光催化二氧化碳还原制多碳产物的先进光催化剂设计与机制: 现状与挑战

doi:10.1016/S1872-2067(23)64642-X

催化学报 ›› 2024, Vol. 60: 25-41.DOI: 10.1016/S1872-2067(23)64642-X

光催化二氧化碳还原制多碳产物的先进光催化剂设计与机制: 现状与挑战

杜晨宇^a, 盛剑平^a^,^b^,^*(), 钟丰忆^a, 何烨^a, 孙艳娟^a, 董帆^a^,^b^,^c^,^*()

^a电子科技大学资源与环境学院, 四川成都 611731, 中国
^b中国气象局气候资源经济转化重点开放实验室, 重庆 401147, 中国
^c电子科技大学基础与前沿研究院, 碳中和与环境能源技术研究中心, 四川成都 611731, 中国
^d乌兹别克斯坦共和国科学院通用和无机化学研究所, 坦什干 100047, 乌兹别克斯

收稿日期:2023-12-29 接受日期:2024-03-02 出版日期:2024-05-18 发布日期:2024-05-20
通讯作者: *电子信箱: jpshengchn@163.com (盛剑平), dongfan@uestc.edu.cn/dfctbu@126.com (董帆).
基金资助:
国家自然科学基金(22361142703);国家自然科学基金(22225606);国家自然科学基金(22261142663);国家自然科学基金(22176029);中国气候学会气候资源向经济转化开放重点实验室(2023005K);四川科技厅项目(2021JDJQ0006)

Rational design and mechanistic insights of advanced photocatalysts for CO₂-to-C₂₊ production: Status and challenges

Chenyu Du^a, Jianping Sheng^a^,^b^,^*(), Fengyi Zhong^a, Ye He^a, Vitaliy P. Guro^d, Yanjuan Sun^a, Fan Dong^a^,^b^,^c^,^*()

^aSchool of Resources and Environment, University of Electronic Science and Technology of China, Chengdu 611731, Sichuan, China
^bCMA Key Open Laboratory of Transforming Climate Resources to Economy, Chongqing 401147, China
^cResearch Center for Carbon-Neutral Environmental & Energy Technology, Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, Chengdu 611731, Sichuan, China
^dInstitute of General and Inorganic Chemistry, Academy of Sciences of the Republic of Uzbekistan, Tashkent 100047, Uzbekistan

Received:2023-12-29 Accepted:2024-03-02 Online:2024-05-18 Published:2024-05-20
Contact: *E-mail: jpshengchn@163.com (J. Sheng), dongfan@uestc.edu.cn/dfctbu@126.com (F. Dong).
About author:Jianping Sheng received his Ph.D. degree in 2018 from the College of Chemistry and Chemical Engineering, Central South University, China. Currently, he is an associate professor at the School of Resources and Environment, University of Electronic Science and Technology of China. His current research interest is the design and synthesis of novel perovskite quantum dot-based catalysts for environment and energy photocatalysis..
Fan Dong received his Ph.D. degree in 2010 from Zhejiang University. Currently, he is a full professor at the Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China. His research interest includes photocatalysis, environmental and energy catalysis.
Supported by:
National Natural Science Foundation of China(22361142703);National Natural Science Foundation of China(22225606);National Natural Science Foundation of China(22261142663);National Natural Science Foundation of China(22176029);CMA Key Open Laboratory of Transforming Climate Resources to Economy(2023005K);Sichuan Science and Technology Program(2021JDJQ0006)

摘要/Abstract

摘要：

在可持续碳资源利用的研究中, 光催化CO₂转化为高附加值化学品的前景日益凸显. 相较于常见的CO₂还原产物如甲烷、一氧化碳或甲酸, 具有两个或更多碳原子的C₂₊化合物因其具有更高的附加值而备受关注. 然而, 目前的研究面临着C-C偶联过程和多质子耦合电子转移效率的限制, 导致光催化CO₂的还原反应产物主要为C₁化合物. 常规光催化剂难以突破这些动力学和热力学壁垒, 导致目标产物C₂₊化合物的生成量远低于实际工业应用所需要的水平. 因此, 开发具有良好性能的光催化剂, 以实现C₂₊化合物的高效制备, 仍是当前面临的重要科学挑战.

