电荷极化光催化剂光转化二氧化碳制多碳化学品的研究进展

doi:10.16085/j.issn.1000-6613.2023-2064

摘要/Abstract

摘要：

二氧化碳（CO₂）光合成高附加值多碳化学品是缓解温室效应和能源危机的极具前景的绿色发展新技术。设计具有电荷极化活性位点的光催化剂能够有效降低C-C偶联反应能垒，进而提高光合成多碳化学品催化选择性和活性。本文综述了光催化CO₂还原制C₂化学品的相关研究，深入研究电荷不对称位点构筑的主要策略，阐明微观层面上电荷极化效应对C₂产物活性和选择性的影响机制，总结出极具前景的高效光催化剂的设计与开发思路，为光催化技术的实际应用提供重要的理论和实践指导。展望未来，应更加注重催化剂在原子层面上的精准调控，开发出更高效、更专一的多碳产物制备系统，助力能源产业结构的低碳转型。

关键词: 碳中和, 二氧化碳, 光催化, C-C偶联反应, 电荷极化

Abstract:

Photosynthesis of high-value multi-carbon chemicals from carbon dioxide (CO₂) represents an exceptionally promising avenue for green technology development, offering a dual solution to the challenges of greenhouse gas accumulation and the looming energy crisis. Designing photocatalysts with charge-polarized active sites can effectively lower the energy barriers for C-C coupling reaction, which significantly boosts the selectivity and efficiency of multi-carbon chemical synthesis. This paper provides a comprehensive review of the latest advances in the photocatalytic reduction of CO₂ to C₂ chemicals, exploring the pivotal strategies for engineering charge asymmetry at active sites. It also elucidates the activity and selectivity of C₂ products regulatory mechanisms at the microscopic level influenced by charge polarization effects. This paper summarizes the most promising approach for the design and development of efficient photocatalysts, providing theoretical and practical guidance for the actual application of photocatalytic technology. Moving forward, it is imperative to concentrate on the precise control at the atomic level of catalysts, and to develop more efficient and specific multi-carbon product preparation systems, thereby supporting the low-carbon transformation of the energy industry structure.

Key words: carbon neutral, carbon dioxide, photocatalysis, C-C coupling reaction, charge polarization

中图分类号:

O643.36

解仲凯, 施伟东. 电荷极化光催化剂光转化二氧化碳制多碳化学品的研究进展[J]. 化工进展, 2024, 43(5): 2714-2722.

XIE Zhongkai, SHI Weidong. Research progress of charge polarized photocatalysts in photoconversion carbon dioxide into multi-carbon chemicals[J]. Chemical Industry and Engineering Progress, 2024, 43(5): 2714-2722.

图/表 8

参考文献 59

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光催化剂	光催化测试条件	光源及光强	C₂化学品产率/μmol·g^-1·h^-1	参考文献
Au₁/RP	50mg光催化剂，0.5g KHCO₃, 1~2mL 6mol/L的HCl	300W氙灯，300mW·cm^-2	1.32 (C₂H₆)	[10]
Bi₁₉S₂₇Cl₃	10mg光催化剂，20mL水，0.4mg Na₂S，2.9mg Na₂SO₃，CO₂	420W氙灯，未提及光强	5.19 (CH₃CH₂OH)	[17]
Cu SAs/UiO-66-NH₂	100mg光催化剂，50mL水，100µL TEOA，100kPa CO₂	300W氙灯，未提及光强	4.22 (CH₃CH₂OH)	[19]
Co-doped NiS₂	10mg光催化剂，10kPa CO₂	300W氙灯，100mW·cm^-2	2.3 (C₂H₄)	[26]
P/Cu SAs@CN	0.5mg光催化剂，25mL水，3.0mL TEOA，65kPa CO₂	300W氙灯，未提及光强	616.6 (C₂H₆)	[27]
CuACs/PCNs	5mg光催化剂，45mL水，5mL TEOA，100kPa CO₂，C₃₀H₂₄Cl₂N₆Ru·6H₂O	300W氙灯，未提及光强	10.2 (C₂H₄)	[28]
WO_3-_x -2	5mg光催化剂，0.2mL水，100kPa CO₂	300W氙灯，未提及光强	61.6 (C₂H₄)	[33]
CuO _X @p-ZnO	5mg光催化剂，水，50kPa CO₂	300W氙灯，100mW·cm^-2	2.7 (C₂H₄)	[40]
In_2.77S₄(P6)	3mg光催化剂，20mL水，100kPa CO₂	300W氙灯，110mW·cm^-2	67.65 (C₂H₄)	[42]

