铜基催化剂电还原二氧化碳为甲酸研究进展

doi:10.16085/j.issn.1000-6613.2023-0843

摘要/Abstract

摘要：

电化学二氧化碳还原（ECO₂RR）通过可再生能源制备高能量化学品或燃料对碳中和具有巨大价值。尤其是以铜基催化剂进行的ECO₂RR，其成本优势和卓越的催化活性使其成为最有前景的策略。在ECO₂RR的各种产物中，甲酸作为优秀的储氢材料和内燃机燃料展现出工业化生产潜力。本文针对近年来过渡金属族的铜基催化剂在制备甲酸的研究进展进行了全面的总结，从ECO₂RR制甲酸机理出发，综述了铜基催化剂在ECO₂RR制甲酸领域取得的重要研究进展，其中以典型催化剂为例分析ECO₂RR生成甲酸的策略，包括形貌结构、表面价态、合金化、晶面效应、空位和碳载体等，重点讨论了活性位点数量以及关键中间体*OCHO的形成对甲酸产物选择性的影响，最后总结了该领域面临的挑战以及从原位表征、科学计算和反应条件等角度的展望。

关键词: 电催化, 二氧化碳还原, 铜基催化剂, 甲酸

Abstract:

The electrochemical reduction of carbon dioxide (ECO₂RR) presents a significant value for carbon neutrality by preparing high-energy chemicals or fuels from renewable energy. Particularly, ECO₂RR using copper-based catalysts, with their advantages of low cost and excellent catalytic activity, has emerged as the most promising strategy. In this paper, the research progress of copper-based catalysts in the preparation of formic acid in recent years is comprehensively summarized. The adjusting strategies of ECO₂RR to formic acid include morphology, surface valence, alloying, crystal plane effect, vacancy and carbon carrier. The effects of the number of active sites and the formation of key intermediate *OCHO on the selectivity of formic acid products are discussed. Finally, the challenges faced in this field and the prospects from the perspectives of in-situ characterization, scientific calculation and reaction condition optimization are summarized.

Key words: electrocatalysis, carbon dioxide reduction, Cu-based catalyst, formic acid

中图分类号:

O646

陈富强, 仲兆平, 戚仁志. 铜基催化剂电还原二氧化碳为甲酸研究进展[J]. 化工进展, 2024, 43(6): 3051-3060.

CHEN Fuqiang, ZHONG Zhaoping, QI Renzhi. Research progress on copper-based catalysts for electrochemical reduction of carbon dioxide to formic acid[J]. Chemical Industry and Engineering Progress, 2024, 43(6): 3051-3060.

图/表 11

图1 二氧化碳还原为甲酸的潜在机理[20]

表1 铜基催化剂改良策略与对应的ECO2RR性能

催化剂	策略	$F E H C O O -$ /%	电流密度/mA·cm^-2	参考文献
多孔树枝Cu	形貌调整	87	6.5	[21]
三维核壳Cu@Sn	形貌调整	100	16.52	[22]
中空纤维Cu	形貌调整	77.1	34.7	[23]
Pd₅Cu₁	合金化	64	—	[24]
CdCu@Cu	合金化	70.5	30.5	[19]
Sn-Cu	合金化	84.4	79	[25]
Pb₁Cu	合金化	96	1000	[18]
Cu₂S/Cu	硫掺杂	85	5.3	[26]
超薄多孔Cu-S NFs	硫掺杂	89.8	404.1	[27]
磷酸盐调控Cu	磷掺杂	79	—	[28]
Cu₂O(111)	晶面暴露	90	—	[29]
Cu₂O (100)	晶面暴露	90	260	[30]
Cu@NC	氮掺杂碳材料	41	—	[31]
Cu₂S/ NDg-C₃N₄	含氮缺陷的石墨相氮化碳	82.3	5.24	[32]
Cu-CDots	碳点载体	79	—	[33]

