电化学CO2还原为CH4的研究进展与挑战

doi:10.1016/S1872-2067(25)64672-9

催化学报 ›› 2025, Vol. 73: 39-61.DOI: 10.1016/S1872-2067(25)64672-9

电化学CO₂还原为CH₄的研究进展与挑战

熊磊^a, 付先彪^b()

^a电子科技大学基础与前沿研究院, 四川成都 610054, 中国
^b新加坡国立大学材料科学与工程系, 新加坡, 新加坡

收稿日期:2024-12-24 接受日期:2025-02-19 出版日期:2025-06-18 发布日期:2025-06-12
通讯作者: *电子信箱: xbfu@nus.edu.sg (付先彪).

Recent advances and challenges in electrochemical CO₂ reduction to CH₄

Lei Xiong^a, Xianbiao Fu^b()

^aInstitute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, Chengdu 610054, Sichuan, China
^bDepartment of Materials Science and Engineering, National University of Singapore, Singapore 117576, Singapore

Received:2024-12-24 Accepted:2025-02-19 Online:2025-06-18 Published:2025-06-12
Contact: *E-mail: xbfu@nus.edu.sg (X. Fu).
About author:Xianbiao Fu (Department of Materials Science and Engineering, National University of Singapore) received his B.S. degree from Central South University (2016) and his Ph.D. from the University of Electronic Science and Technology of China (2021). During his Ph.D. studies, he spent 2 years as a visiting graduate student at Northwestern University and 1 year at Johns Hopkins University. From 2021 to 2024, he conducted postdoctoral research Surface Physics & Catalysis (SurfCat) Center within the Department of Physics at the Technical University of Denmark. In 2022, he was awarded the prestigious Marie Skłodowska-Curie Postdoctoral Fellowship by the European Union. In 2025, he joined the Department of Materials Science and Engineering at the National University of Singapore as an Assistant Professor. His research focuses on electrocatalysis, electrochemical engineering, and electrosynthesis, specifically concentrating on electrochemical ammonia synthesis, nitrogen activation, and ammonia energy. He has published more than 40 peer-reviewed papers in esteemed international journals, with over 20 as the first or co-first author. He is the first or co-first author of publications in Science (2), Nature Materials, Nature Energy, Nature Chemical Engineering (also as corresponding author), Nature Catalysis, and Nature Communications. He is a Young Editorial Board Member of the Nano Letters, Journal of Energy Chemistry, Materials Horizons, Nano Research, and other leading journals. He won the MIT TR35 Innovator Award in 2023, the Carbon Future Young Investigator Award, and the Best Editor Award in 2023 of Nano Research. He is the winner of the 1^st Rising Stars in Materials Today Catalysis in 2024.

摘要/Abstract

摘要：

利用可再生能源电力将CO₂电化学还原(ECR)为燃料和基础化学品, 是减少CO₂排放和建立碳中和过程极具吸引力的途径. 在ECR产物中, 甲烷(CH₄)因其高热值(55.5 MJ·kg⁻¹)和清洁燃烧而脱颖而出, 也是天然气的主要成分. 然而, ECR产CH₄涉及8质子耦合电子转移步骤, 其缓慢的动力学过程导致活性和选择性难以控制, 是目前ECR产CH₄技术面临的主要挑战. 因此, 系统的反应机理研究和高效的催化剂开发是亟待解决的问题.

