电催化还原CO2生成多种产物催化剂研究进展

doi:10.16085/j.issn.1000-6613.2021-1936

摘要/Abstract

摘要：

电催化还原CO₂生成含碳产物技术，能有效解决CO₂过量导致的温室效应及能源短缺问题。但是，电催化还原CO₂会生成多种产物，因此，研究制备催化活性较好的高选择性催化剂是研究重点。本文简述了电催化还原CO₂的基本原理、不同还原产物的形成途径、活性中间体、速控步及活性催化剂，分析了电催化还原CO₂生成不同产物存在的问题。并且针对催化剂催化活性及催化反应过程中的这些问题，提出了提高催化剂催化活性的方法，总结了催化剂发展趋势，一般策略包括制造纳米结构材料、催化剂负载在高比表面积的载体上、杂原子掺杂、合金化、引入缺陷等，分析了这些方法通过改变电子传输等因素对催化剂活性及选择性的影响。

关键词: 电催化, 二氧化碳, 还原产物, 催化剂, 改性

Abstract:

The electrocatalytic reduction of carbon dioxide (CO₂) to produce carbon-containing products can effectively relieve the greenhouse effect and energy shortage caused by excessive CO₂. However, the electrocatalytic reduction of CO₂ could form a variety of products simultaneously, and thus catalysts with both high selectivity and catalytic activity is the focus of such researches. This review briefly describes the basic principles of electrocatalytic reduction of CO₂, the formation pathways of different reduction products, the active intermediates, the rate control steps, the active catalysts. The existing problems are also analyzed, and a method to improve the catalytic activity is proposed. The development trend of the catalyst is summarized and the common strategies include manufacturing nanostructured materials, supporting catalysts on carriers with high specific surface areas, heteroatom doping, alloying, and introducing defects. The effects of changing the factors such as electron transport by using these methods on the catalyst activity and selectivity are analyzed.

Key words: electrocatalytic, carbon dioxide, reduction product, catalyst, modification

中图分类号:

TQ035

郑元波, 张前, 石坚, 李佳霖, 梅苏宁, 余秦伟, 杨建明, 吕剑. 电催化还原CO₂生成多种产物催化剂研究进展[J]. 化工进展, 2022, 41(3): 1209-1223.

ZHENG Yuanbo, ZHANG Qian, SHI Jian, LI Jialin, MEI Suning, YU Qinwei, YANG Jianming, LYU Jian. Research progress of catalysts for electrocatalytic reduction of CO₂ to various products[J]. Chemical Industry and Engineering Progress, 2022, 41(3): 1209-1223.

