Cu-Ag纳米团簇CO2电催化还原性能和机理

doi:10.16085/j.issn.1000-6613.2024-0392

摘要/Abstract

摘要：

电催化二氧化碳还原是有效减少二氧化碳排放和促进能源绿色发展的技术，要实现将CO₂转化为高价值化合物和燃料（C₂₊）且走向工业化规模仍面临诸多难题。本文利用磁控共溅射技术在碳纸（CP）上成功负载Cu-Ag合金纳米团簇，并通过调控Ag靶材的溅射频率，制备了5种不同Cu/Ag配比的碳基Cu-Ag电极（Cu-Ag/CP），其中Cu-Ag20W/CP颗粒尺寸在228~285nm之间，并评估其电化学性能。结果表明，Cu-Ag/CP有效抑制析氢反应和提高C₂₊产物的产量，其C₂₊法拉第效率（ $F E C 2 +$ ）是碳基Cu电极的2.21倍。Cu-Ag20W/CP在恒电位为-1.07V（vs.RHE）和CO₂气体流速为5sccm下， $F E C 2 +$ 达78.74%，电流密度达67.92mA/cm²，且在连续运行8h后其催化性能和表面结构较为稳定。Cu-Ag/CP具有较大的电化学活性面积和导电性，且明显具有串联催化剂的特征，Ag引入使得*CO生成位点增加，脱附*CO转移至Cu表面进行*CO二聚反应。Cu-Ag/CP是一种具有前景的电催化材料，同时该材料合成方法适合大批量连续生产模式，且产物是高价值的C₂₊产品，有望为未来电催化CO₂工业化提供技术参考。

关键词: Cu-Ag催化剂, 电化学, 二氧化碳, 还原, 磁控共溅射, C₂₊产物

Abstract:

Electrocatalytic carbon dioxide reduction is an effective technology to mitigate CO₂ emissions and promote green energy development. However, the conversion of CO₂ into high-value compounds and fuels (C₂₊) on an industrial scale still faces many challenges. In this paper, Cu-Ag alloy nanoclusters were successfully loaded on carbon paper (CP) by magnetron co-sputtering technology, and five carbon-based Cu-Ag electrodes (Cu-Ag/CP) with different Cu/Ag ratios were prepared by adjusting the sputtering frequency of Ag targets, in which Cu-Ag20W/CP particle sizes ranged from 228nm to 285nm, and their electrochemical performance were evaluated. The results showed that Cu-Ag/CP could effectively inhibit the hydrogen evolution reaction and increase the production of C₂₊. Its Faraday efficiency of C₂₊ ( $F E C 2 +$ ) was 2.21 times that of carbon-based Cu electrode. Under constant potential of -1.07V vs. RHE and CO₂ gas flow rate of 5 sccm, the $F E C 2 +$ could reach 78.74% and the current density could reach 67.92mA/cm². After continuous operation for 8h, its catalytic performance and surface structure were relatively stable. Cu-Ag/CP had a large electrochemical active area and electrical conductivity, and obviously had the characteristics of tandem catalyst. The introduction of Ag increased the formation site of *CO, and desorption *CO transferred to the Cu surface for *CO dimerization. Cu-Ag/CP was a promising electrocatalytic material, the synthesis method of this material was suitable for large-scale continuous production mode, and the product was a high-value C₂₊ product, which was expected to provide a technical reference for the industrialization of electrocatalytic CO₂ in the future.

Key words: Cu-Ag catalyst, electrochemistry, carbon dioxide, reduction, magnetron co-sputtering, C₂₊ products

中图分类号:

TQ151.1

谢鑫瑶, 万芬, 伏炫羽, 范雨婷, 陈令修, 李鹏. Cu-Ag纳米团簇CO₂电催化还原性能和机理[J]. 化工进展, 2025, 44(3): 1387-1395.

XIE Xinyao, WAN Fen, FU Xuanyu, FAN Yuting, CHEN Lingxiu, LI Peng. Catalytic performance and mechanism of CO₂ electroreduction of Cu-Ag nanoclusters[J]. Chemical Industry and Engineering Progress, 2025, 44(3): 1387-1395.