本文系统总结并讨论了目前ECR产CH₄的研究进展和未来应用策略. 首先, 本文结合前期的实验结果、原位表征以及理论计算, 深入探讨了ECR产CH₄的反应机理, 包括三种公认的反应途径, 涉及三种关键中间体, 即*CO, *CHO (或*COH)和*H, 且反应决速步均为*CO的第一次氢化即*CO+H⁺+e^-→*CHO(或*COH). 根据ECR产CH₄的关键催化剂—Cu基材料出发, 从晶面依赖性、尺寸效应和价态调结等方面概括了影响其本征活性的关键因素. 其中, (111)晶面取向和小尺寸的Cu有利于催化ECR产CH₄, 而Cu的价态(即Cu⁰和Cu^x⁺)对ECR产物选择性的影响仍存在争议. 随后, 归纳了近期关于ECR转CH₄催化剂的设计策略, 包括亚纳米催化剂的开发、Cu/氧化物界面工程和Cu表面改性等. 这些调控策略主要基于三个基本原理: (1)调控ECR关键中间体(*CO)的吸附强度, 诸如电解液离子影响(HCO₃^-, Cl^-, Br^-, I^-等)、价态调控、界面工程(Cu/氧化物)等; (2)抑制C-C耦合, 诸如降低活性位点数(Cu单原子催化剂和Cu纳米团簇)和降低中间体(*CO)表面覆盖度(如稀释CO₂); (3)适度的活性*H物种的活化和转移促进CO₂的加氢, 诸如修饰H活化能力优异的组分(金属Mn、甲醛树脂等)、降低pH值等. 最后, 本文基于高分辨率原位表征方法、高效反应器设计和高通量筛选方法应用于ECR高效转化为CH₄的未来发展提出了展望.

总而言之, 本文从反应机理的研究和催化剂调控的角度总结了ECR产CH₄研究的最新进展, 结合反应机理的研究, 提出了催化剂优化策略的基本原理, 可为今后通过ECR工业化生产CH₄的调控策略提供有力参考.

关键词: 电化学CO₂还原, CO₂-CH₄转化, 晶面依赖性, 尺寸效应, Cu基催化剂界面

Abstract:

The electrochemical CO₂ reduction (ECR) to hydrocarbon products is an attractive pathway to decrease CO₂ emission and advance a carbon-neutral process. Among the products of ECR, methane (CH₄) stands out due to its high calorific value, serving as the main component of natural gas. However, the development of ECR catalysts capable of producing CH₄ with both high activity and stability remains critically urgent. This review summarizes and explores the research progress and future application strategies for ECR toward CH₄ production. Combining experiments, in-situ characterizations, and theoretical calculations, this review examines mechanism of CH₄ formation in ECR. It then clarifies key factors affecting Cu-based catalysts for CH₄ production, including facet dependence, size effects, and valence states. Next, this review details emerging strategies such as sub-nanoscale catalysts, Cu/oxides interface engineering, and Cu surface modification. Finally, future directions highlight in-situ characterization, reactor design, and high-throughput screening, guiding industrial CH₄ production.

Key words: Electrochemical CO₂ reduction, CO₂-to-CH₄ conversion, Facet dependence, Size effects, Cu-based catalysts interface

熊磊, 付先彪. 电化学CO₂还原为CH₄的研究进展与挑战[J]. 催化学报, 2025, 73: 39-61.

Lei Xiong, Xianbiao Fu. Recent advances and challenges in electrochemical CO₂ reduction to CH₄[J]. Chinese Journal of Catalysis, 2025, 73: 39-61.

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图/表 20

Table 1 The equilibrium potentials for the ECR reaction to different products [16].

Reaction	E⁰ (V, vs. RHE)	Product
2H⁺ + 2e^- → H₂	0	H₂
CO₂+ 2H⁺ + 2e^- → HCOOH(aq)	-0.12	HCOOH
CO₂ + 2H⁺ + 2e^- → CO(g) + H₂O	-0.10	CO
CO₂ + 6H⁺ + 6e^- → CH₃OH(aq) + H₂O	0.03	CH₃OH
CO₂ + 8H⁺ + 8e^- → CH₄(g) + 2H₂O	0.17	CH₄
2CO₂ + 8H⁺ + 8e^- → CH₃COOH(aq) + 2H₂O	0.11	CH₃COOH
2CO₂ +12H⁺ + 12e^- → C₂H₄(g) + 4H₂O	0.08	C₂H₄
2CO₂ + 12H⁺ + 12e^- → C₂H₅OH(aq) + 3H₂O	0.19	CH₃CH₂OH
2CO₂ +14H⁺ + 14e^- → C₂H₆(g) + 4H₂O	0.14	C₂H₆
3CO₂ + 18H⁺ + 18e^- → C₃H₇OH(aq) + 5H₂O	0.10	n-CH₃CH₂CH₂OH

Fig. 1. Schematic illustration of mechanism study and enhanced strategies for ECR to CH4.