图/表 9

参考文献 77

1	BENN D I, SUGDEN D E. West Antarctic ice sheet and CO₂ greenhouse effect: a threat of disaster[J]. Scottish Geographical Journal, 2020, 136(1/2/3/4): 13-23.
2	SCHNEIDER S H. The greenhouse effect: science and policy[J]. Science, 1989, 243(4892): 771-781.
3	QIAO J, LIU Y, HONG F, et al. A review of catalysts for the electroreduction of carbon dioxide to produce low-carbon fuels[J]. Chemical Society Reviews, 2014, 43(2): 631-675.
4	LIU M, PANG Y J, ZHANG B, et al. Enhanced electrocatalytic CO₂ reduction via field-induced reagent concentration[J]. Nature, 2016, 537(7620): 382-386.
5	YANG H P, YUE Y N, QIN S, et al. Selective electrochemical reduction of CO₂ to different alcohol products by an organically doped alloy catalyst[J]. Green Chemistry, 2016, 18(11): 3216-3220.
6	HANC-SCHERER F A, MONTIEL M A, MONTIEL V, et al. Surface structured platinum electrodes for the electrochemical reduction of carbon dioxide in imidazolium based ionic liquids[J]. Physical Chemistry Chemical Physics, 2015, 17(37): 23909-23916.
7	QIU Y L, ZHONG H X, ZHANG T T, et al. Copper electrode fabricated via pulse electrodeposition: toward high methane selectivity and activity for CO₂ electroreduction[J]. ACS Catalysis, 2017, 7(9): 6302-6310.
8	SONG R B, ZHU W L, FU J J, et al. Electrode materials engineering in electrocatalytic CO₂ reduction: energy input and conversion efficiency[J]. Advanced Materials, 2020, 32(27): 1903796.
9	KATURI K P, KALATHIL S, RAGAB A, et al. Dual-function electrocatalytic and macroporous hollow-fiber cathode for converting waste streams to valuable resources using microbial electrochemical systems[J]. Advanced Materials, 2018, 30(26): 1707072.
10	WHITE J L, HERB J T, KACZUR J J, et al. Photons to formate: Efficient electrochemical solar energy conversion via reduction of carbon dioxide[J]. Journal of CO₂ Utilization, 2014, 7: 1-5.
11	KORTLEVER R, SHEN J, SCHOUTEN K J, et al. Catalysts and reaction pathways for the electrochemical reduction of carbon dioxide[J]. The Journal of Physical Chemistry Letters, 2015, 6(20): 4073-4082.
12	FAVARO M, XIAO H, CHENG T, et al. Subsurface oxide plays a critical role in CO₂ activation by Cu(111) surfaces to form chemisorbed CO₂, the first step in reduction of CO₂ [J]. Proceedings of the National Academy of Sciences of the United States of America, 2017, 114(26): 6706-6711.
13	CHANG X X, WANG T, GONG J L. CO₂ photo-reduction: insights into CO₂ activation and reaction on surfaces of photocatalysts[J]. Energy & Environmental Science, 2016, 9(7): 2177-2196.
14	苏文礼, 范煜. 金属基材料电催化CO₂还原的研究进展[J]. 化工进展, 2021, 40(3): 1384-1394.
	SU Wenli, FAN Yu. Progress of electrocatalytic reduction of CO₂ on metal-based materials[J]. Chemical Industry and Engineering Progress, 2021, 40(3): 1384-1394.
15	HANSEN H A, VARLEY J B, PETERSON A A, et al. Understanding trends in the electrocatalytic activity of metals and enzymes for CO₂ reduction to CO[J]. The Journal of Physical Chemistry Letters, 2013, 4(3): 388-392.
16	ZHANG S, KANG P, MEYER T J. Nanostructured tin catalysts for selective electrochemical reduction of carbon dioxide to formate[J]. Journal of the American Chemical Society, 2014, 136(5): 1734-1737.
17	BARUCH M F, PANDER J E, WHITE J L, et al. Mechanistic insights into the reduction of CO₂ on tin electrodes using in situ ATR-IR spectroscopy[J]. ACS Catalysis, 2015, 5(5): 3148-3156.
18	SUN Z Y, MA T, TAO H C, et al. Fundamentals and challenges of electrochemical CO₂ reduction using two-dimensional materials[J]. Chem, 2017, 3(4): 560-587.