图/表 6

图1 疏水碳纸表面的SEM图、碳基Cu与Cu-Ag电极的SEM图和碳基Cu-Ag20W电极EDX、高分辨TEM图

图2 碳基Cu和Cu-Ag电极的XRD与XPS谱图

图3 碳基Cu和Cu-Ag电极CO2电催化还原性能以及本文开发的材料与文献报道中的铜催化剂性能对比

图4 碳基Cu-Ag20W电极的CO2电催化还原反应稳定性测试性能

图5 碳基Cu-Ag20W电极稳定性测试前后的XPS谱图

图6 碳基Cu电极和Cu-Ag电极的电化学性能测试

参考文献 43

1	JORDAAN Sarah M, WANG Chao. Electrocatalytic conversion of carbon dioxide for the Paris goals[J]. Nature Catalysis, 2021, 4(11): 915-920.
2	KONDRATENKO Evgenii V, Guido MUL, BALTRUSAITIS Jonas, et al. Status and perspectives of CO₂ conversion into fuels and chemicals by catalytic, photocatalytic and electrocatalytic processes[J]. Energy & Environmental Science, 2013, 6(11): 3112-3135.
3	MA Wenchao, HE Xiaoyang, WANG Wei, et al. Electrocatalytic reduction of CO₂ and CO to multi-carbon compounds over Cu-based catalysts[J]. Chemical Society Reviews, 2021, 50(23): 12897-12914.
4	KONG Qingquan, AN Xuguang, LIU Qian, et al. Copper-based catalysts for the electrochemical reduction of carbon dioxide: Progress and future prospects[J]. Materials Horizons, 2023, 10(3): 698-721.
5	Ana SOMOZA-TORNOS, GUERRA Omar J, CROW Allison M, et al. Process modeling, techno-economic assessment, and life cycle assessment of the electrochemical reduction of CO₂: A review[J]. iScience, 2021, 24(7): 102813.
6	GATTRELL M, GUPTA N, CO A. A review of the aqueous electrochemical reduction of CO₂ to hydrocarbons at copper[J]. Journal of Electroanalytical Chemistry, 2006, 594(1): 1-19.
7	MA Wenchao, XIE Shunji, LIU Tongtong, et al. Electrocatalytic reduction of CO₂ to ethylene and ethanol through hydrogen-assisted C—C coupling over fluorine-modified copper[J]. Nature Catalysis, 2020, 3(6): 478-487.
8	KUANG Siyu, SU Yaqiong, LI Minglu, et al. Asymmetrical electrohydrogenation of CO₂ to ethanol with copper-gold heterojunctions[J]. Proceedings of the National Academy of Sciences of the United States of America, 2023, 120(4): e2214175120.
9	VASILEFF Anthony, XU Chaochen, JIAO Yan, et al. Surface and interface engineering in copper-based bimetallic materials for selective CO₂ electroreduction[J]. Chem, 2018, 4(8): 1809-1831.
10	ZHENG Yiqun, ZHANG Jiawei, MA Zesong, et al. Seeded growth of gold-copper Janus nanostructures as a tandem catalyst for efficient electroreduction of CO₂ to C₂₊ products[J]. Small, 2022, 18(19): 2201695.
11	CAI Zhizhou, CAO Ning, ZHANG Fanxing, et al. Hierarchical Ag-Cu interfaces promote C—C coupling in tandem CO₂ electroreduction[J]. Applied Catalysis B: Environmental, 2022, 1325: 122310.
12	XIE Yi, Pengfei OU, WANG Xue, et al. High carbon utilization in CO₂ reduction to multi-carbon products in acidic media[J]. Nature Catalysis, 2022, 5(6): 564-570.
13	ZI Xin, ZHOU Yajiao, ZHU Li, et al. Breaking K⁺ concentration limit on Cu nanoneedles for acidic electrocatalytic CO₂ reduction to multi-carbon products[J]. Angewandte Chemie International Edition, 2023, 62(42): e202309351.
14	WANG Pengtang, YANG Hao, TANG Cheng, et al. Boosting electrocatalytic CO₂-to-ethanol production via asymmetric C－C coupling[J]. Nature Communications, 2022, 13(1): 3754.