Fig. 2. The proposed reaction mechanisms of ECR to CH4.

Fig. 3. (a) FEs of ECR to deep-reduction products over single-crystal Cu with (100) and (111) facet. Reprinted with permission from Ref. [41]. Copyright 2020, American Chemical Society. (b) The high-potential methane and ethylene path via COH* on the Cu(100) facet at 0 V vs. reversible hydrogen electrode (RHE) and at -0.9 V vs. RHE. (c) Optimized structures of the transition states involved in *CO reduction to *CHO with the water-solvated model on the Cu(100) facet and to *COH with the H-shuttling model on the Cu(111) facet. (d) The closeup of the H3Oσ+ moiety in the transition state of *COH formation on Cu(100) and Cu(111). Reprinted with permission from Ref. [33]. Copyright 2016, American Chemical Society.

Fig. 4. (a) The ECR FE over Cu nanoparticles with the size range of 2-15 nm and relative population of surface atoms with a specific CN as a function of the particle diameter. Reprinted with permission from Ref. [42]. Copyright 2014, American Chemical Society. (b) The ECR FEs of Cu Oh-NCs with three sizes. Reprinted with permission from Ref. [43]. Copyright 2019, Royal Society of Chemistry. (c) The relative C2+/C1 products ratio of CO reduction over Cu/GDY catalysts with different nano sizes of Cu. Reprinted with permission from Ref. [44]. Copyright 2020, Wiley-VCH GmbH. (d) The relative free energy diagrams of CO2 reduction on the Cu55 NC and the comparison of the potential-limiting steps (*CO → *CHO) for the Cu13, Cu55, and Cu(111) models. Reprinted with permission from Ref. [45]. Copyright 2017, Elsevier.

Fig. 5. (a) Quasi in-situ Cu LMM Auger spectra of Cu nanocubes supported on C paper and on Cu foil before and after 1 h of ECR. (b) The relative FECH4 over different catalysts. Reprinted with permission from Ref. [50]. Copyright 2018, Wiley-VCH GmbH. (c) The scheme of SPVP-Cu NPs and DPVP-Cu NPs with different content of PVP as capping agent. (d) The relative in-situ Raman spectroscopy under ECR condition over SPVP-Cu NPs and DPVP-Cu NPs. Reprinted with permission from Ref. [51]. Copyright 2021, Wiley-VCH GmbH. (e) The Scheme of the self-sacrifice mechanism to protect Cu2+. (f) The Cu 2p XPS spectra of Cu-Ce-Ox before and after ECR. (g) The gas product FEs at different potentials of Cu-Ce-Ox. Reprinted with permission from Ref. [53]. Copyright 2022, American Chemical Society.

Fig. 6. (a) The schematic Cu clusters/DRC with small Cu clusters. The Adsorption energies of *CO (b) and *H (c) intermediates over different structures. Reprinted with permission from Ref. [55]. Copyright 2020, Wiley-VCH GmbH. (d) Schematic of the atomic agglomeration (marked with orange arrows) from CuPc reduction with CNP. (e) Comparison of the metallic Cu-Cu coordination number determined from EXAFS analysis and methanation selectivity. (f) The maximum FE toward CH4 and C2H4 for samples with different CNP to CuPc ratios. Reprinted with permission from Ref. [57]. Copyright 2021, Springer Nature. (g) The schematic of Cu2O@CuHHTP with Cu2O clusters. (h) TEM images of Cu2O@CuHHTP. (i) The free-energy diagrams of CO2 reduction to CH4 for Cu2O-(111)@HHTP and pristine Cu2O(111) crystal plane. Reprinted with permission from Ref. [58]. Copyright 2020, Wiley-VCH GmbH.

