催化学报 ›› 2022, Vol. 43 ›› Issue (3): 595-610.DOI: 10.1016/S1872-2067(21)63923-2
收稿日期:
2021-07-21
修回日期:
2021-07-21
出版日期:
2022-03-18
发布日期:
2022-02-18
通讯作者:
邵明飞
基金资助:
Received:
2021-07-21
Revised:
2021-07-21
Online:
2022-03-18
Published:
2022-02-18
Contact:
Mingfei Shao
About author:
Prof. Dr. Mingfei Shao (State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology (BUCT)) received his Ph.D degree in 2014 from Beijing University of Chemical Technology under the supervision of Prof. Xue Duan, after which he joined the staff of BUCT. He was also a visiting student at the University of Oxford in 2013. His research directions include intercalation chemistry and energy materials, electrocatalysis/photoelectrocatalysis and advanced energy devices. He has been published in more than 80 SCI papers as the first or corresponding/co-corresponding author in international journals such as J. Am. Chem. Soc, Angew. Chem. Int. Ed., Adv. Mater., Chem, which have been cited more than 7500 times (H index = 45). More than 10 Chinese patents have been authorized respect to his work. He proposed a new idea of photoelectronsyhthesis/electrosynthesis for the hydrogen generation coupled with organic oxidation. He also proposed a new method of integrated electrode design based on layered double hydroxides. He has obtained and award from the National Natural Science Foundation of China--Outstanding Youth Foundation in 2019, and Catalysis Rising Star Award from the Catalysis Society of China in 2021. He joined the editorial board of Chin. J. Catal. in 2020.
Supported by:
摘要:
化石燃料的过度消耗导致了能源短缺和环境破坏, 因此可再生清洁能源的开发已成为当务之急. 在众多可再生能源中, 太阳能因其环境友好, 储量巨大且分布广泛等特点而引起了研究者们的兴趣. 光电催化(PEC)是一种能够将可再生太阳能转化为化学能的方法, 而最受关注的是通过PEC水分解来获得高附加值的氢能源. 欲使PEC系统实现水分解, 理论上应利用带隙至少为1.23 eV的半导体光电极, 在光激发下使产生的光生空穴和电子分别在阳极进行水的氧化以产生氧气, 并在阴极实现水的还原来产生氢气. 然而在此过程中, 阳极发生的析氧反应(OER)是一个动力学缓慢的四电子过程, 并且反应产出的氧气相对于氢气是一种低附加值的产物. 这就导致了PEC水分解体系效率较低, 经济性也不令人满意. 实际上, 除水分解之外, PEC体系还有许多其他应用, 包括水氧化制过氧化氢、有机物选择性氧化、有机污染物氧化降解以及二氧化碳还原等. 这些应用能够提升产物的附加值, 如水能被氧化为更高价值的过氧化氢而不是氧气. 此外, 例如甘油这一价格低廉的有机生物质可以被氧化转化为1,3-二羟基丙酮和甘油醛等高附加值化学品, 此类反应加快反应速率的特点同样能使得PEC系统的实用性提升. 最近, 在光阴极上进行二氧化碳还原反应同样得到了许多关注, 因为它能够同时起到将太阳能转换为化学能和减少温室气体来保护环境的双重目的. 但想要实现以上的目标, 必须选择合适的半导体材料以满足各体系的需要. 因此, 在一个PEC系统中同时设计能够带来更多效益的反应和与之匹配的高效光电极是一个巨大的挑战.
以往有许多优秀的文章总结了PEC水分解体系的设计和优化, 但目前还缺少对如何实现PEC系统中各种高附加值产品生产以及环境处理应用的全面讨论. 基于此目的, 本述评聚焦于PEC系统中多种面向现实应用的反应体系, 详细讨论了系统中光电极的设计制备、反应环境调控, 并揭示工作机理. 相信这篇关于PEC技术应用拓展的详细述评将对太阳能-化学能转化以发展清洁能源和环境保护的方向带来有效的借鉴和启示.
苗昱聪, 邵明飞. 光电催化用于高附加值化学品合成[J]. 催化学报, 2022, 43(3): 595-610.
Yucong Miao, Mingfei Shao. Photoelectrocatalysis for high-value-added chemicals production[J]. Chinese Journal of Catalysis, 2022, 43(3): 595-610.
Fig. 1. (a) The conversion of reactants required to achieve high-value-added chemicals production through photoelectrocatalysis; (b) The energy band structure of several common semiconductors and the redox potential [26-28].
Fig. 3. (a) Schematic diagram of dye-sensitized TiO2/[CoFe-JG] electrode constructed by in-situ modification of Prussian blue analog on TiO2 photoanode. Reprinted with permission from Ref. [56]. Copyright 2020, John Wiley and Sons. (b) Au/UCN/TiO2 photoelectrode and its working mechanism of absorbing UV-vis-NIR light. Reprinted with permission from Ref. [59]. Copyright 2019, American Chemical Society. TEM (c) and HRTEM (d) images of Au/CdSe nanodumbbells; (e) Photocurrent stability of the Au/CdSe nanodumbbell photoanode at 0.4 V vs. RHE under light illumination at λ > 700 nm. (c?e) Reprinted with permission from Ref. [60]. Copyright 2019, John Wiley and Sons.