本文系统性地概述了光催化CO₂还原为C₂₊化合物领域的最新研究进展. 首先, 从光催化的基本原理及C₂₊产物的生成路径出发, 在光催化剂设计方面, 为突破C-C偶联和多质子耦合电子转移的限制, 需要解决以下问题: (1) 关键中间产物的生成与吸附转移; (2) 活性位点对于中间产物的选择性; (3) 光生电子的寿命与定向转移. 随后, 详细介绍了高效、高选择性光催化剂的合理设计策略, 包括缺陷工程、双金属位点、表面等离子体共振以及异质结构造等. 同时, 深入探讨了C-C偶联和多电子偶联的质子转移过程的催化机制. 最后, 展望了光催化CO₂还原制C₂₊高附加值产物的未来研究方向, 催化剂设计与机制研究的关键方向包括: (1) 设计高选择性和高效吸附*CO中间体的活性位点, 以提升催化性能; (2) 设计具有轨道匹配的双活性位点以减少邻近*CO中间体间的静电排斥, 促进C-C耦合; (3) 从分子轨道相互作用角度深入理解C-C耦合和电子转移过程, 揭示反应机制; (4) 鉴别反应过程中的自由基组分, 阐明多质子耦合电子转移过程的机理.

综上所述, 本文系统地梳理了光催化CO₂还原制C₂₊高附加值产物的研究进展、关键问题、催化剂设计原理以及未来研究方向, 旨在为开发设计高效、高选择性催化剂提供有益的参考.

关键词: CO₂还原, C₂₊产物, 光催化, 活性位, 反应机理

Abstract:

Photocatalytic CO₂ conversion into high-value chemicals is becoming an increasingly promising avenue of research in the quest for sustainable carbon resource utilization. Particularly, compounds with two or more carbons (C₂₊) have higher added value than methane, carbon monoxide, or formate, which are typically the major products of CO₂ reduction. In this review, we present a detailed account of recent advancements in the field of photocatalytic CO₂ conversion, with a specific focus on the synthesis of multi-carbon oxygenates. We systematically introduce the rational design of photocatalysts with high effectivity and selectivity, which follows a methodical inside-to-outside order. These strategies consider various aspects of photocatalyst optimization, from the core structure to the surface properties. Meanwhile, we delve into an in-depth analysis of the underlying catalytic mechanisms, particularly emphasizing the C-C coupling and multi-electron-coupled proton transfer processes. Lastly, we examine the prospects and challenges in developing photocatalysts for CO₂ conversion, providing valuable insights for researchers and practitioners. This review aims to serve as a valuable resource for those seeking to design advanced catalysts for efficient photocatalytic CO₂ reduction.

Key words: CO₂ reduction, C₂₊ product, Photocatalysis, Active site, Reaction mechanism

杜晨宇, 盛剑平, 钟丰忆, 何烨, 孙艳娟, 董帆. 光催化二氧化碳还原制多碳产物的先进光催化剂设计与机制: 现状与挑战[J]. 催化学报, 2024, 60: 25-41.

Chenyu Du, Jianping Sheng, Fengyi Zhong, Ye He, Vitaliy P. Guro, Yanjuan Sun, Fan Dong. Rational design and mechanistic insights of advanced photocatalysts for CO₂-to-C₂₊ production: Status and challenges[J]. Chinese Journal of Catalysis, 2024, 60: 25-41.

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图/表 11

Fig. 1. The scheme illustrates the sequence of events involved in CO2 photoreduction to yield C2+ products, encompassing light absorption, charge carrier separation, and surface redox reactions. These processes can be significantly improved by employing a systematic design approach for photocatalyst development.

Table 1 Reaction enthalpy and redox potentials of various photocatalytic CRR reference to NHE at pH 7 [32,44,45].