Fig. 7. (a) Schematic of the Cu-N-C-T catalysts with different Cu-Cu distances. (b) The faradaic efficiencies, partial current densities of CH4 and C2H4 (top panel, right y-axis), and the ratios of CH4/C2H4 (bottom panel) for Cu-N-C-T catalysts. Reprinted with permission from Ref. [61]. Copyright 2020, American Chemical Society. (c) Schematic illustration of Cu SAs/GDY for ECR to CH4. Reprinted with permission from Ref. [62]. Copyright 2022, Wiley-VCH GmbH. (d) Schematic illustration of electron-push-pull. (e) The average valance state of the prepared Cu SA/R-GDY. Reprinted with permission from Ref. [63]. Copyright 2022, Wiley-VCH GmbH. (f) Scheme of the Cu-CD catalysts with Cu-N2O2 configuration. (g) DFT simulations of hydrogen evolution on CuN2O2 (Cu-CDs), CuN4, and Cu(111). Reprinted with permission from Ref. [65]. Copyright 2021, Springer Nature. (h) The thermodynamic trend for ECR to CH4 at -1.2 V vs. RHE, as a function with Gad(CHO*) on Cu-NxBy. Reprinted with permission from Ref. [66]. Copyright 2023, Springer Nature.

Fig. 8. (a) The adsorption energy profile of *CO, *H, and co-adsorption of *CO and *H on CoPc and ZnN4, respectively. (b) CH4/CO production rate ratio over CoPc@Zn-N-C and Zn-N-C. (c) A proposed reaction mechanism of ECR to CH4 over CoPc@Zn-N-C. Reprinted with permission from Ref. [67]. Copyright 2020, American Chemical Society. (d) Schematic illustration of SA-Zn/MNC for ECR to CH4. (e) The comparison of CH4. Faradic efficiency for SA-Zn/MNC with other catalysts. Reprinted with permission from Ref. [68]. Copyright 2023, Wiley-VCH GmbH.

Fig. 9. (a) Schematic of switching ECR production toward CH4 and C2H4 as well as the reaction-free energies of the C2H4 pathway and the CH4 pathway over Cu(111), Cu1/CeO2(111), and Cu7/CeO2(111). Reprinted with permission from Ref. [71]. Copyright 2024, American Chemical Society. (b) Schematic illustration of regulating the ECR pathway for C2+ and CH4 production by CuSm-Ox with distinct ratios. (c) Average FEs of C2+ and CH4 products at the current density of 500 mA·cm-2 over different feeding ratios of Cu/Sm catalysts. Reprinted with permission from Ref. [72]. Copyright 2023, American Chemical Society.

Fig. 10. (a) Schematic illustration of the influence of *CO configuration on the ECR selectivity towards C2+ or CH4 over different catalysts. (b) The percentage of *COLFB at different potentials over different catalysts. Reprinted with permission from Ref. [74]. Copyright 2022, American Chemical Society. (c) In-situ ATR-SEIRA study of key reaction intermediate *COads. (d) Potential-dependent *COads population normalized by ECSA. (e) Normalized *COads population of the three samples at -1.1 V and their corresponding COads composition. Reprinted with permission from Ref. [76]. Copyright 2024, American Chemical Society.

Fig. 11. (a) Schematic illustration for the Synthesis of Cu/CeO2@C. Reprinted with permission from Ref. [88]. Copyright 2023, American Chemical Society. (b) Schematic illustration of the accelerating *CO hydrogenation over Cu-np/NC catalysts. Reprinted with permission from Ref. [89]. Copyright 2022, The Royal Society of Chemistry. (c) The scheme for synthesizing core-shell Cu@NxC catalysts. (d) The potential-dependent integral area ratio of *COL and *COB. (e) The DFT calculation for ΔE of *CO intermediate on different surfaces. (f) The scheme for the proposed mechanistic pathways of CH4 and C2H4 over the Cu@NxC-350 °C and Cu@NxC-400 °C catalysts. Reprinted with permission from Ref. [90]. Copyright 2023, American Chemical Society.