光催化剂	光催化测试条件	光源及光强	C₂化学品产率/μmol·g^-1·h^-1	参考文献
Au₁/RP	50mg光催化剂，0.5g KHCO₃, 1~2mL 6mol/L的HCl	300W氙灯，300mW·cm^-2	1.32 (C₂H₆)	[10]
Bi₁₉S₂₇Cl₃	10mg光催化剂，20mL水，0.4mg Na₂S，2.9mg Na₂SO₃，CO₂	420W氙灯，未提及光强	5.19 (CH₃CH₂OH)	[17]
Cu SAs/UiO-66-NH₂	100mg光催化剂，50mL水，100µL TEOA，100kPa CO₂	300W氙灯，未提及光强	4.22 (CH₃CH₂OH)	[19]
Co-doped NiS₂	10mg光催化剂，10kPa CO₂	300W氙灯，100mW·cm^-2	2.3 (C₂H₄)	[26]
P/Cu SAs@CN	0.5mg光催化剂，25mL水，3.0mL TEOA，65kPa CO₂	300W氙灯，未提及光强	616.6 (C₂H₆)	[27]
CuACs/PCNs	5mg光催化剂，45mL水，5mL TEOA，100kPa CO₂，C₃₀H₂₄Cl₂N₆Ru·6H₂O	300W氙灯，未提及光强	10.2 (C₂H₄)	[28]
WO_3-_x -2	5mg光催化剂，0.2mL水，100kPa CO₂	300W氙灯，未提及光强	61.6 (C₂H₄)	[33]
CuO _X @p-ZnO	5mg光催化剂，水，50kPa CO₂	300W氙灯，100mW·cm^-2	2.7 (C₂H₄)	[40]
In_2.77S₄(P6)	3mg光催化剂，20mL水，100kPa CO₂	300W氙灯，110mW·cm^-2	67.65 (C₂H₄)	[42]

光催化剂	光催化测试条件	光源及光强	C₂化学品产率/μmol·g^-1·h^-1	参考文献
InCu/PCN	50mg光催化剂，3mL水，21mL DMF，80kPa CO₂	300W氙灯，1000mW·cm^-2	28.5 (CH₃CH₂OH)	[18]
CuGaS₂	5mg光催化剂，20mL水，100kPa CO₂，pH=12	450W氙灯，未提及光强	20.6 (C₂H₄)	[22]
FeCoS₂	10mg光催化剂，100kPa CO₂	300W氙灯，100mW·cm^-2	20.1 (C₂H₄)	[25]
V_S-AgInP₂S₆	4~5mg光催化剂，0.4mL水，100kPa CO₂	300W氙灯，未提及光强	44.3 (C₂H₄)	[31]
CuGaS₂/Ga₂S₃	20mg光催化剂，3mL水，TEOA，70kPa CO₂	300W氙灯，未提及光强	335.7 (C₂H₄)	[32]
Cu_0.8Au_0.2/TiO₂	2.0mg光催化剂，0.15mL水，90kPa CO₂	300W氙灯，500mW·cm^-2	369.8 (C₂H₄)	[34]
Cu_0.8Ag_0.2/TiO₂	2.0mg光催化剂，0.15mL水，90kPa CO₂	300W氙灯，500mW·cm^-2	1110.6 (C₂H₄)	[35]
Pt_0.35%-Cu_1.00%-BT	40mg光催化剂，水，CO₂	300W氙灯，100mW·cm^-2	25 (C₂H₆)	[36]
CuPt/WO₃	40mg光催化剂，20mL水，HCl，90kPa CO₂	300W氙灯，未提及光强	19.41 (CH₃COOH)	[37]
In₂O₃/Cu-O₃	10mg光催化剂，10mL水，CO₂	300W氙灯，未提及光强	20.7 (CH₃CH₂OH)	[38]
Cu ^δ⁺/CeO₂-TiO₂	10mg光催化剂，30mL水，100kPa CO₂	300W氙灯，200mW·cm^-2	4.51 (C₂H₄)	[39]
r-In₂O₃/InP	50mg光催化剂，100mL水，80kPa CO₂	300W氙灯，未提及光强	9.67 (CH₃COOH)	[41]
Bi₂S₃@In₂S₃	5mg光催化剂，1mL水，100kPa CO₂	300W氙灯，1150mW·cm^-2	11.81 (C₂H₄)	[43]