Product	Reaction	NHE at pH 7 & reaction enthalpy
(COOH)₂	2CO₂ + 2e^‒ + 2H⁺ = (COOH)₂	E₀ = ‒0.88 V
	2CO₂ +H₂O = (COOH)₂ + 1/2O₂	ΔH = 458.6 kJ mol⁻¹
	2CO₂ +H₂O = (COOH)₂ + 1/2O₂	ΔG = 873.17 kJ mol⁻¹
CH₃COOH	2CO₂ + 8e^‒ + 8H⁺ = CH₃COOH + 2H₂O	E₀ = ‒0.3 V
	2CO₂ +2H₂O = CH₃COOH + 2O₂	ΔH = 874.53 kJ mol⁻¹
	2CO₂ +2H₂O = CH₃COOH + 2O₂	ΔG = 873.17 kJ mol⁻¹
CH₃CHO	2CO₂ + 10e^‒ + 10H⁺ = CH₃CHO + 3H₂O	E₀ = ‒0.3 V
	2CO₂ + 2H₂O = CH₃CHO + 5/2O₂	ΔH = 1166.96 kJ mol⁻¹
	2CO₂ + 2H₂O = CH₃CHO + 5/2O₂	ΔG = 1129.56 kJ mol⁻¹
CH₃CH₂OH	2CO₂ + 12e^‒ + 12H⁺ = CH₃CH₂OH + 3H₂O	E₀ = ‒0.32 V
	2CO₂ +3H₂O = CH₃CH₂OH + 3O₂	ΔH = 1090.53 kJ mol⁻¹
	2CO₂ +3H₂O = CH₃CH₂OH + 3O₂	ΔG = 1470.31 kJ mol⁻¹
C₂H₄	2CO₂ + 12e^‒ + 12H⁺ = C₂H₄ + 4H₂O	E₀ = 0.06 V
	2CO₂ +2H₂O = C₂H₄ + 3O₂	ΔH = 1411.06 kJ mol⁻¹
	2CO₂ +2H₂O = C₂H₄ + 3O₂	ΔG = 1324.52 kJ mol⁻¹
C₂H₆	2CO₂ + 14e^‒ + 14H⁺ = C₂H₆ + 4H₂O	E₀ = ‒0.27 V
	2CO₂ + 3H₂O = C₂H₆ + 7/2O₂	ΔH = 1559.8 kJ mol⁻¹
	2CO₂ + 3H₂O = C₂H₆ + 7/2O₂	ΔG = 1467.5 kJ mol⁻¹
C₃H₈	3CO₂ + 20e^‒ + 20H⁺ = C₃H₈ + 6H₂O	E₀ = ‒0.32 V
	3CO₂ + 4H₂O = C₃H₈ + 5O₂	ΔH = 2220.6 kJ mol⁻¹
	3CO₂ + 4H₂O = C₃H₈ + 5O₂	ΔG = 1903.4 kJ mol⁻¹

Fig. 2. Possible activation modes and first intermediates of CO2 reduction reaction [2,44?-46].

Fig. 3. (a) The role of photoinduced peat in the photothermal reduction of CO2 to CH3COOH. (b) Quasi-in situ Raman spectra of the Vo-rich Zn2GeO4 nanobelts in simulated air, depicting the behavior of sample under controlled illumination and dark conditions. (c) The rates of evolution for CO, HCOOH, and CH3COOH over the Vo-rich Zn2GeO4 nanobelts under diverse testing conditions in simulated air. Reprinted with permission from Ref. [61]. Copyright 2021, American Chemical Society. Visual representations of a relaxed slab model with four layers for pristine anatase TiO2 (d) and Nb-doped anatase TiO2(001) (e) surfaces. Reprinted with permission from Ref. [67]. Copyright 2020, American Chemical Society.

Fig. 4. (a) Band edge positions and photocatalytic mechanism: A comparative band diagram displaying SnS2-C and SnS2, along with the proposed separation of photo-excited electron-hole pairs in SnS2-C. (b) Comparison of solar fuel formation rates and quantum efficiencies under visible light (300?W halogen lamp) for SnS2-C, SnS2, and commercial SnS2. Reprinted with permission from Ref. [68]. Copyright 2018, Springer Nature. (c) Charge density differences (yellow represents electron accumulation, and purple denotes electron depletion). (d) Fourier transforms of EXAFS spectra at the Cu K-edge. Reprinted with permission from Ref. [31]. Copyright 2023, Springer Nature.

Fig. 5. (a) Schematic depiction of the CO2 photoreduction process using Cu-Ag ASNCs/TiO2, showcasing Ti, O, Cu, Ag, and C atoms as blue, red, gray-blue, violet, and brown spheres, respectively. (b) Formation rates of C2H4, CH4, H2, and CO by the catalysts after 8-hour simulated sunlight (AM1.5G) irradiation. (c) Gibbs free energy calculations depicting the reaction pathways and C-C coupling step during CO2 photoreduction on Cu-Ag alloy/TiO2. Reprinted with permission from Ref. [79]. Copyright 2023, the National Academy of Sciences of the United States of America.