表1 铜基催化剂改良策略与对应的ECO2RR性能

催化剂	策略	$F E H C O O -$ /%	电流密度/mA·cm^-2	参考文献
多孔树枝Cu	形貌调整	87	6.5	[21]
三维核壳Cu@Sn	形貌调整	100	16.52	[22]
中空纤维Cu	形貌调整	77.1	34.7	[23]
Pd₅Cu₁	合金化	64	—	[24]
CdCu@Cu	合金化	70.5	30.5	[19]
Sn-Cu	合金化	84.4	79	[25]
Pb₁Cu	合金化	96	1000	[18]
Cu₂S/Cu	硫掺杂	85	5.3	[26]
超薄多孔Cu-S NFs	硫掺杂	89.8	404.1	[27]
磷酸盐调控Cu	磷掺杂	79	—	[28]
Cu₂O(111)	晶面暴露	90	—	[29]
Cu₂O (100)	晶面暴露	90	260	[30]
Cu@NC	氮掺杂碳材料	41	—	[31]
Cu₂S/ NDg-C₃N₄	含氮缺陷的石墨相氮化碳	82.3	5.24	[32]
Cu-CDots	碳点载体	79	—	[33]

图2 形貌调整策略

图3 合金化CdCu@Cu催化剂甲酸盐法拉第效率与电流密度

图4 合金化装饰共沉淀法制备Sn-Cu合金

图5 合金化Pb1Cu上CO2转化为HCOOH的示意图

图6 非金属元素掺杂铜、硫化物衍生铜催化剂原位表面增强红外光谱图

图7 非金属掺杂铜箔上磷酸盐的电沉积扫描电镜图

图8 Cu（100）表面甲酸盐与CO的吉布斯自由能台阶图

图9 晶面效应

图10 空位效应铜空位对产物的影响

参考文献 51

1	WEI Jian, YAO Ruwei, HAN Yu, et al. Towards the development of the emerging process of CO₂ heterogenous hydrogenation into high-value unsaturated heavy hydrocarbons[J]. Chemical Society Reviews, 2021, 50(19): 10764-10805.
2	YAASHIKAA P R, SENTHIL KUMAR P, VARJANI Sunita J, et al. A review on photochemical, biochemical and electrochemical transformation of CO₂ into value-added products[J]. Journal of CO₂ Utilization, 2019, 33: 131-147.
3	DUARAH Prangan, HALDAR Dibyajyoti, YADAV VSK, et al. Progress in the electrochemical reduction of CO₂ to formic acid: A review on current trends and future prospects[J]. Journal of Environmental Chemical Engineering, 2021, 9(6): 106394.
4	张轩, 黄耀桢, 邵秀丽, 等. 结构化铜基催化剂电化学还原CO₂为多碳产物研究进展[J]. 化工进展, 2021, 40(7): 3736-3746.
	ZHANG Xuan, HUANG Yaozhen, SHAO Xiuli, et al. Recent progress in structured Cu-based catalysts for electrochemical CO₂ reduction to C²⁺ products[J]. Chemical Industry and Engineering Progress, 2021, 40(7): 3736-3746.
5	李喆, 李泽洋, 杨宇森, 等. 电化学二氧化碳还原制甲酸催化剂的研究进展[J]. 化工进展, 2023, 42(1): 53-66.
	LI Zhe, LI Zeyang, YANG Yusen, et al. Research progress on catalysts for electrocatalytic reduction of carbon dioxide to formic acid[J]. Chemical Industry and Engineering Progress, 2023, 42(1): 53-66.
6	WU Yahui, CHEN Chunjun, YAN Xupeng, et al. Enhancing CO₂ electroreduction to CH₄ over Cu nanoparticles supported on N-doped carbon[J]. Chemical Science, 2022, 13(28): 8388-8394.
7	RASUL Shahid, ANJUM Dalaver H, JEDIDI Abdesslem, et al. A highly selective copper-indium bimetallic electrocatalyst for the electrochemical reduction of aqueous CO₂ to CO[J]. Angewandte Chemie International Edition, 2015, 54(7): 2146-2150.
8	Yeongdong MUN, LEE Seunghyun, CHO Ara, et al. Cu-Pd alloy nanoparticles as highly selective catalysts for efficient electrochemical reduction of CO₂ to CO[J]. Applied Catalysis B: Environmental, 2019, 246: 82-88.
9	ZHANG Qiang, YUE Ruirui, JIANG Fengxing, et al. Au as an efficient promoter for electrocatalytic oxidation of formic acid and carbon monoxide: A comparison between Pt-on-Au and PtAu alloy catalysts[J]. Gold Bulletin, 2013, 46(3): 175-184.
10	Sally Fae HO, Adriana MENDOZA-GARCIA, GUO Shaojun, et al. A facile route to monodisperse MPd (M = Co or Cu) alloy nanoparticles and their catalysis for electrooxidation of formic acid[J]. Nanoscale, 2014, 6(12): 6970-6973.