Fig. 12. (a) Dopant addition blocks C-C coupling and shifts the product distribution toward methane. Reprinted with permission from Ref. [91]. Copyright 2022, Elsevier. (b) Schematic Illustration of CO2-dilution strategy to regulate the ECR selectivity to CH4. (c) Reaction energies of two competing reactions (protonation of *CO to *CHO, and C-C coupling) under different *CO coverages. (d) The ECR gas product distribution under different applied current densities using pure CO2 and CO2 concentration of 75%. Reprinted with permission from Ref. [92]. Copyright 2020, American Chemical Society. (e) Schematic diagrams showing the *CO flux in Ag@Cu2O-x NCs with varying envelope sizes of the OD-Cu, and the modulation of reduction products by emanative *CO molecules generated from the Ag core. Reprinted with permission from Ref. [93]. Copyright 2021, Wiley-VCH GmbH.

Fig. 13. (a) Schematic illustration of the different *CO and *H coverages for ECR to CH4, C2H4, and H2 on CuxZnyMnz catalysts. Reprinted with permission from Ref. [94]. Copyright 2023, Wiley-VCH GmbH. (b) Schematic illustration of the hydrophobic core-shell architecture, which can constrain H2O availability via hydrophobic carbon coating. Reprinted with permission from Ref. [95]. Copyright 2022, The Royal Society of Chemistry. (c) Schematic illustration of the regulation of proton-transfer dynamics to control the ECR products over C2+ or CH4. (d) Energy barriers of *CO hydrogenation and coupling processes with different hydrogen coverage situations. Reprinted with permission from Ref. [96]. Copyright 2024, American Chemical Society.

Fig. 14. (a) Stationary CH4 Faradaic selectivity of ECR as a function of potentials and schematic illustration of how the presence of I- affects the net charge of Cu, making it more negative and facilitating the charge transfer for CO reduction. Reprinted with permission from Ref. [97]. Copyright 2016 American Chemical Society. (b) Schematic illustrations for the structures of an electric double layer under pulsed CP mode. (c) Schematic illustration for the ECR route in the electrolyte with F-, Cl-, and HCO3-. Reprinted with permission from Ref. [99]. Copyright 2023, American Chemical Society.

Fig. 15. The free energy profiles of electrochemical CO reduction at pH = 1 (a) and pH = 7 (b). Reprinted with permission from Ref. [101]. Copyright 2016, American Chemical Society. (c) The logarithms of CH4 partial current densities plotted in RHE scale. The logarithms of partial current densities for CH4 formation vs. logarithms of pCO at electrolyte pH of 13.9 (d) and 9.0 (e). Reprinted with permission from Ref. [102]. Copyright 2021, Springer Nature.

Table 2 The summary of proposed reaction schemes for CH4 formation.

	Proposed reaction path	Tafel slope^a	CO order (high θ_CO)	pH dependent
A	CO + H₂O + e^- →CO(H) + OH^- (RDS)	118 mV∙dec^-1	0	No
A	CO(H) + H → CO(H)₂ +	118 mV∙dec^-1	0	No
B	CO + H₂O + e^- →CO(H) + OH^-	59 mV∙dec^-1	Negative	Yes
B	CO(H) + H → CO(H)₂ + (RDS)	59 mV∙dec^-1	Negative	Yes

Table 3 Comparison of catalytic performance for recently reported electrocatalysts towards ECR to CH4.

