催化学报 ›› 2024, Vol. 60: 1-24.DOI: 10.1016/S1872-2067(23)64637-6
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房文健a,e, 严嘉玮a, 韦之栋a,b, 刘军营c, 郭伟琦d, 江治a, 上官文峰a,*()
收稿日期:
2023-12-05
接受日期:
2024-02-10
出版日期:
2024-05-18
发布日期:
2024-05-20
通讯作者:
电子信箱: 基金资助:
Wenjian Fanga,e, Jiawei Yana, Zhidong Weia,b, Junying Liuc, Weiqi Guod, Zhi Jianga, Wenfeng Shangguana,*()
Received:
2023-12-05
Accepted:
2024-02-10
Online:
2024-05-18
Published:
2024-05-20
Contact:
E-mail: About author:
Wenfeng Shangguan (Shanghai Jiao Tong University) received his B.S. in 1983 and M.S. in 1988 from Wuhan University of Technology, and Ph.D degree in 1996 from Nagasaki University, Japan. He carried out postdoctoral research at the Kyushu Institute of Industrial Technology in Japan from 1996 to 2000. Since April 2000, he has been working in the School of Mechanical and Power Engineering at Shanghai Jiao Tong University as a professor. His research interests include environment catalysis and photocatalysis, solar hydrogen production and air quality controlling. He has published more than 200 peer-reviewed papers and secured over 30 invention patents. He has published 7 books including monographs and translations. He is in the list of the Most Cited Chinese Researchers by Elsevier China from 2014 to 2023. He received the First Prize of the Shanghai Natural Science Award and the National Baosteel Excellent Teachers Award. He is involved in various academic roles, serving as a Member of the Catalysis Committee of the Chinese Chemical Society and holding Editorial Board positions at journals such as the Journal of Environmental Science and Frontiers in Energy.
Supported by:
摘要:
光催化分解水制氢, 作为一种绿色、安全、高效且低成本的制氢技术, 因其清洁性和巨大的发展潜力而受到广泛关注. 尽管光催化分解水制氢在理论上具有显著优势, 但在实际应用中仍面临捕光效率低、电荷分离难、表面反应速率慢以及光腐蚀等挑战. 为解决上述问题并突破效率瓶颈, 研究者们积极探索新的方法, 如构建异质结、调控微观结构、引入助催化剂、掺杂和诱导缺陷等, 以期提高光催化剂的性能. 其中, 光催化剂掺杂改性是研究热点之一. 通过对光催化剂进行掺杂改性, 可以有效调节其能带结构、光吸收性能以及电荷传输性能, 进而提升光催化分解水制氢的效率. 因此, 对光催化剂掺杂在光催化分解水制氢中的作用机制和研究进展进行系统地梳理和总结, 有助于深化对该领域的理解, 具有重要意义.
本文系统地介绍了近年来本课题组利用掺杂改性光催化剂提升光解水制氢性能的研究成果. 首先, 总结了光催化剂掺杂的合成方法和表征手段, 并详细介绍了用于分析掺杂离子在催化剂中的分布及价态的原位表征方法. 其次, 以铋基复合氧化物为例, 介绍了通过固溶法将稀土元素掺杂到铋基复合氧化物中, 实现可见光下完全分解水, 并探讨了掺杂对光催化剂能带结构的影响及作用机制. 进一步, 阐述了掺杂后铋基复合氧化物微观结构的变化, 特别是暴露面、表面特性和缺陷态等对光生载流子分离与迁移的影响, 归纳了掺杂诱导的结构变化与光催化分解水制氢性能之间的构效关系. 此外, 介绍了一种新颖的多局域梯度掺杂方法: 利用离子扩散使预先储存掺杂离子的“纳米胶囊”持续、非均匀地释放入半导体材料中, 诱导导带位置连续弯曲, 从而在导带势能面内构建出多局域的势阱, 从而延长了光生电子空穴对的寿命, 为光生载流子提供了更多迁移至表面的通道, 明显提高了光解水效率. 最后, 展望了光催化剂掺杂技术未来的研究方向: (1) 通过对光催化分解水制氢中的析氢和析氧助催化剂进行掺杂改性, 提高表面催化反应速率; (2) 发展纳米催化剂上的非对称掺杂技术, 在纳米颗粒内的特定区域或表面掺杂的精确调控, 以提高光催化分解水制氢性能; (3) 随着机器学习的进步, AI模型可以用于预测和优化掺杂条件, 从而大幅减少实验量.
综上, 本文总结了掺杂在光催化分解水制氢研究中的研究进展, 希望能为探索开发可见光光催化水分解的新型材料和提高能量转换效率提供参考和借鉴.
