.24 V (vs. RHE); the conduction band position of COF-Ben is about 0.34 V (vs. RHE), so the valence band position is about 2.73 V (vs. RHE); the conduction band position of BiVO4 is about 0.84 V (vs. RHE) and the forbidden bandwidth is 2.53 eV, so the valence band position is about 3.37 V (vs. RHE). According to the above values, the energy band structure diagram was shown in Fig. 7f. It can be seen that the conduction band and valence band of COF-Azo and COF-Ben were higher than those of BiVO4. Therefore, heterojunction can be formed by combination so that the separation efficiency of photogenerated carriers was enhanced and the recombination rate was reduced. As a result, electrons gathered at BiVO4, while holes moved to COFs. It made more photogenerated holes reach the surface of photoanodes to participate in the reaction, which further improved the photoelectrocatalytic OER performance.
Fig. 7 (a) M–S curve of COF-Azo; (b) M–S curve of COF-Ben; (c) Tauc curve of COF-Azo; (d) Tauc curve of COF-Ben; (e) M–S curve of BiVO4; (f) band structure diagram of BiVO4, COF-Azo and COF-Ben. |
Footnotes |
† Electronic supplementary information (ESI) available. See DOI: https://doi.org/10.1039/d4ra00899e |
‡ These authors contributed equally to this work. |
This journal is © The Royal Society of Chemistry 2024 |