Category	Catalyst	Reactor	Electrolyte	E (V vs. RHE)	FE_CH4 (%)	j_CH4 (mA·cm^-2)	CEE^a (%)	Stability	Ref.
Sub- nanoscale catalysts	CuPc	H-Cell	0.5 mol·L^-1 KHCO₃	-1.06	66	13	30.6	—	[56]
	CNP:CuPc (4:1)	MEA	0.05 mol·L^-1 KHCO₃	—	62	136	—	> 110 h	[57]
	Cu clusters/DRC	H-Cell	0.5 mol·L^-1 KHCO₃	-1.0	81.7	—	38.8	40 h	[55]
	Cu₂O@CuHHTP	H-Cell	0.1 mol·L^-1 KCl + 0.1 mol·L^-1 KHCO₃	-1.4	73	10.8	29.4	1.5 h	[58]
	us-Cu-np.	flow cell	1 mol·L^-1 KOH	-1.2	68	323	29.7	> 8 h	[106]
	Cu-N-C-900	H-Cell	0.5 mol·L^-1 KHCO₃	-1.6	38.6	14.8	14.5	—	[61]
	Cu SAs/GDY	H-Cell	0.1 mol·L^-1 KHCO₃	-1.2	66	40	28.8	10 h	[62]
	Cu SA/F-GDY	flow cell	1 mol·L^-1 KOH	-1.2	72.3	—	31.5	11 h	[63]
	Cu SAs/HGDY	flow cell	1 mol·L^-1 KOH	-1.1	72.1	230.7	32.8	11 h/MEA	[64]
	Cu-CDs	H-Cell	0.5 mol·L^-1 KHCO₃	-1.44	78	40	31.0	6 h	[65]
	BNC-Cu	H-Cell	0.5 mol·L^-1 KHCO₃	-1.46	73	292	28.8	8 h	[66]
	EDTA/CuPc/CNP	MEA	0.005 mol·L^-1 H₂SO₄	—	71	71	—	5 h	[107]
	CoPc@Zn-N-C	flow cell	1 mol·L^-1 KOH	-1.24	18 ± 2	44±7	7.7±0.9	—	[67]
	SA-Zn/MNC	H-Cell	1 mol·L^-1 KHCO₃	-1.8	85	31.8	29.7	35 h	[68]
	DAT electrode	MEA	0.1 mol·L^-1 KHCO₃	—	52 ± 4	130 ± 10	—	10 h/10 A	[108]
Cu/oxides interface engineering	La₂CuO₄	flow cell	1 mol·L^-1 KOH	-1.4	56.3	117	22.7	—	[70]
	Cu-Ce-O_x	flow cell	1 mol·L^-1 KOH	-1.4	67.8	135.6	27.3	6 h	[53]
	Cu₁Sm₉-Ox	flow cell	1 mol·L^-1 KOH	—	65	325	—	84 h	[72]
	Cu₂O-CeO₂-w	H-Cell	0.1 mol·L^-1 KHCO₃	-1.1	40 ± 1	—	18.2 ± 0.5	10 h	[76]
	Cu₅Ce₉₅O_x	flow cell	1 mol·L^-1 KOH	-1.2	61.2	230	26.7	500 h	[71]
	Cu‐CeO₂‐4%	H-Cell	0.1 mol·L^-1 KHCO₃	-1.8	58	56	20.3	2.5 h	[109]
	CeO₂cluster-7%Cu	flow cell	1 mol·L^-1 KOH	—	67.1	268.4	—	3.3 h	[78]
	Cu/ceria-H₂	flow cell	1 mol·L^-1 KOH	-1.49	70.0	105	27.3	7.5 h	[80]
	Cu/p-Al₂O₃SAC	flow cell	—	-1.2	62	153.0	27.0	—	[81]
Cu surface modification	Cu_8-(MMI)₄(tBuS)₄	flow cell	1 mol·L^-1 KOH	-1.2	53.7	89.1	23.4	24 h/MEA	[110]
	Ga-doped CuAl	flow cell	1 mol·L^-1 KHCO₃	-1.4	53	109	21.4	11 h	[91]
	Cu catalysts	flow cell	1 mol·L^-1 KHCO₃	—	48 ± 2	108 ± 5	—	22 h	[92]
	Ag@Cu₂O-6.4 NCs	flow cell	1 mol·L^-1 KOH	-1.2	74 ± 2	178 ± 5	32.3 ± 0.9	5.5 h	[93]
	Cu/CeO₂@C	flow cell	1 mol·L^-1 KOH	-1.5	80.3	138.6	31.2	9 h	[88]
	Cu-np/NC	flow cell	1 mol·L^-1 KOH	—	73.4	234	—	50 h/MEA	[89]
	Cu₈ZnMn	flow cell	1 mol·L^-1 KOH	-2.2	55 ± 2.8	418 ± 22	17.0 ± 0.9	6 h	[94]
	H-CuO_x@C	flow cell	1 mol·L^-1 KOH	-1.6	73 ± 6	366.5	27.3 ±2.2	6 h	[95]
	Cu₂O@RF	flow cell	1 mol·L^-1 KHCO₃	—	51	561	—	—	[96]
	Sputtered Cu	flow cell	1 mol·L^-1 H₃PO₄+3 mol·L^-1 KCl	—	27	162	—	—	[103]
	Cu-PTFE	flow cell	0.005 mol·L^-1 H₂SO₄ + 1 mol·L^-1 Na₂SO₄	—	48	105.6	—	—	[104]
	Cu-3	flow cell	0.005 mol·L^-1 H₂SO₄ + 0.5 mol·L^-1 Na₂SO₄	—	51.2	307.2	—	4.4 h	[105]