15	ZHANG Tingting, YUAN Bowen, WANG Wenlong, et al. Tailoring *H intermediate coverage on the CuAl₂ O₄/CuO catalyst for enhanced electrocatalytic CO₂ reduction to ethanol[J]. Angewandte Chemie International Edition, 2023, 62(29): e202302096.
16	ALEXEEVA O K, FATEEV V N. Application of the magnetron sputtering for nanostructured electrocatalysts synthesis[J]. International Journal of Hydrogen Energy, 2016, 41(5): 3373-3386.
17	WANG Hongzhi, QIN Ning, LI Yingzhi, et al. Nafion as a facile binder additive stabilizes solid electrolyte interphase on graphite anode[J]. Carbon, 2023, 205: 435-443.
18	SANDHYA Athira Lekshmi Mohandas, PLESKUNOV P, BOGAR Marco, et al. Tuning the morphology of sputter-deposited platinum catalyst: From compact layers to dispersed nanoparticles[J]. Surfaces and Interfaces, 2023, 40: 103079.
19	ZHAO Yu, ZHANG Jie, ZHANG Wusheng, et al. Growth of Ni/Mo/Cu on carbon fiber paper: An efficient electrocatalyst for hydrogen evolution reaction[J]. International Journal of Hydrogen Energy, 2021, 46(72): 35550-35558.
20	LEE Hyunju, KIM Junhyeong, CHOI Insoo, et al. Nanostructured Ag/In/Cu foam catalyst for electrochemical reduction of CO₂ to CO[J]. Electrochimica Acta, 2019, 323: 133102.
21	ZHANG Shuaishuai, ZHAO Shulin, QU Dongxue, et al. Electrochemical reduction of CO₂ toward C₂ valuables on Cu@Ag core-shell tandem catalyst with tunable shell thickness[J]. Small, 2021, 17(37): 2102293.
22	WANG Zhiqiang, DENG Chenghua, LI Bo, et al. Hierarchical surface-modification of nano-Cu toward one pot H-transfer-coupling-cyclization-CO₂ fixation tandem reactions[J]. Materials Horizons, 2024, 11(8): 1957-1963.
23	SUN Min, ZHANG Luxiao, TIAN Fuli, et al. Mechanistic investigation on Ag-Cu₂O in electrocatalytic CO₂ to CH₄ by in situ/operando spectroscopic and theoretical analysis[J]. Journal of Energy Chemistry, 2024, 88: 521-531.
24	ZHANG Tao, LIU Yan, YANG Chuncheng, et al. Monotonically increasing relationship between conversion selectivity from CO₂ to CO and the interface area of Cu-Ag biphasic electrochemical catalyst[J]. Journal of Alloys and Compounds, 2023, 947: 169638.
25	ZHANG Yong, CHEN Feifei, HAO Xiaoya, et al. Enhanced interfacial effect-induced asymmetric coupling boost electroreduction of CO₂ to ethylene[J]. Applied Catalysis B: Environmental and Energy, 2024, 344: 123666.
26	SHAO Ping, ZHANG Haixia, HONG Qinlong, et al. Enhancing CO₂ electroreduction to ethylene via copper-silver tandem catalyst in boron-imidazolate framework nanosheet[J]. Advanced Energy Materials, 2023, 13(19): 2300088.
27	CHATTERJEE Swarnendu, GRIEGO Charles, HART James L, et al. Free standing nanoporous palladium alloys as CO poisoning tolerant electrocatalysts for the electrochemical reduction of CO₂ to formate[J]. ACS Catalysis, 2019, 9(6): 5290-5301.
28	KLINKOVA Anna, DE LUNA Phil, DINH Cao-Thang, et al. Rational design of efficient palladium catalysts for electroreduction of carbon dioxide to formate[J]. ACS Catalysis, 2016, 6(12): 8115-8120.