Fig. 6. (a) The schematic illustrates the fabrication process of NiCo-TiO2. (b) The comparison of CO2 adsorption on NiC-TiO2. (c) C-C coupling activation barriers in NiCo-TiO2, Ni-TiO2, and Co-TiO2. (d) The CO2RR reaction pathway on NiCo-TiO2. Reprinted with permission from Ref. [80]. Copyright 2022, John Wiley and Sons.

Fig. 7. Differential charge density maps of ZnPor-RuCuDAC (a), ZnPorRu2DAC (b), and ZnPorCu2DAC (c). Diagrammatic representation of the interactions between the adsorbed CO (5σ,2π*) orbitals and the Cu 3d (d) and Ru 4d (e) orbitals in ZnPor-RuCuDAC. Reprinted with permission from Ref. [81]. Copyright 2023, Springer Nature.

Fig. 8. (a) Diagram showing the chemical mechanism for the plasmonic excitation-catalyzed Au-NP photocatalyzed CO2 conversion to hydrocarbons. Gas chromatography was used to track product turnover (GC). It was discovered that the characteristics of the light excitation, such as photon energy (excitation wavelength) and photon flux (light intensity), affected the hydrocarbon selectivity (C2 vs. C1). Reprinted with permission from Ref. [92]. Copyright 2018, American Chemical Society. (b) Schematic showing the mild conditions and selective conversion of CO2 and CH4 to ethylene through the combination of photocatalytic and plasma processes. (c) The impact of the primary photocatalyst type under simulated solar irradiation. Reproduced with permission from Ref. [93]. Copyright 2019, American Chemical Society.

Fig. 9. (a) Diagrammatic representation of the process of photoexcited electron-hole separation. (b) The potential reaction pathway engaged in the g-C3N4/CuO@MIL-125(Ti) photocatalyst. Reprinted with permission from Ref. [106]. Copyright 2018, Elsevier. (c) Diagram outlining the synthesis procedure of Bi2S3@In2S3. (d) Proposed CRR catalytic mechanisms for Bi2S3@In2S3, Bi2S3, and In2S3. Reprinted with permission from Ref. [107]. Copyright 2023, American Chemical Society.

Table 2 Photocatalytic CRR to C2+ products performance.