Table 3 Comparison of catalytic performance for recently reported electrocatalysts towards ECR to CH4.

Category	Catalyst	Reactor	Electrolyte	E (V vs. RHE)	FE_CH4 (%)	j_CH4 (mA·cm^-2)	CEE^a (%)	Stability	Ref.
Sub- nanoscale catalysts	CuPc	H-Cell	0.5 mol·L^-1 KHCO₃	-1.06	66	13	30.6	—	[56]
	CNP:CuPc (4:1)	MEA	0.05 mol·L^-1 KHCO₃	—	62	136	—	> 110 h	[57]
	Cu clusters/DRC	H-Cell	0.5 mol·L^-1 KHCO₃	-1.0	81.7	—	38.8	40 h	[55]
	Cu₂O@CuHHTP	H-Cell	0.1 mol·L^-1 KCl + 0.1 mol·L^-1 KHCO₃	-1.4	73	10.8	29.4	1.5 h	[58]
	us-Cu-np.	flow cell	1 mol·L^-1 KOH	-1.2	68	323	29.7	> 8 h	[106]
	Cu-N-C-900	H-Cell	0.5 mol·L^-1 KHCO₃	-1.6	38.6	14.8	14.5	—	[61]
	Cu SAs/GDY	H-Cell	0.1 mol·L^-1 KHCO₃	-1.2	66	40	28.8	10 h	[62]
	Cu SA/F-GDY	flow cell	1 mol·L^-1 KOH	-1.2	72.3	—	31.5	11 h	[63]
	Cu SAs/HGDY	flow cell	1 mol·L^-1 KOH	-1.1	72.1	230.7	32.8	11 h/MEA	[64]
	Cu-CDs	H-Cell	0.5 mol·L^-1 KHCO₃	-1.44	78	40	31.0	6 h	[65]
	BNC-Cu	H-Cell	0.5 mol·L^-1 KHCO₃	-1.46	73	292	28.8	8 h	[66]
	EDTA/CuPc/CNP	MEA	0.005 mol·L^-1 H₂SO₄	—	71	71	—	5 h	[107]
	CoPc@Zn-N-C	flow cell	1 mol·L^-1 KOH	-1.24	18 ± 2	44±7	7.7±0.9	—	[67]
	SA-Zn/MNC	H-Cell	1 mol·L^-1 KHCO₃	-1.8	85	31.8	29.7	35 h	[68]
	DAT electrode	MEA	0.1 mol·L^-1 KHCO₃	—	52 ± 4	130 ± 10	—	10 h/10 A	[108]
Cu/oxides interface engineering	La₂CuO₄	flow cell	1 mol·L^-1 KOH	-1.4	56.3	117	22.7	—	[70]
	Cu-Ce-O_x	flow cell	1 mol·L^-1 KOH	-1.4	67.8	135.6	27.3	6 h	[53]
	Cu₁Sm₉-Ox	flow cell	1 mol·L^-1 KOH	—	65	325	—	84 h	[72]
	Cu₂O-CeO₂-w	H-Cell	0.1 mol·L^-1 KHCO₃	-1.1	40 ± 1	—	18.2 ± 0.5	10 h	[76]
	Cu₅Ce₉₅O_x	flow cell	1 mol·L^-1 KOH	-1.2	61.2	230	26.7	500 h	[71]
	Cu‐CeO₂‐4%	H-Cell	0.1 mol·L^-1 KHCO₃	-1.8	58	56	20.3	2.5 h	[109]
	CeO₂cluster-7%Cu	flow cell	1 mol·L^-1 KOH	—	67.1	268.4	—	3.3 h	[78]
	Cu/ceria-H₂	flow cell	1 mol·L^-1 KOH	-1.49	70.0	105	27.3	7.5 h	[80]
	Cu/p-Al₂O₃SAC	flow cell	—	-1.2	62	153.0	27.0	—	[81]
Cu surface modification	Cu_8-(MMI)₄(tBuS)₄	flow cell	1 mol·L^-1 KOH	-1.2	53.7	89.1	23.4	24 h/MEA	[110]
	Ga-doped CuAl	flow cell	1 mol·L^-1 KHCO₃	-1.4	53	109	21.4	11 h	[91]
	Cu catalysts	flow cell	1 mol·L^-1 KHCO₃	—	48 ± 2	108 ± 5	—	22 h	[92]
	Ag@Cu₂O-6.4 NCs	flow cell	1 mol·L^-1 KOH	-1.2	74 ± 2	178 ± 5	32.3 ± 0.9	5.5 h	[93]
	Cu/CeO₂@C	flow cell	1 mol·L^-1 KOH	-1.5	80.3	138.6	31.2	9 h	[88]
	Cu-np/NC	flow cell	1 mol·L^-1 KOH	—	73.4	234	—	50 h/MEA	[89]
	Cu₈ZnMn	flow cell	1 mol·L^-1 KOH	-2.2	55 ± 2.8	418 ± 22	17.0 ± 0.9	6 h	[94]
	H-CuO_x@C	flow cell	1 mol·L^-1 KOH	-1.6	73 ± 6	366.5	27.3 ±2.2	6 h	[95]
	Cu₂O@RF	flow cell	1 mol·L^-1 KHCO₃	—	51	561	—	—	[96]
	Sputtered Cu	flow cell	1 mol·L^-1 H₃PO₄+3 mol·L^-1 KCl	—	27	162	—	—	[103]
	Cu-PTFE	flow cell	0.005 mol·L^-1 H₂SO₄ + 1 mol·L^-1 Na₂SO₄	—	48	105.6	—	—	[104]
	Cu-3	flow cell	0.005 mol·L^-1 H₂SO₄ + 0.5 mol·L^-1 Na₂SO₄	—	51.2	307.2	—	4.4 h	[105]