11	LI Sirui, ZUO Yu, TANG Yuming, et al. The electroplated Pd-Co alloy film on 316L stainless steel and the corrosion resistance in boiling acetic acid and formic acid mixture with stirring[J]. Applied Surface Science, 2014, 321: 179-187.
12	Elías MARDONES-HERRERA, Carmen CASTRO-CASTILLO, NANDA Kamala Kanta, et al. Reduced graphene oxide overlayer on copper nanocube electrodes steers the selectivity towards ethanol in electrochemical reduction of carbon dioxide[J]. ChemElectroChem, 2022, 9(10): e202200259.
13	BAEK Yeji, SONG Hakhyeon, HONG Deokgi, et al. Electrochemical carbon dioxide reduction on copper-zinc alloys: Ethanol and ethylene selectivity analysis[J]. Journal of Materials Chemistry A, 2022, 10(17): 9393-9401.
14	XIANG Kaisong, LIU Yucheng, LI Chaofang, et al. Microenvironmental feeding and stabilization of C₂H₄ intermediates by iodide-doped copper nanowire arrays to boost C₂H₆ formation[J]. Energy & Fuels, 2021, 35(19): 15987-15994.
15	SHAN Jingjing, SHI Yaoxuan, LI Huiyi, et al. Effective CO₂ electroreduction toward C₂H₄ boosted by Ce-doped Cu nanoparticles[J]. Chemical Engineering Journal, 2022, 433: 133769.
16	LAN Yangchun, NIU Gaoqiang, WANG Fei, et al. SnO₂-modified two-dimensional CuO for enhanced electrochemical reduction of CO₂ to C₂H₄ [J]. ACS Applied Materials & Interfaces, 2020, 12(32): 36128-36136.
17	BULUSHEV Dmitri A, ROSS Julian R H. Towards sustainable production of formic acid[J]. ChemSusChem, 2018, 11(5): 821-836.
18	ZHENG Tingting, LIU Chunxiao, GUO Chenxi, et al. Copper-catalysed exclusive CO₂ to pure formic acid conversion via single-atom alloying[J]. Nature Nanotechnology, 2021, 16(12): 1386-1393.
19	VENKATA Sai Sriram Mosali, ZHANG Xiaolong, ZHANG Ying, et al. Electrocatalytic CO₂ reduction to formate on Cu based surface alloys with enhanced selectivity[J]. ACS Sustainable Chemistry & Engineering, 2019, 7(24): 19453-19462.
20	AI Ling, Sue-Faye NG, Wee-Jun ONG. Carbon dioxide electroreduction into formic acid and ethylene: A review[J]. Environmental Chemistry Letters, 2022, 20(6): 3555-3612.
21	HUAN Tran Ngoc, SIMON Philippe, ROUSSE Gwenaëlle, et al. Porous dendritic copper: An electrocatalyst for highly selective CO₂ reduction to formate in water/ionic liquid electrolyte[J]. Chemical Science, 2017, 8(1): 742-747.
22	HOU Xiaofan, CAI Yixiao, ZHANG Dan, et al. 3D core-shell porous-structured Cu@Sn hybrid electrodes with unprecedented selective CO₂-into-formate electroreduction achieving 100%[J]. Journal of Materials Chemistry A, 2019, 7(7): 3197-3205.
23	LIU Defei, HU Yan, SHOKO Elvis, et al. High selectivity of CO₂ conversion to formate by porous copper hollow fiber: Microstructure and pressure effects[J]. Electrochimica Acta, 2021, 365: 137343.
24	TAKASHIMA Toshihiro, SUZUKI Tomohiro, IRIE Hiroshi. Electrochemical reduction of carbon dioxide to formate on palladium-copper alloy nanoparticulate electrode[J]. Electrochemistry, 2019, 87(2): 134-138.