Fig. 4. (a) Separation of hole and charge during water oxidation of TiO2 photoelectrode. Adapted with permission from Ref. [43]. Copyright 2016, Royal Society of Chemistry. (b) Mechanism of water oxidation of MOs-[PDDA-Aux@GSH]n photoanode. (a,b) Reprinted with permission from Ref. [65]. Copyright 2020, American Chemical Society. (c) Schematic diagram of selective deposition of reduction and oxidation cocatalysts on different facets of BiVO4 with the help of the separation of electrons and holes; (d) SEM images of Pt/MnOx/BiVO4. (c,d) Reprinted with permission from Ref. [77]. Copyright 2014, Royal Society of Chemistry. (e)
Fig. 5. (a) Comparison of PEC and EC water oxidation processes to produce H2O2; (b) The path of each product and the thermodynamic trend in the water oxidation process.
Fig. 6. (a) Volcano plots of H2O2 production activity. Reprinted with permission from Ref. [83]. Copyright 2017, Springer Nature. (b) Yield of O2 and Faraday efficiency of O2 and H2O2 of BiVO4, SnO2/BiVO4 and SnO2-x/BiVO4 photoanodes; (c) Mechanism of suppression of OER by SnO2-x/BiVO4 photoanodes. (b,c) Reprinted with permission from Ref. [23]. Copyright 2020, American Chemical Society. (d) Diagram of free energy of BiVO4 (001) with or without oxygen vacancies. Reprinted with permission from Ref. [13]. Copyright 2021, John Wiley and Sons.
Fig. 8. (a) Table of TiO2/C photoanode oxidation of various aromatic alcohols; (b) Mechanism of oxidation of benzyl alcohol on TiO2/C photoanode. (a,b) Reprinted with permission from Ref. [15]. Copyright 2017, John Wiley and Sons. (c) Mass spectra of benzaldehyde obtained by oxidation of G@U-LDH@BVO photoanode in (I) H2O solution, (II) 10% H218O solution, (III) 80% H218O solution; (d) Article proposed mechanism of oxidation of benzyl alcohol to benzaldehyde by G@U-LDH@BVO photoanode. (c,d) Reprinted with permission from Ref. [87]. Copyright 2020, American Chemical Society.
Fig. 9. (a) Energy profile diagram of BiVO4 oxidized glycerol intermediates. Reprinted with permission from Ref. [92]. Copyright 2019, Springer Nature. (b) Diagram of the oxidation mechanism of HMF in a photoelectrocatalysis system using TEMPO as the medium. Reprinted with permission from Ref. [14]. Copyright 2015, Springer Nature. (c) Schematic illustration for different facets of WO3 nanobar arrays; (d) SEM images of WO3 nanobar arrays; (e) PEC oxidation process of methane. (c?e) Reprinted with permission from Ref. [90]. Copyright 2021, John Wiley and Sons.
Fig. 10. (a) Photocurrent-potential curves under illumination of SnO2@BiVO4/Co-Pi photoanode in 0.1M PBS with/without urea. Reprinted with permission from Ref. [88]. Copyright 2019, Royal Society of Chemistry. (b) Durability of F-BiVO4@NiFe-LDH photoanode for degradation of TCH. Reprinted with permission from Ref. [106]. Copyright 2020, Elsevier. (c) Photoelectrocatalytic CBZ oxidation couple with HER/CO2RR system. (d) Recycling test for CBZ degradation. (c,d) Reprinted with permission from Ref. [107]. Copyright 2021, Elsevier. (e) Schematic of the fabrication process of the (S)-DCPP-molecular-imprinted single-crystalline TiO2 photoelectrodes. Reprinted with permission from Ref. [100]. Copyright 2017, Elsevier. (f) Path of SnO2/010-BVO controlled conversion 2,4-DCP. Reprinted with permission from Ref. [108]. Copyright 2020, American Chemical Society.
Fig. 11. (a) Relaxation after CO2 adsorbed on AZO surface; (b) Calculation of free energy for different reduction paths of CO2. (a,b) Reprinted with permission from Ref. [119]. Copyright 2020, Elsevier. (c) Diagram of composite photocathode. Reprinted with permission from Ref. [121]. Copyright 2020, John Wiley and Sons. (d) Schematic mechanism of CoPcP for converting CO2 to CO. Reprinted with permission from Ref. [122]. Copyright 2021, American Chemical Society.
Fig. 12. (a) Diagram of the mechanism of the conversion of CO2 to methanol on the surface of Cu/Cu2O. Reprinted with permission from Ref. [117]. Copyright 2018, John Wiley and Sons.. (b) Adsorption behavior on g-C3N4/ZnTe heterojunction of CO2 (1) and CO (2); (c) Schematic diagram of g-C3N4/ZnTe heterojunction photocathode. (b,c) Reprinted with permission from Ref. [127]. Copyright 2019, Elsevier.
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