19	ZHAO Y, LIU X, LIU Z, et al. Spontaneously Sn-doped Bi/BiO _x core-shell nanowires toward high-performance CO₂ electroreduction to liquid fuel[J]. Nano Letters, 2021, 21(16): 6907-6913.
20	ZHANG M, WEI W B, ZHOU S H, et al. Engineering a conductive network of atomically thin bismuthene with rich defects enables CO₂ reduction to formate with industry-compatible current densities and stability[J]. Energy & Environmental Science, 2021, 14(9): 4998-5008.
21	GONG Q F, DING P, XU M Q, et al. Structural defects on converted bismuth oxide nanotubes enable highly active electrocatalysis of carbon dioxide reduction[J]. Nature Communications, 2019, 10: 2807.
22	JIA L, SUN M Z, XU J, et al. Phase-dependent electrocatalytic CO₂ reduction on Pd₃Bi nanocrystals[J]. Angewandte Chemie, 2021, 133(40): 21909-21913.
23	ZHANG T T, QIU Y L, YAO P F, et al. Bi-modified Zn catalyst for efficient CO₂ electrochemical reduction to formate[J]. ACS Sustainable Chemistry & Engineering, 2019, 7(18): 15190-15196.
24	WANG Z T, ZHOU Y S, XIA C F, et al. Efficient electroconversion of carbon dioxide to formate by a reconstructed amino-functionalized indium-organic framework electrocatalyst[J]. Angewandte Chemie International Edition, 2021, 60(35): 19107-19112.
25	NIE X W, ESOPI M R, JANIK M J, et al. Selectivity of CO₂ reduction on copper electrodes: the role of the kinetics of elementary steps[J]. Angewandte Chemie International Edition, 2013, 52(9): 2459-2462.
26	MONTEIRO M C O, DATTILA F, HAGEDOORN B, et al. Absence of CO₂ electroreduction on copper, gold and silver electrodes without metal cations in solution[J]. Nature Catalysis, 2021, 4(8): 654-662.
27	ZHENG T T, JIANG K, WANG H T. Recent advances in electrochemical CO₂-to-CO conversion on heterogeneous catalysts[J]. Advanced Materials, 2018, 30(48): 1802066.
28	ZHU W, ZHANG Y J, ZHANG H, et al. Active and selective conversion of CO₂ to CO on ultrathin Au nanowires[J]. Journal of the American Chemical Society, 2014, 136(46): 16132-16135.
29	ZHUANG S L, CHEN D, LIAO L W, et al. Hard-sphere random close-packed Au₄₇Cd₂(TBBT)₃₁ nanoclusters with a faradaic efficiency of up to 96% for electrocatalytic CO₂ reduction to CO[J]. Angewandte Chemie International Edition, 2020, 59(8): 3073-3077.
30	GAO D, ZHANG Y, ZHOU Z, et al. Enhancing CO₂ electroreduction with the metal-oxide interface[J]. Journal of the American Chemical Society, 2017, 139(16): 5652-5655.
31	LU Q, ROSEN J, ZHOU Y, et al. A selective and efficient electrocatalyst for carbon dioxide reduction[J]. Nature Communications, 2014, 5: 3242.
32	BI W T, LI X G, YOU R, et al. Surface immobilization of transition metal ions on nitrogen-doped graphene realizing high-efficient and selective CO₂ reduction[J]. Advanced Materials, 2018, 30(18): 1706617.
33	KUMAR B, ASADI M, PISASALE D, et al. Renewable and metal-free carbon nanofibre catalysts for carbon dioxide reduction[J]. Nature Communications, 2013, 4: 2819.
34	PETERSON A A, ABILD-PEDERSEN F, STUDT F, et al. How copper catalyzes the electroreduction of carbon dioxide into hydrocarbon fuels[J]. Energy & Environmental Science, 2010, 3(9): 1311.
35	徐敏杰, 朱明辉, 陈天元, 等. CO₂高值化利用：CO₂加氢制甲醇催化剂研究进展[J]. 化工进展, 2021, 40(2): 565-576.
	XU Minjie, ZHU Minghui, CHEN Tianyuan, et al. High value utilization of CO₂: research progress of catalyst for hydrogenation of CO₂ to methanol[J]. Chemical Industry and Engineering Progress, 2021, 40(2): 565-576.