房文健, 严嘉玮, 韦之栋, 刘军营, 郭伟琦, 江治, 上官文峰. 光解水制氢催化剂的掺杂改性[J]. 催化学报, 2024, 60: 1-24.
Wenjian Fang, Jiawei Yan, Zhidong Wei, Junying Liu, Weiqi Guo, Zhi Jiang, Wenfeng Shangguan. Account of doping photocatalyst for water splitting[J]. Chinese Journal of Catalysis, 2024, 60: 1-24.
Fig. 3. Various chemical methods for doping in photocatalysis. Schematic representation of the various doping processes. (A) Co-nucleation doping; (B) growth doping; (C) dopant-nucleation; (D) diffusion doping; (E) ion-exchange doping; (F) atomically precise doping; (G) digital doping [27], Copyright 2017, Wiley. (H) multilocal gradient-doping [42]. Copyright 2023, Elsevier.
Fig. 4. Several advanced characterization methods. (A) In-situ high-temperature TEM and XRD [45]. Copyright 2016, American Chemical Society. (B) Raman imaging and scanning electron microscopy (RISE) [42]. Copyright 2023, Elsevier. (C) XPS with different depths etched by argon ions [46]. Copyright 2019, American Chemical Society. (D) Transient IR absorption combining UV lamp irradiation [47]. (E) potential-sensing electrochemical AFM (PS-EC-AFM) technique [48]. Copyright 2017, Nature. (F) X-ray absorption spectroscopy [49].
Fig. 5. (A) Three schemes of the band gap modifications for visible light sensitization with a lower shift of CBM (a), a higher shift of VBM (b), and impurity states (c). (B) Strategies of solid solution for band engineering.
Fig. 6. (A) Band gap structure of K4Ce2M10O30 (M = Ta, Nb) and comparison with redox couples for the photocatalytic production of H2 and O2 from water. (B) Schematic crystal structure of K4Ce2M10O30 (M = Ta, Nb) [57]. Copyright 2007, Elsevier. (C) Band gap structure of K4Ce2Ta10-xNbxO30. (D) UV-vis diffuse reflectance spectra of H2 evolution of K4Ce2Ta10-xNbxO30 [58]. Copyright 2007, Elsevier. TEM images for NiOx anchoring on K4Ce2Ta10O30 (E) and K4Ce2Nb10O30 (F) [57]. Copyright 2007, Elsevier. (G) Photocatalysts K4Ce2M10O30 (M = Ta, Nb) without loading and with loading of Pt, RuO2, and NiOx. 0.1 g catalyst was dispersed in 20 mL of Na2SO3 solution (0.2 mol L?1) under visible light irradiation (> 420 nm) for 4 h [58]. Copyright 2007, Elsevier.
Fig. 7. (A) Diffuse reflection spectra of BiYWO6, Bi2O3, Y2O3, WO3, Bi2WO6, and Y2WO6 samples [40].Copyright 2008, American Chemical Society. (B) Diffuse reflectance UV-vis spectra of the BYV mixed oxides [41]. Copyright 2011, Royal Society of Chemistry. (C) UV-visible diffuse reflectance spectra of BMV solid solutions [65].Copyright 2012, Elsevier. (D) Schematic band structures of YVO4, BYV (0.5), zircon type BiVO4, and fergusonite BiVO4 [41]. Copyright 2011, Royal Society of Chemistry. (E) Time courses of photocatalytic water splitting over BYV (0.375) loaded with 0.275% Rh-0.4% Cr2O3 cocatalyst under full arc light irradiation (> 300 nm). Catalyst weight: 0.2 g [41]. Copyright 2011, Royal Society of Chemistry. (F) Photocatalytic activities of BMV solid solutions and effective ionic radii of M cations [65]. Copyright 2012, Elsevier.
Fig. 8. (A) XRD patterns of Bi3-xYxO4Cl. (B) UV-vis diffuse reflectance spectra (DRS) of Bi3-xYxO4Cl. (C) Crystal structure of Bi3-xYxO4Cl, and Elemental mappings of Bi3-xYxO4Cl. (D) H2 evolution rate of Bi3-xYxO4Cl under visible light. (E) H2 evolution rate of Bi2YO4Cl with different sacrificial agents under visible light [66]. Copyright 2021, Elsevier.