29	LEE Seunghwa, PARK Gibeom, LEE Jaeyoung. Importance of Ag-Cu biphasic boundaries for selective electrochemical reduction of CO₂ to ethanol[J]. ACS Catalysis, 2017, 7(12): 8594-8604.
30	CHEN Chunjun, SUN Xiaofu, YAN Xupeng, et al. A strategy to control the grain boundary density and Cu⁺/Cu⁰ ratio of Cu-based catalysts for efficient electroreduction of CO₂ to C₂ products[J]. Green Chemistry, 2020, 22(5): 1572-1576.
31	CUI Wengang, LI Yanting, YU Lei, et al. Zeolite-encapsulated ultrasmall Cu/ZnO _x nanoparticles for the hydrogenation of CO₂ to methanol[J]. ACS Applied Materials & Interfaces, 2021, 13(16): 18693-18703.
32	CHEN Zhao, SONG Yao, ZHANG Zhenyu, et al. Mechanically induced Cu active sites for selective C－C coupling in CO₂ electroreduction[J]. Journal of Energy Chemistry, 2022, 74: 198-202.
33	ZHONG Yongzhi, KONG Xiangdong, SONG Zhimin, et al. Adjusting local CO confinement in porous-shell Ag@Cu catalysts for enhancing C－C coupling toward CO₂ eletroreduction[J]. Nano Letters, 2022, 22(6): 2554-2560.
34	LIU Chunxiao, ZHANG Menglu, LI Jiawei, et al. Nanoconfinement engineering over hollow multi-shell structured copper towards efficient electrocatalytical C－C coupling[J]. Angewandte Chemie International Edition, 2022, 61(3): e202113498.
35	JIAO Jiqing, LIN Rui, LIU Shoujie, et al. Copper atom-pair catalyst anchored on alloy nanowires for selective and efficient electrochemical reduction of CO₂ [J]. Nature Chemistry, 2019, 11(3): 222-228.
36	ZHANG Jianfang, WANG Yan, LI Zhengyuan, et al. Grain boundary-derived Cu⁺/Cu⁰ interfaces in CuO nanosheets for low overpotential carbon dioxide electroreduction to ethylene[J]. Advanced Science, 2022, 9(21): 2200454.
37	刘毅, 房强, 钟达忠, 等. Ag/Cu耦合催化剂的Cu晶面调控用于电催化二氧化碳还原[J]. 化工进展, 2023, 42(8): 4136-4142.
	LIU Yi, FANG Qiang, ZHONG Dazhong, et al. Cu facets regulation of Ag/Cu coupled catalysts for electrocatalytic reduction of carbon dioxide[J]. Chemical Industry and Engineering Progress, 2023, 42(8): 4136-4142.
38	YUAN Lei, ZENG Shaojuan, ZHANG Xiangping, et al. Advances and challenges of electrolyzers for large-scale CO₂ electroreduction[J]. Materials Reports: Energy, 2023, 3(1): 100177.
39	CAO Yufei, CHEN Zhu, LI Peihao, et al. Surface hydroxide promotes CO₂ electrolysis to ethylene in acidic conditions[J]. Nature Communications, 2023, 14(1): 2387.
40	CIGNONI Paolo, HOSSEINI Pouya, KAISER Christoph, et al. Validating electrochemical active surface area determination of nanostructured electrodes: Surface oxide reduction on AuPd nanoparticles[J]. Journal of the Electrochemical Society, 2023, 170(11): 116505.
41	JIANG Yong, ZHONG Dazhong, WANG Lei, et al. Roughness effect of Cu on electrocatalytic CO₂ reduction towards C₂H₄ [J]. Chemistry—An Asian Journal, 2022, 17(14): e202200380.
42	ANANTHARAJ Sengeni, NODA Suguru. Appropriate use of electrochemical impedance spectroscopy in water splitting electrocatalysis[J]. ChemElectroChem, 2020, 7(10): 2297-2308.
43	MA Jiamin, LIU Chunmei, BAI Meng, et al. Recent advances in application of tandem catalyst for electrocatalytic CO₂ reduction[J]. Molecular Catalysis, 2023, 551: 113632.