25	YE Ke, CAO Ang, SHAO Jiaqi, et al. Synergy effects on Sn-Cu alloy catalyst for efficient CO₂ electroreduction to formate with high mass activity[J]. Science Bulletin, 2020, 65(9): 711-719.
26	ZHU Qinggong, SUN Xiaofu, KANG Xinchen, et al. Cu₂S on Cu foam as highly efficient electrocatalyst for reduction of CO₂ to formic acid[J]. Acta Physico-Chimica Sinica, 2016, 32(1): 261-266.
27	LIU Lixia, LI Xiang, CAI Yanming, et al. Hierarchical S-modified Cu porous nanoflakes for efficient CO₂ electroreduction to formate[J]. Nanoscale, 2022, 14(37): 13679-13688.
28	ZHAO Jian, SUN Libo, CANEPA Silvia, et al. Phosphate tuned copper electrodeposition and promoted formic acid selectivity for carbon dioxide reduction[J]. Journal of Materials Chemistry A, 2017, 5(23): 11905-11916.
29	QIU Yanling, XU Wenbin, YAO Pengfei, et al. Electrochemical production of formic acid from CO₂ with cetyltrimethylammonium bromide-assisted copper-based catalysts[J]. ChemSusChem, 2021, 14(8): 1962-1969.
30	MA Xintao, ZHANG Yinggan, FAN Tingting, et al. Facet dopant regulation of Cu₂O boosts electrocatalytic CO₂ reduction to formate[J]. Advanced Functional Materials, 2023, 33(16): 2213145.
31	JIANG Chengjie, HOU Yue, LIU Hua, et al. CO₂ electrocatalytic reduction on Cu nanoparticles loaded on nitrogen-doped carbon[J]. Journal of Electroanalytical Chemistry, 2022, 915: 116353.
32	HU Shengnan, TIAN Na, LI Mengying, et al. Sulfur-modified copper synergy with nitrogen-defect sites for the electroreduction of CO₂ to formate at low overpotentials[J]. Electrochimica Acta, 2022, 422: 140557.
33	GUO Sijie, ZHAO Siqi, GAO Jin, et al. Cu-CDots nanocorals as electrocatalyst for highly efficient CO₂ reduction to formate[J]. Nanoscale, 2017, 9(1): 298-304.
34	Weixin LYU, ZHOU Jing, BEI Jingjing, et al. Electrodeposition of tin based film on copper plate for electrocatalytic reduction of carbon dioxide to formate[J]. International Journal of Electrochemical Science, 2016, 11(7): 6183-6191.
35	Weixin LYU, ZHOU Jing, KONG Fenying, et al. Porous tin-based film deposited on copper foil for electrochemical reduction of carbon dioxide to formate[J]. International Journal of Hydrogen Energy, 2016, 41(3): 1585-1591.
36	CHEN Zhipeng, WANG Nailiang, YAO Shuyu, et al. The flaky Cd film on Cu plate substrate: An active and efficient electrode for electrochemical reduction of CO₂ to formate[J]. Journal of CO₂ Utilization, 2017, 22: 191-196.
37	LI Yinshi, HE Yaling, YANG Weiwei. A high-performance direct formate-peroxide fuel cell with palladium-gold alloy coated foam electrodes[J]. Journal of Power Sources, 2015, 278: 569-573.
38	Önder METIN, SUN Xiaolian, SUN Shouheng. Monodisperse gold-palladium alloy nanoparticles and their composition-controlled catalysis in formic acid dehydrogenation under mild conditions[J]. Nanoscale, 2013, 5(3): 910-912.