36	ZHENG Y, VASILEFF A, ZHOU X, et al. Understanding the roadmap for electrochemical reduction of CO₂ to multi-carbon oxygenates and hydrocarbons on copper-based catalysts[J]. Journal of the American Chemical Society, 2019, 141(19): 7646-7659.
37	ZHAO R B, DING P, WEI P P, et al. Recent progress in electrocatalytic methanation of CO₂ at ambient conditions[J]. Advanced Functional Materials, 2021, 31(13): 2009449.
38	AZUMA M, HASHIMOTO K, HIRAMOTO M, et al. Carbon dioxide reduction at low temperature on various metal electrodes[J]. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, 1989, 260(2): 441-445.
39	AZUMA M, HASHIMOTO K, HIRAMOTO M, et al. Electrochemical reduction of carbon dioxide on various metal electrodes in low-temperature aqueous KHCO₃ media[J]. Journal of the Electrochemical Society, 1990, 137(6): 1772-1778.
40	MANTHIRAM K, BEBERWYCK B J, ALIVISATOS A P. Enhanced electrochemical methanation of carbon dioxide with a dispersible nanoscale copper catalyst[J]. Journal of the American Chemical Society, 2014, 136(38): 13319-13325.
41	CHOI C, CAI J, LEE C, et al. Intimate atomic Cu-Ag interfaces for high CO₂RR selectivity towards CH₄ at low over potential[J]. Nano Research, 2021, 14(10): 3497-3501.
42	YE J J, RAO D W, YAN X H. Regulating the electronic properties of MoSe₂ to improve its CO₂ electrocatalytic reduction performance via atomic doping[J]. New Journal of Chemistry, 2021, 45(12): 5350-5356.
43	GUO W W, LIU S J, TAN X X, et al. Highly efficient CO₂ electroreduction to methanol through atomically dispersed Sn coupled with defective CuO catalysts[J]. Angewandte Chemie International Edition, 2021, 60(40): 21979-21987.
44	ZHANG W Y, QIN Q, DAI L, et al. Electrochemical reduction of carbon dioxide to methanol on hierarchical Pd/SnO₂ nanosheets with abundant Pd-O-Sn interfaces[J]. Angewandte Chemie International Edition, 2018, 57(30): 9475-9479.
45	HORI Y, TAKAHASHI R, YOSHINAMI Y, et al. Electrochemical reduction of CO at a copper electrode[J]. The Journal of Physical Chemistry B, 1997, 101(36): 7075-7081.
46	YANG K D, LEE C W, JIN K, et al. Current status and bioinspired perspective of electrochemical conversion of CO₂ to a long-chain hydrocarbon[J]. The Journal of Physical Chemistry Letters, 2017, 8(2): 538-545.
47	GENOVESE C, AMPELLI C, PERATHONER S, et al. Mechanism of C—C bond formation in the electrocatalytic reduction of CO₂ to acetic acid. A challenging reaction to use renewable energy with chemistry[J]. Green Chemistry, 2017, 19(10): 2406-2415.
48	SUN X F, ZHU Q G, KANG X C, et al. Design of a Cu(‍Ⅰ)/C-doped boron nitride electrocatalyst for efficient conversion of CO₂ into acetic acid[J]. Green Chemistry, 2017, 19(9): 2086-2091.
49	ZHANG S S, ZHAO S L, QU D X, 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.
50	SIKDAR N, JUNQUEIRA J R C, DIECKHÖFER S, et al. A metal-organic framework derived Cu _x O _y C _z catalyst for electrochemical CO₂ reduction and impact of local pH change[J]. Angewandte Chemie International Edition, 2021, 60(43): 23427-23434.
51	RAAIJMAN S J, SCHELLEKENS M P, CORBETT P J, et al. High-pressure CO electroreduction at silver produces ethanol and propanol[J]. Angewandte Chemie International Edition, 2021, 60(40): 21732-21736.
52	LI M H, MA Y Y, CHEN J, et al. Residual chlorine induced cationic active species on a porous copper electrocatalyst for highly stable electrochemical CO₂ reduction to C 2 + [J]. Angewandte Chemie International Edition, 2021, 60(20): 11588-11594.