Fig. 9. (A) Bi16Sb4O32Cl4 supercell with space group P21cn. (B) XRD patterns of Bi4SbO8Cl. (C) Raman spectra of Bi4SbO8Cl. (D) UV-vis diffuse reflectance spectra (DRS) of Bi4SbO8Cl; inset: bandgaps of Bi4SbO8Cl estimated by related curves of (αhν)^2 vs. hν. (E) H2 evolution rate of Bi4SbO8Cl under visible light. (F,I) Band structures of Bi4NbO8Cl and Bi4SbO8Cl; (G,J) the full density of states for Bi4NbO8Cl and Bi4SbO8Cl; (H,K) the Bi partial density of states for Bi4NbO8Cl and Bi4SbO8Cl [67]. Copyright 2022, Elsevier.
Fig. 10. (A) XRD patterns of BixY1-xVO4 prepared by hydrothermal procedure (pH = 4, reaction temperature = 453 K, and reaction time = 48 h) [69]. Copyright 2017, Elsevier. (B) SEM images of BiVO4 (Scale bar, 500 nm) [68]. Copyright 2013, Springer Nature. (C) SEM images of BixY1-xVO4. (D) (100), (010), and (001) faces of BixY1-xVO4 (red: O; gray: V; purple: Bi; cyan: Y) [69]. (E) Sketch for the transfer of photogenerated charges [69]. Copyright 2017, Elsevier. (F) Raman spectrum of the prepared samples [61]. (G) Simulated photogenerated electric field distribution after the light irradiation [61]. Copyright 2020, Elsevier.
Fig. 11. (A) The migration of Bi elements within the crystal structure of tetragonal zircon-type BixY1-xVO4 mixed oxides toward the surface under increased pressure and elevated temperatures. (B) Diffuse reflectance UV-vis spectra of the BixY1-xVO4 under increased pressure. (C) Diffuse reflectance UV-vis spectra of the BixY1-xVO4 under elevated temperatures. (D) HRTEM images for the BixY1-xVO4 under increased pressure. (E) Schematic of relative band energy positions and the proposed photocatalytic OWS mechanism for BixY1-xVO4 and BixY1-xVO4 under increased pressure [71]. Copyright 2022, Elsevier. (F) a and d SEM images of BYVO and BYVO@PCN; b and e TEM images of BYVO and BYVO@PCN. (G) The schematic diagram of in-situ polycondensation melamine on the surface of BixY1-xVO4; (blue: N; gray: C; white: H; red: O; purple: Bi; green: Y; black gray: V); b the schematic diagram of the energy band alignment, electron charge transfer, and water splitting mechanism for BYVO@PCN [72]. Copyright 2023, Elsevier.
Fig. 12. HRTEM images of STO-N2 (A?C) and Blue-STO (D?F). (G) UV-vis-NIR diffuse reflectance spectra of STO-N2 and Blue-STO. (H) EPR spectra of STO-N2 and Blue-STO. (I) H2 and O2 evolution of STO-N2 and Blue-STO in pure water. (J) Schematic diagram for the influence of bulk and surface defects on photocatalytic activity [73]. Copyright 2023, Elsevier.
Fig. 13. (A) Scheme for Ge doped cobalt oxide for electrocatalytic and photocatalytic water splitting. (B) Photocatalytic OWS activity of BYV, BYV/CoOOH (PD), BYV/CO3O4 (WI), and BYV/CO2Ge1 (WI). (C) AQY values and UV-visible absorbance spectra for BYV and BYV/CO2Ge1 (WI). (D) Photocatalytic OWS system comprising a BYV solid solution and HEC and OEC cocatalysts, (E) energy band diagram of BYV, BYV/ CO3O4 (WI), and BYV/CO2Ge1 (WI) [86]. Copyright 2022, American Chemical Society.
Fig. 14. (A) Scheme of (Na, O) co doped g-C3N4 obtained by solvothermal method. (B) UV-vis absorption spectra of bulk g-C3N4 and (Na,O)-g-C3N4 [108]. Copyright 2017, Elsevier. (C,D) Polymerizable complex synthesis of SrTiO3:(Cr/Ta) photocatalysts to improve photocatalytic water splitting activity under visible light [109]. Copyright 2016, Elsevier.
Fig. 15. (A) Schematic representation of Kohn-Sham one-electron states and spin density plot of the substitutionally doped anatase TiO2. (B) Schematic representation of Kohn-Sham one-electron states and spin density plot of the interstitially doped anatase TiO2 [112]. Copyright 2023, Elsevier. (C) Diffusing reflectance spectra of N doped TiO2 powders at different N doped contents. (D) Photocatalytic activities for H2 evolution over N doped TiO2 (0.1 g) in 0.2 mol L?1 Na2SO3 solution. Light source: Xe lamp (300 W). Urea/TiO2 = 1, 3, 5, and 5 for samples (a), (b), (c) and (d) (> 400 nm), respectively, calcined at 350 °C; urea/TiO2 = 3 and calcined at 350 and 500 °C for samples (e) and (f), respectively [113]. Copyright 2006, Elsevier.