Type	Catalyst	C₂₊ products and production rate(μmol g⁻¹ h⁻¹)	Selectivity (%)	Condition	Ref.
Defect engineering	V_o-rich Zn₂GeO₄nanobelts	CH₃COOH 12.7	66.9	Xe lamp AM 1.5G (100 mW cm⁻²)	[61]
	SnS₂-C	CH₃CHO 9.2	—	300 W Halogen lamp	[68]
	Sn_xNb_1-xO₂	C₂H₅OH 292.5	87.6	Xe arc lamp (200 mW cm⁻²)	[110]
	CN-KRb	CH₃CHO 303.1	93.9	5 W white LED Slight panel (100 mW cm⁻²)	[111]
	CCN	C₂H₅OH 2.4	14.8	350 W Xe lamp AM 1.5G	[50]
	MIL-88B-NS40	C₂H₄17.7	10.6	300 W Xe lamp (> 420 nm), H₂O	[59]
	Ce-MOF-RuII-bpy	CH₃COOH 128	99.8	300 W Xenon lamp (99.5 mW cm⁻²)	[112]
	0.5Ru-0.6LGCN	C₂H₆ 153.68; C₂H₅OH 130.38; CH₃CH(OH) CH₃133.33	75.8	UV-Vis & 100 °C	[66]
	Pt_1%-0.50-G/RBT	C₂H₆ 11	22.9	AM 1.5G	[113]
	Nb-doped TiO₂nanotube	CH₃CHO 500	98.1	simulated solar illumination at 200 mW cm⁻²	[67]
	SCN-Cu/TiO₂-SBO-3	C₂H₄ 4.8	40	300 W Xenon lamp	[114]
	V_s-SAL₁₀	C₂H₄ 44.3	88.9	300 W Xenon arc lamp	[58]
Dual-metal sites	NiCo-TiO₂	CH₃COOH 2.6	71	300 W Xe lamp, water with 0.1 M Na₂SO₃ and 0.2 M CsOH	[80]
	AuIr@InGaN NWs/Si	C₂H₆ 59000	7.3	300 W Xenon lamp (3.5 W cm⁻²)	[115]
	CuACs/PCN	C₂H4 10.17	53.2	300 W Xe lamp, TEOA + C₃₀H₂₄Cl₂N₆Ru·6H₂O/H₂O	[20]
	Cu-Ag ASNCs/TiO₂	C₂H₄ 1110.6	49.1	300 W Xenon lamp (500 mW cm⁻²)	[79]
	InCu/PCN	C₂H₅OH 28.5	92	300 W Xenon lamp (1 W cm⁻²)	[82]
	Co-CoO_x/MAO	C₂₊H_x 1156	91.6	300 W Xenon lamp (1200 mW/ cm⁻²)	[30]
	Co-Cu/TiO₂	C₂H₆ 892	69.3	300 W Xenon lamp	[116]
	AgCu/TNTAs	C₂H₆ 23.88	60.7	300 W Xe AM 1.5G, TEOA/H₂O	[85]
	P/Cu SAs@CN	C₂H₆ 616.6	33.4	300 W Xenon lamp, TEOA/H₂O	[23]
Surface plasmon resonance	AgCu-TNTA	C₂H₆ 9.38	39.3	AM1.5G 1-sun simulated sunlight	[27]
	Au/TiO_2‒_x	C₂H₄ 686	37.4	84.2 mW cm⁻² xenon lamp	[93]
	Ag/AgClBr	CH₃CHO 209.3	96.9	500 W Xenon lamp (100 mW cm⁻²), NaHCO₃ (0.1 M)/TEA(1 mL)	[117]
Heterojunction construction	WO₃/In₂O₃	C₃H₆ 15.6 (μmol m⁻² h⁻¹)	—	80 °C and 2 cm³ min⁻¹ flow rate	[118]
	g-C₃N₄/CuO@MIL-125(Ti)	C₂H₅OH 501.9; CH₃COOH 177.2	63.4	1 mL of H₂O, 1.0 MPa CO₂, and 300 W Xe lamp	[106]
	CuO/TiO₂	CH₃CH₂OH 27.1	68.4	water containing Na₂SO₃, 500 W Hg lamp at 365 nm	[119]
	RGO/ZnV₂O₆	CH₃COOH 38.5	5.15	35W HID Xe lamp, water with 0.1 mo L⁻¹ NaOH	[120]
	Cu-CuTCPP/Cu₂O/CoAl-LDH	C₂H₄ 1.56; C₂H₆ 1.92	37.45	Ar/Air/H₂ mass gas flow, Xe lamp	[121]
	Bi₂S₃@In₂S₃	C₂H₄ 11.81	86	UV-vis irradiation (320 nm < λ < 780 nm, 0.20 W cm⁻²), 123 °C	[107]
	CuGaS₂@CuO	C₂H₄ 20.6	75.1	450 W xenon lamp, 0.1 mo L⁻¹ NaOH	[108]
	ZIF-8/CdS	C₂H₄ 0.8	12.8	300 W Xe lamp	[122]
	CuOX@p-ZnO	C₂H₄ 22.3	32.9	300 W Xe lamp	[123]
	Cu^δ+/CeO₂-TiO₂	C₂H₄ 0.81	73.9	200 mW cm⁻² Xe lamp	[124]

Table 2 Photocatalytic CRR to C2+ products performance.

