光催化用于有机物选择性转移氢化研究进展

doi:10.16085/j.issn.1000-6613.2023-1957

摘要/Abstract

摘要：

近几十年，光催化的发展为能源的有效利用开辟了新的道路。基于光催化的转移氢化技术无需使用气态氢气、反应条件温和、能量来源清洁可持续、反应进程易控，有望用于新时代背景下的有机物选择性转化。本文综述了近年来光催化体系用于有机物选择性转移氢化的研究进展。首先，阐述了光催化转移氢化的原理。其次，从不同官能团选择性氢化的角度，梳理和归纳了不同光催化剂及其反应体系的研究成果，解释了典型催化体系的反应机理，介绍了新型的氢化体系和底物高值化的途径。最后，指出了光催化加氢仍存在反应速率及量子效率低、用于可见光的光催化剂较少、传统反应器不适用和使用耗电模拟光源等不足。对此，对光催化与电催化协同、开发新型光催化剂、设计适用于光催化的反应器及直接利用太阳能进行光催化等作出了展望。

关键词: 催化, 光化学, 加氢, 选择性, 能源

Abstract:

In recent decades, the development of photocatalysis has opened up new paths for the efficient utilization of energy. Transfer hydrogenation based on photocatalysis offers advantages such as the absence of gaseous hydrogen, mild reaction conditions, reliance on clean and renewable energy sources, and controllable reaction processes. In this paper, research progress in recent years on photocatalysis for selective transfer hydrogenation of organic compounds is reviewed. Firstly, the mechanism of photocatalytic transfer hydrogenation is presented. Secondly, based on the different functional groups being hydrogenated, the research achievements of various photocatalysts and reaction systems are summarized and the reaction mechanism of typical catalytic systems is explained. New hydrogenation systems and ways of substrate valorization are also introduced. Finally, it is pointed out that photocatalytic hydrogenation still encounters challenges such as low reaction rate and low quantum efficiency, limited photocatalysts suitable for visible light, incompatible to traditional reactors, and the use of power-consuming simulated light sources. In this regard, the prospects including the combination of photocatalysis and electrocatalysis, the development of new photocatalysts, the design of reactors suitable for photocatalysis, and the direct utilization of solar energy for photocatalysis, are made.

Key words: catalysis, photochemistry, hydrogenation, selectivity, energy

中图分类号:

潘晟昊, 陈伦刚, 张兴华, 张琦, 马隆龙, 刘建国. 光催化用于有机物选择性转移氢化研究进展[J]. 化工进展, 2024, 43(12): 6723-6734.

PAN Shenghao, CHEN Lungang, ZHANG Xinghua, ZHANG Qi, MA Longlong, LIU Jianguo. Research progress on photocatalysis for selective transfer hydrogenation of organic compounds[J]. Chemical Industry and Engineering Progress, 2024, 43(12): 6723-6734.

图/表 17

参考文献 67

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催化剂	制备方法	价带/eV	导带/eV	带隙/eV	光源波长/nm	氢供体	参考文献
Pt/TiO₂	浸渍-光还原	—	—	—	365	异丙醇	[16]
Pt/TiO₂	浸渍-煅烧-氢气还原	—	—	—	365	甲醇	[25]
Au/TiO₂	浸渍-光还原	—	—	—	可见光	异丙醇	[16]
Au/CuCo₂O₄	聚丙烯腈纤维为模板-沉淀-煅烧-光还原	2.66	1.30	1.36	>420	异丙醇	[26]
Co₃O₄/MgAl-LDH	共沉淀-煅烧-水中搅拌	0.54	-1.53	2.07	480~800	异丙醇	[27]
Ov-WO₃@CB[5]	两步煅烧-两步组装	2.25	-0.5	2.75	415~425	氨硼烷	[28]
AEROXIDE^® P25 TiO₂	—	2.5	-0.7	3.2	紫外光	对甲氧基苯甲醇	[29]
MIL-100(Fe_0.63Al_0.37)	水热-真空加热	2.32	-0.28	2.60	≥400	苯甲醇	[30]

催化剂	制备方法	价带/eV	导带/eV	带隙/eV	光源波长/nm	氢供体	参考文献
Pt/TiO₂	浸渍-光还原	—	—	—	365	异丙醇	[16]
Pt/TiO₂	浸渍-煅烧-氢气还原	—	—	—	365	甲醇	[25]
Au/TiO₂	浸渍-光还原	—	—	—	可见光	异丙醇	[16]
Au/CuCo₂O₄	聚丙烯腈纤维为模板-沉淀-煅烧-光还原	2.66	1.30	1.36	>420	异丙醇	[26]
Co₃O₄/MgAl-LDH	共沉淀-煅烧-水中搅拌	0.54	-1.53	2.07	480~800	异丙醇	[27]
Ov-WO₃@CB[5]	两步煅烧-两步组装	2.25	-0.5	2.75	415~425	氨硼烷	[28]
AEROXIDE^® P25 TiO₂	—	2.5	-0.7	3.2	紫外光	对甲氧基苯甲醇	[29]
MIL-100(Fe_0.63Al_0.37)	水热-真空加热	2.32	-0.28	2.60	≥400	苯甲醇	[30]

催化剂	制备方法	光源波长/nm	氢供体	参考文献
Pt/TiO₂	浸渍-光还原	385	甲醇	[41]
Ni/C₃N₄	热聚合-浸渍-还原	420	甲醇	[42]
BCN+NiP	煅烧+原位生成	455	甲醇/水溶液	[43]
CoTPPS+[Ru(bpy)₃]²⁺	—	450	水	[44]

催化剂	制备方法	光源波长/nm	氢供体	参考文献
Pt/TiO₂	浸渍-光还原	385	甲醇	[41]
Ni/C₃N₄	热聚合-浸渍-还原	420	甲醇	[42]
BCN+NiP	煅烧+原位生成	455	甲醇/水溶液	[43]
CoTPPS+[Ru(bpy)₃]²⁺	—	450	水	[44]

催化剂	制备方法	价带/eV	导带/eV	带隙/eV	光源波长/nm	氢供体	参考文献
P25	HF处理	—	—	3.15	>300	异丙醇	[46]
TiO₂@N-AC	浸渍-两次煅烧-硝酸处理	—	—	—	可见光	异丙醇	[47]
TiO₂-Pd NO	水热-浸渍	—	—	—	365±15	乙醇	[48]
Pt/BMO-NS	水热-光还原	—	—	2.56	>400	醋酸铵	[49]
Pd/MIL-101(Fe)-2MI(300)	水热-光还原-热处理	—	—	2.22	蓝光	苯甲醇	[50]
sPS/P25	凝胶法	—	—	—	365	乙醇	[51]
g-C₃N₄	热沉积	1.3	-1.4	2.7	可见光	肼	[52]
CuFeS₂ NCs	共沉淀	—	—	—	400~500	肼	[53]
Ce-Ga-Zn(O,S)	共沉淀	—	—	3.5	紫外光	水	[54]
Pd/KPCN	水热-光还原	1.68	-1.05	2.73	420~780	水	[55]