39	JIANG Junhua, KUCERNAK Anthony. Probing anodic reaction kinetics and interfacial mass transport of a direct formic acid fuel cell using a nanostructured palladium-gold alloy microelectrode[J]. Electrochimica Acta, 2009, 54(19): 4545-4551.
40	CHEN Guoqin, LI Yunhua, WANG Dong, et al. Carbon-supported PtAu alloy nanoparticle catalysts for enhanced electrocatalytic oxidation of formic acid[J]. Journal of Power Sources, 2011, 196(20): 8323-8330.
41	MARCINKOWSKI Matthew D, LIU Jilei, MURPHY Colin J, et al. Selective formic acid dehydrogenation on Pt-Cu single-atom alloys[J]. ACS Catalysis, 2017, 7(1): 413-420.
42	ZHAO Xi, DAI Pingwang, XU Dongyan, et al. Ultra\ufb01ne PdAg alloy nanoparticles anchored on NH₂-functionalized 2D/2D TiO₂ nanosheet/rGO composite as efficient and reusable catalyst for hydrogen release from additive-free formic acid at room temperature Journal of Energy Chemistry[J]. Journal of Energy Chemistry, 2021, 59: 455-464.
43	WANG Miao, LIU Shuai, CHEN Bo, et al. Synergistic geometric and electronic effects in Bi-Cu bimetallic catalysts for CO₂ electroreduction to formate over a wide potential window[J]. ACS Sustainable Chemistry & Engineering, 2022, 10(17): 5693-5701.
44	PHILLIPS Katherine R, KATAYAMA Yu, HWANG Jonathan, et al. Sulfide-derived copper for electrochemical conversion of CO₂ to formic acid[J]. The Journal of Physical Chemistry Letters, 2018, 9(15): 4407-4412.
45	XIAO Hai, GODDARD William A, CHENG Tao, et al. Cu metal embedded in oxidized matrix catalyst to promote CO₂ activation and CO dimerization for electrochemical reduction of CO₂ [J]. Proceedings of the National Academy of Sciences of the United States of America, 2017, 114(26): 6685-6688.
46	LAURSEN Anders B, CALVINHO Karin U D, GOETJEN Timothy A, et al. CO₂ electro-reduction on Cu₃P: Role of Cu(Ⅰ) oxidation state and surface facet structure in C₁-formate production and H₂ selectivity[J]. Electrochimica Acta, 2021, 391: 138889.
47	CHENG Tao, XIAO Hai, GODDARD William A. Reaction mechanisms for the electrochemical reduction of CO₂ to CO and formate on the Cu(100) surface at 298 K from quantum mechanics free energy calculations with explicit water[J]. Journal of the American Chemical Society, 2016, 138(42): 13802-13805.
48	Lihui OU, HE Zixi. Potential-dependent competitive electroreduction of CO₂ into CO and formate on Cu(111) from an improved H coverage-dependent electrochemical model with explicit solvent effect[J]. ACS Omega, 2020, 5(22): 12735-12744.
49	ZHAO Xiuhui, CHEN Qingsong, ZHUO Dehuang, et al. Oxygen vacancies enriched Bi based catalysts for enhancing electrocatalytic CO₂ reduction to formate[J]. Electrochimica Acta, 2021, 367: 137478.
50	LI Simeng, DUAN Huan, YU Jun, et al. Cu vacancy induced product switching from formate to CO for CO₂ reduction on copper sulfide[J]. ACS Catalysis, 2022, 12(15): 9074-9082.
51	ZHOU Wenjing, YANG Huimin, GAO Nan, et al. Vacancies and electronic effects enhanced photoelectrochemical activity of Cu-doped Bi₂Se₃ for efficient CO₂ reduction to formate[J]. Journal of Alloys and Compounds, 2022, 903: 163707.