Fig. 16. (A) Schematic illustration of the structure and electronic DOS of a semiconductor in the form of a disorder engineered nanocrystal with dopant incorporation. Dopants are depicted as black dots and disorder is represented in the outer layer of the nanocrystal. The conduction and valence levels of a bulk semiconductor, Ec and Ev, respectively, are also shown, and the bands of the nanocrystals are shown on the left. The effect of disorder, which creases broadened tails of states extending into the otherwise forbidden band gap, is shown at the right, (B) A photo comparing unmodified white and disorder-engineered black, nanocrystals. (C,D) HRTEM images of TiO2, nanocrystals before and after hydrogenation, respectively. In (D), a short-dashed curve is applied to outline a portion of the interface between the crystalline core and the disordered outer layer (marked by white arrows) of black TiO2 [38]. Copyright 2011, Science. (E) SEM images of BYVO. (F) HRTEM images of BYVO. (G) SEM images of R-BYVO. (H)HRTEM images of R-BYVO. (I) Electronic band structure of BYVO and R-BYVO derived from UPS spectra and XPS Valence band spectra. (J) The apparent quantum yield. (K) The schematic diagram of the surface phosphorization process; (orchid: P; white: H; red: O; purple: Bi; green: Y; black gray: V). (L) The schematic diagram of the energy band structures for BYVO and R-BYVO [114]. Copyright 2023, American Chemical Society.
Fig. 17. (A) BF (a) and HAADF (b) STEM images of ZnmIn2S3+m/In(OH)3-1; Elemental mappings of In (c), Zn (d), O (e), and S (f). Inset: intensity profile corresponding to the red rectangle area. (B) (a) HRTEM image of the selected area A marked in Fig. 17(A); (b) HRTEM image and (c) SEAD pattern of the selected area I; (d) HRTEM image of the selected area II; (e) HRTEM image and (f) SEAD pattern of the selected area III. (g) Intensity profile corresponding to the yellow rectangle area in (d). (C) UV-vis diffuse reflectance spectra of ZnmIn2S3+m/In(OH)3-X. (D) H2 evolution rate of samples: (a) ZnIn2S4; (b) 1 wt % Pt/ZnIn2S4; (c) 1 wt% Pt/ ZnmIn2S3+m/In(OH)3-0.25; (d) 1 wt% Pt/ ZnmIn2S3+m/In(OH)3-0.5; (e) 1 wt% Pt/ ZnmIn2S3+m/In(OH)3-1; (f) 1 wt% Pt/ ZnmIn2S3+m/In(OH)3-2; (g) 1 wt% Pt/ In(OH)3. Reaction conditions: catalyst 50 mg; 60 mL aqueous solution containing 0.35 mol L?1 Na2S and 0.25 mol L?1 Na2SO3; 300 W Xe lamp with a 420 nm cut filter. (E) Schematic for charge separation and transfer in the concentration gradient ZnmIn2S3+m/In(OH)3 heterojunction composites [125]. Copyright 2020, Elsevier.
Fig. 18. (A,B,E) Schematic illustrations of K+ ion release controlled via point-diffusion occurring on PCN substrate with the resulting gradient K+ doping distribution, which exhibits an outstanding photocatalytic performance in hydrogen evolution. (C) The atomic arrangement of KTOpyr crystalline structure displays a unique coadjacent network with 3D channels for K+ storing and transfer. (D) The morphology characterization and microstructure observed in SEM imaging. Octahedral KTOpyr particles are embedded into the substrate and tightly wrapped by PCN layers. (F) Activity contrasts of different K+ doping sources with regard to photocatalytic hydrogen evolution from water splitting. Error bars are noted with black lines. (G) The apparent quantum yield. (H) In-situ XRD patterns recorded during the calcination of KTOpyr solely. (I) In-situ XRD patterns recorded during the calcination of KTOpyr embedded into PCN (M). (J) a-b, The BSE image (b) with the scale bar of 1 μm and five tagged collected points are schematized via RISE measurement (a), which is recorded on gradient K+ doped PCN&KTO sample. c-d, Raman spectra (c) at five points (#1-5) compared to pristine PCN with corresponding magnified windows of two dotted sections after smoothing and the variation trend of Raman intensity with the location (d) [42]. Copyright 2023, Elsevier.
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