Fig. 16. (a) Schematic illustration of cation-augmenting layer (CAL) in acidic electrolyte. (b) FE toward H2 and CH4 on sputtered Cu catalyst at different current densities in 1 mol·L-1 H3PO4 and 3 mol·L-1 KCl. (c) FE toward all products on sputtered Cu catalyst in 1 mol·L-1 H3PO4 with different KCl concentrations at 400 mA?cm-2. Reprinted with permission from Ref. [103]. Copyright 2021, American Association for the Advancement of Science. (d) FECH4:FEC2+ on Cu-PTFE with different electrolytes at different current densities. (e) The adsorption energy comparisons for proton and CO2 on Cu surfaces with different cations. (f) The adsorption energy comparisons of key adsorbates CHO* and OCCO* on Cu surfaces with different cations. Reprinted with permission from Ref. [104]. Copyright 2022, Wiley-VCH GmbH. Schematic of proposed mechanism for hydrogenation of *CO intermediate near electrode surface without (g) or with (h) 18-C-6 molecule. (i) Formation rate and KIE value of CH4 on Cu and Cu-3 catalysts at 1.05 V using 0.5 M K2SO4 electrolyte with H2O or D2O as the solvent. Reprinted with permission from Ref. [105]. Copyright 2023, Wiley-VCH GmbH.

Fig. 17. The development outlook of the ECR mechanisms and catalytic performance suitable for industrial application. (a) The development of high-resolution in-situ characterization method. (b) The schematic diagram of the cascade ECR device. (c) The high-throughput screening.

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电化学CO₂还原为CH₄的研究进展与挑战

Recent advances and challenges in electrochemical CO₂ reduction to CH₄

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