Type	Catalyst	C₂₊ products and production rate(μmol g⁻¹ h⁻¹)	Selectivity (%)	Condition	Ref.
Defect engineering	V_o-rich Zn₂GeO₄nanobelts	CH₃COOH 12.7	66.9	Xe lamp AM 1.5G (100 mW cm⁻²)	[61]
	SnS₂-C	CH₃CHO 9.2	—	300 W Halogen lamp	[68]
	Sn_xNb_1-xO₂	C₂H₅OH 292.5	87.6	Xe arc lamp (200 mW cm⁻²)	[110]
	CN-KRb	CH₃CHO 303.1	93.9	5 W white LED Slight panel (100 mW cm⁻²)	[111]
	CCN	C₂H₅OH 2.4	14.8	350 W Xe lamp AM 1.5G	[50]
	MIL-88B-NS40	C₂H₄17.7	10.6	300 W Xe lamp (> 420 nm), H₂O	[59]
	Ce-MOF-RuII-bpy	CH₃COOH 128	99.8	300 W Xenon lamp (99.5 mW cm⁻²)	[112]
	0.5Ru-0.6LGCN	C₂H₆ 153.68; C₂H₅OH 130.38; CH₃CH(OH) CH₃133.33	75.8	UV-Vis & 100 °C	[66]
	Pt_1%-0.50-G/RBT	C₂H₆ 11	22.9	AM 1.5G	[113]
	Nb-doped TiO₂nanotube	CH₃CHO 500	98.1	simulated solar illumination at 200 mW cm⁻²	[67]
	SCN-Cu/TiO₂-SBO-3	C₂H₄ 4.8	40	300 W Xenon lamp	[114]
	V_s-SAL₁₀	C₂H₄ 44.3	88.9	300 W Xenon arc lamp	[58]
Dual-metal sites	NiCo-TiO₂	CH₃COOH 2.6	71	300 W Xe lamp, water with 0.1 M Na₂SO₃ and 0.2 M CsOH	[80]
	AuIr@InGaN NWs/Si	C₂H₆ 59000	7.3	300 W Xenon lamp (3.5 W cm⁻²)	[115]
	CuACs/PCN	C₂H4 10.17	53.2	300 W Xe lamp, TEOA + C₃₀H₂₄Cl₂N₆Ru·6H₂O/H₂O	[20]
	Cu-Ag ASNCs/TiO₂	C₂H₄ 1110.6	49.1	300 W Xenon lamp (500 mW cm⁻²)	[79]
	InCu/PCN	C₂H₅OH 28.5	92	300 W Xenon lamp (1 W cm⁻²)	[82]
	Co-CoO_x/MAO	C₂₊H_x 1156	91.6	300 W Xenon lamp (1200 mW/ cm⁻²)	[30]
	Co-Cu/TiO₂	C₂H₆ 892	69.3	300 W Xenon lamp	[116]
	AgCu/TNTAs	C₂H₆ 23.88	60.7	300 W Xe AM 1.5G, TEOA/H₂O	[85]
	P/Cu SAs@CN	C₂H₆ 616.6	33.4	300 W Xenon lamp, TEOA/H₂O	[23]
Surface plasmon resonance	AgCu-TNTA	C₂H₆ 9.38	39.3	AM1.5G 1-sun simulated sunlight	[27]
	Au/TiO_2‒_x	C₂H₄ 686	37.4	84.2 mW cm⁻² xenon lamp	[93]
	Ag/AgClBr	CH₃CHO 209.3	96.9	500 W Xenon lamp (100 mW cm⁻²), NaHCO₃ (0.1 M)/TEA(1 mL)	[117]
Heterojunction construction	WO₃/In₂O₃	C₃H₆ 15.6 (μmol m⁻² h⁻¹)	—	80 °C and 2 cm³ min⁻¹ flow rate	[118]
	g-C₃N₄/CuO@MIL-125(Ti)	C₂H₅OH 501.9; CH₃COOH 177.2	63.4	1 mL of H₂O, 1.0 MPa CO₂, and 300 W Xe lamp	[106]
	CuO/TiO₂	CH₃CH₂OH 27.1	68.4	water containing Na₂SO₃, 500 W Hg lamp at 365 nm	[119]
	RGO/ZnV₂O₆	CH₃COOH 38.5	5.15	35W HID Xe lamp, water with 0.1 mo L⁻¹ NaOH	[120]
	Cu-CuTCPP/Cu₂O/CoAl-LDH	C₂H₄ 1.56; C₂H₆ 1.92	37.45	Ar/Air/H₂ mass gas flow, Xe lamp	[121]
	Bi₂S₃@In₂S₃	C₂H₄ 11.81	86	UV-vis irradiation (320 nm < λ < 780 nm, 0.20 W cm⁻²), 123 °C	[107]
	CuGaS₂@CuO	C₂H₄ 20.6	75.1	450 W xenon lamp, 0.1 mo L⁻¹ NaOH	[108]
	ZIF-8/CdS	C₂H₄ 0.8	12.8	300 W Xe lamp	[122]
	CuOX@p-ZnO	C₂H₄ 22.3	32.9	300 W Xe lamp	[123]
	Cu^δ+/CeO₂-TiO₂	C₂H₄ 0.81	73.9	200 mW cm⁻² Xe lamp	[124]

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光催化二氧化碳还原制多碳产物的先进光催化剂设计与机制: 现状与挑战

Rational design and mechanistic insights of advanced photocatalysts for CO₂-to-C₂₊ production: Status and challenges

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光催化二氧化碳还原制多碳产物的先进光催化剂设计与机制: 现状与挑战

Rational design and mechanistic insights of advanced photocatalysts for CO2-to-C2+ production: Status and challenges

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Rational design and mechanistic insights of advanced photocatalysts for CO₂-to-C₂₊ production: Status and challenges