[1]	王文, 金央, 李军, 陈建钧, 陈明, 孟昕. 基于FeOOH原位生长制备用于CO₂吸收的超疏水PVDF膜[J]. 化工进展, 2025, 44(3): 1570-1577.
[2]	张茂润, 孙伟如, 马天麟, 辛志玲. Mo改性MnCe/SiC低温SCR脱硝催化剂抗SO₂中毒性能[J]. 化工进展, 2025, 44(3): 1378-1386.
[3]	杨帆, 赵溢涛, 朱学栋, 王达锐. 三元尖晶石与孪晶ZSM-5分子筛在苯与二氧化碳甲基化中的应用[J]. 化工进展, 2025, 44(2): 856-866.
[4]	张海兵, 刘云遏, 黄志昊, 沈蓉. Ti foam-Ni-Sn/Bi电极制备及其电还原NO₃^--N的性能[J]. 化工进展, 2025, 44(2): 1100-1109.
[5]	刘法志, 张鹏威, 刘涛, 谢玉仙, 何建乐, 苏胜, 徐俊, 向军. Sb改性钒钛SCR脱硝催化剂抗CO中毒性能[J]. 化工进展, 2025, 44(2): 1129-1137.
[6]	靳钰阳, 牛传峰, 刘英硕, 丁石. 石墨粉/Nafion-铅复合电极电还原草酸制乙醇酸[J]. 化工进展, 2025, 44(2): 1003-1013.
[7]	张晓方, 甘汶, 纪之骄, 许明, 李初福, 何广利. 电化学氮还原合成氨电解质利用现状与调控策略[J]. 化工进展, 2025, 44(2): 809-819.
[8]	贾亦静, 陶金泉, 黄文斌, 刘昊然, 李蓉蓉, 姚荣鹏, 白天瑜, 魏强, 周亚松. CO₂加氢制低碳烯烃Fe基催化剂研究进展[J]. 化工进展, 2025, 44(2): 820-833.
[9]	廖旭, 王玮, 黄文婷, 熊文涛, 王泽宇, 覃佐东, 林金清. 生物质基催化剂在二氧化碳转化为环状碳酸酯中的研究进展[J]. 化工进展, 2025, 44(2): 834-846.
[10]	洪思琦, 顾方伟, 郑金玉. PEM水电解制氢低铱催化剂发展现状及展望[J]. 化工进展, 2025, 44(1): 158-168.
[11]	王世鑫, 闫锋, 刘晓利, 宋光春, 李玉星, 胡其会. “双碳”背景下二氧化碳管道输送技术研究进展[J]. 化工进展, 2025, 44(1): 17-26.
[12]	李雪莲, 曹志会, 雷普瑛, 白冰, 王璇, 张金鑫, 侯凯, 刘爱芳, 齐凯, 高丽丽. 珊瑚状Mo₂C/Mo₃P@NC异质结电极高效催化Li-CO₂电池[J]. 化工进展, 2025, 44(1): 202-211.
[13]	秦婷婷, 牛强. 二氧化碳加氢制高级醇Fe基催化剂研究进展[J]. 化工进展, 2025, 44(1): 253-265.
[14]	庄柯, 陈宏, 许芸, 仲兆平, 周峻伍, 周凯, 董月红. SiO₂改性Ce-V-W/Ti催化剂载体的抗碱（土）金属中毒性能[J]. 化工进展, 2025, 44(1): 266-276.
[15]	董家彤, 单梦晴, 王华. Au-CuO/Cu₂O串联催化增强电催化CO₂还原制乙醇[J]. 化工进展, 2025, 44(1): 277-285.

Cu-Ag纳米团簇CO₂电催化还原性能和机理

Catalytic performance and mechanism of CO₂ electroreduction of Cu-Ag nanoclusters

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 6

参考文献 43

相关文章 15

编辑推荐

Metrics

本文评价