[1]	时永兴, 林刚, 孙晓航, 蒋韦庚, 乔大伟, 颜彬航. 二氧化碳加氢制甲醇过程中铜基催化剂活性位点研究进展[J]. 化工进展, 2023, 42(S1): 287-298.
[2]	刘炫麟, 王驿凯, 戴苏洲, 殷勇高. 热泵中氨基甲酸铵分解反应特性及反应器结构优化[J]. 化工进展, 2023, 42(9): 4522-4530.
[3]	葛全倩, 徐迈, 梁铣, 王凤武. MOFs材料在光电催化领域应用的研究进展[J]. 化工进展, 2023, 42(9): 4692-4705.
[4]	王耀刚, 韩子姗, 高嘉辰, 王新宇, 李思琪, 杨全红, 翁哲. 铜基催化剂电还原二氧化碳选择性的调控策略[J]. 化工进展, 2023, 42(8): 4043-4057.
[5]	符淑瑢, 王丽娜, 王东伟, 刘蕊, 张晓慧, 马占伟. 析氧助催化剂增强光阳极光电催化分解水性能研究进展[J]. 化工进展, 2023, 42(5): 2353-2370.
[6]	刘丹, 范云洁, 王慧敏, 严政, 李鹏飞, 李家成, 曹雪波. 基于废弃PET的高值化功能性多孔碳材料及其应用进展[J]. 化工进展, 2023, 42(2): 969-984.
[7]	黄世慧, 潘相玉, 张榴萍, 周丽绘, 王斯峥, 罗世龙, 张颖霞, 胡军. 分子印迹电化学传感器对食用油中塑化剂邻苯二甲酸二异壬酯的快速检测[J]. 化工进展, 2023, 42(12): 6469-6477.
[8]	张会霞, 周立山, 张程蕾, 钱光磊, 谢陈鑫, 朱令之. Bi₂S₃/TiO₂纳米锥光阳极的制备及其光电催化降解土霉素[J]. 化工进展, 2023, 42(10): 5548-5557.
[9]	郭峰, 张尚杰, 蒋羽佳, 姜万奎, 信丰学, 章文明, 姜岷. 一碳资源在酵母中的利用与转化[J]. 化工进展, 2023, 42(1): 30-39.
[10]	李喆, 李泽洋, 杨宇森, 卫敏. 电化学二氧化碳还原制甲酸催化剂的研究进展[J]. 化工进展, 2023, 42(1): 53-66.
[11]	赵同心, 赵磊, 张延平, 李寅. 甲酸微生物转化研究进展[J]. 化工进展, 2023, 42(1): 67-72.
[12]	孟令玎, 毛梦雷, 廖奇勇, 孟子晖, 刘文芳. 碳酸酐酶和甲酸脱氢酶的稳定性研究进展[J]. 化工进展, 2022, 41(S1): 436-447.
[13]	寇佳伟, 程淑艳, 程芳琴. 类水滑石基催化剂光催化二氧化碳还原研究进展[J]. 化工进展, 2022, 41(S1): 190-198.
[14]	尹爽, 梁伟杰, 陈沛嘉, 张志聪, 葛建芳. 聚己二酸丁二醇酯-共对苯二甲酸酯基可降解塑料改性研究进展[J]. 化工进展, 2022, 41(S1): 307-317.
[15]	李志斌, 唐辉, 罗大伟, 应俏. 废弃PET化学回收及制备不饱和聚酯树脂的研究进展[J]. 化工进展, 2022, 41(6): 3279-3292.