光催化剂	光催化测试条件	光源及光强	C₂化学品产率/μmol·g^-1·h^-1	参考文献
InCu/PCN	50mg光催化剂，3mL水，21mL DMF，80kPa CO₂	300W氙灯，1000mW·cm^-2	28.5 (CH₃CH₂OH)	[18]
CuGaS₂	5mg光催化剂，20mL水，100kPa CO₂，pH=12	450W氙灯，未提及光强	20.6 (C₂H₄)	[22]
FeCoS₂	10mg光催化剂，100kPa CO₂	300W氙灯，100mW·cm^-2	20.1 (C₂H₄)	[25]
V_S-AgInP₂S₆	4~5mg光催化剂，0.4mL水，100kPa CO₂	300W氙灯，未提及光强	44.3 (C₂H₄)	[31]
CuGaS₂/Ga₂S₃	20mg光催化剂，3mL水，TEOA，70kPa CO₂	300W氙灯，未提及光强	335.7 (C₂H₄)	[32]
Cu_0.8Au_0.2/TiO₂	2.0mg光催化剂，0.15mL水，90kPa CO₂	300W氙灯，500mW·cm^-2	369.8 (C₂H₄)	[34]
Cu_0.8Ag_0.2/TiO₂	2.0mg光催化剂，0.15mL水，90kPa CO₂	300W氙灯，500mW·cm^-2	1110.6 (C₂H₄)	[35]
Pt_0.35%-Cu_1.00%-BT	40mg光催化剂，水，CO₂	300W氙灯，100mW·cm^-2	25 (C₂H₆)	[36]
CuPt/WO₃	40mg光催化剂，20mL水，HCl，90kPa CO₂	300W氙灯，未提及光强	19.41 (CH₃COOH)	[37]
In₂O₃/Cu-O₃	10mg光催化剂，10mL水，CO₂	300W氙灯，未提及光强	20.7 (CH₃CH₂OH)	[38]
Cu ^δ⁺/CeO₂-TiO₂	10mg光催化剂，30mL水，100kPa CO₂	300W氙灯，200mW·cm^-2	4.51 (C₂H₄)	[39]
r-In₂O₃/InP	50mg光催化剂，100mL水，80kPa CO₂	300W氙灯，未提及光强	9.67 (CH₃COOH)	[41]
Bi₂S₃@In₂S₃	5mg光催化剂，1mL水，100kPa CO₂	300W氙灯，1150mW·cm^-2	11.81 (C₂H₄)	[43]

光催化剂	光催化测试条件	光源及光强	C₁化学品产率/μmol·g^-1·h^-1	参考文献
BP-Bi₂₄O₃₁Br₁₀	30mg光催化剂，50mL水，80kPa CO₂	300W氙灯，未提及光强	39.8 (CO)	[44]
V_BiO-Bi₂₄O₃₁Br₁₀	30mg光催化剂，50mL水，80kPa CO₂	300W氙灯，300mW·cm^-2	24.9 (CO)	[45]
V_W-Bi₂WO₆	10mg光催化剂，1.7g NaHCO₃，15mL 4mol/L的H₂SO₄	300W氙灯，未提及光强	30.62 (CO)	[46]
Cu_1.95S_1-_x	10mg光催化剂，10mL水，100kPa CO₂	300W氙灯，未提及光强	13.63 (CH₄)	[47]
Ni:CdS	催化剂，5mL水，1mL三乙醇胺，100kPa CO₂	300W氙灯，未提及光强	9.5 (CO)	[48]
Mn-CsPbBr₃	2mg光催化剂，10mL水，100kPa CO₂	300W氙灯，100mW·cm^-2	45.4 (CO)/约3.5 (CH₄)	[49]
Mo/TiO₂	光催化剂，20uL水，20mL CO₂	300W氙灯，未提及光强	8.2 (CO)/约9.8 (CH₄)	[50]
Ni-BiOBr	5mg光催化剂，1mL水，5mg [Ru(bpy)₃]Cl₂·6H₂O，1mL三乙醇胺，4mL CH₃CN，100kPa CO₂	300W氙灯，未提及光强	378.7 (CO) μ	[51]
PtRu/TiO₂	100mg光催化剂，2mL水，CO₂	300W氙灯，80mW·cm^-2	38.7 (CH₄)	[52]
SnS₂/Pt₃Co	20mg光催化剂，100mL水，140kPa CO₂	300W氙灯，未提及光强	27.34 (CO)/约14.02 (CH₄)	[53]
TiO₂-AuCu-V	15mg光催化剂，1mL水，150kPa CO₂	300W氙灯，未提及光强	3.4 (CO)/约33.5 (CH₄)	[54]
Pd₇Cu₁-TiO₂	5mg光催化剂，1mL水，200kPa CO₂	300W氙灯，未提及光强	19.6 (CH₄)	[55]
TiO₂-Pd	15mg光催化剂，2mL水，150kPa CO₂	300W氙灯，未提及光强	12.6 (CO)/约3.0 (CH₄)	[56]
Au-TiO₂	50mg光催化剂，0.084g NaHCO₃，0.6mL 4mol/L的HCl	300W氙灯，未提及光强	70.34 (CO)/约19.75 (CH₄)	[57]
Ni/SOM-ZIF-8	3mg光催化剂，2mL水，10mg [Ru(bpy)₃]Cl₂·6H₂O，2mL三乙醇胺，6mL CH₃CN，100kPa CO₂	300W氙灯，未提及光强	4.2 (CO) mmol/(g·h)	[58]
Co₁/ZnO	1mg光催化剂，4mL水，10mg [Ru(bpy)₃]Cl₂·6H₂O，4mL三乙醇胺，16mL CH₃CN，100kPa CO₂	300W氙灯，未提及光强	22.5 (CO) mmol/(g·h)	[59]