53	ZHU Q G, SUN X F, YANG D X, et al. Carbon dioxide electroreduction to C₂ products over copper-cuprous oxide derived from electrosynthesized copper complex[J]. Nature Communications, 2019, 10: 3851.
54	WANG H X, TZENG Y K, JI Y F, et al. Synergistic enhancement of electrocatalytic CO₂ reduction to C₂ oxygenates at nitrogen-doped nanodiamonds/Cu interface[J]. Nature Nanotechnology, 2020, 15(2): 131-137.
55	MUNIR S, VARZEGHANI A R, KAYA S. Electrocatalytic reduction of CO₂ to produce higher alcohols[J]. Sustainable Energy & Fuels, 2018, 2(11): 2532-2541.
56	WANG G, CHEN J, DING Y, et al. Electrocatalysis for CO₂ conversion: from fundamentals to value-added products[J]. Chemical Society Reviews, 2021, 50(8): 4993-5061.
57	HUSSAIN J, JÓNSSON H, SKÚLASON E. Calculations of product selectivity in electrochemical CO₂ reduction[J]. ACS Catalysis, 2018, 8(6): 5240-5249.
58	BENCK J D, HELLSTERN T R, KIBSGAARD J, et al. Catalyzing the hydrogen evolution reaction (HER) with molybdenum sulfide nanomaterials[J]. ACS Catalysis, 2014, 4(11): 3957-3971.
59	RESKE R, MISTRY H, BEHAFARID F, et al. Particle size effects in the catalytic electroreduction of CO₂ on Cu nanoparticles[J]. Journal of the American Chemical Society, 2014, 136(19): 6978-6986.
60	HOANG T T H, MA S C, GOLD J I, et al. Nanoporous copper films by additive-controlled electrodeposition: CO₂ reduction catalysis[J]. ACS Catalysis, 2017, 7(5): 3313-3321.
61	LI Z, JI S, LIU Y, et al. Well-defined materials for heterogeneous catalysis: from nanoparticles to isolated single-atom sites[J]. Chemical Reviews, 2020, 120(2): 623-682.
62	SUN M, LIU H J, LIU Y, et al. Graphene-based transition metal oxide nanocomposites for the oxygen reduction reaction[J]. Nanoscale, 2015, 7(4): 1250-1269.
63	ZHANG Z, AHMAD F, ZHAO W, et al. Enhanced electrocatalytic reduction of CO₂ via chemical coupling between indium oxide and reduced graphene oxide[J]. Nano Letters, 2019, 19(6): 4029-4034.
64	HUANG H J, WANG X. Recent progress on carbon-based support materials for electrocatalysts of direct methanol fuel cells[J]. J. Mater. Chem. A, 2014, 2(18): 6266-6291.
65	MA S C, LAN Y C, PEREZ G M J, et al. Silver supported on titania as an active catalyst for electrochemical carbon dioxide reduction[J]. ChemSusChem, 2014, 7(3): 866-874.
66	LI Z, YANG Y, YIN Z L, et al. Interface-enhanced catalytic selectivity on the C₂ products of CO₂ electroreduction[J]. ACS Catalysis, 2021, 11(5): 2473-2482.
67	HUANG Y, ZHANG W Y, YUE Z, et al. Performance of SiO₂-TiO₂ binary oxides supported Cu-ZnO catalyst in ethyl acetate hydrogenation to ethanol[J]. Catalysis Letters, 2017, 147(11): 2817-2825.
68	ZHAO C, DAI X, YAO T, et al. Ionic exchange of metal-organic frameworks to access single nickel sites for efficient electroreduction of CO₂ [J]. Journal of the American Chemical Society, 2017, 139(24): 8078-8081.
69	LIU Y M, CHEN S, QUAN X, et al. Efficient electrochemical reduction of carbon dioxide to acetate on nitrogen-doped nanodiamond[J]. Journal of the American Chemical Society, 2015, 137(36): 11631-11636.
70	XU J Q, LI X D, LIU W, et al. Carbon dioxide electroreduction into syngas boosted by a partially delocalized charge in molybdenum sulfide selenide alloy monolayers[J]. Angewandte Chemie International Edition, 2017, 56(31): 9121-9125.
71	LIM H K, SHIN H, GODDARD W A III, et al. Embedding covalency into metal catalysts for efficient electrochemical conversion of CO₂ [J]. Journal of the American Chemical Society, 2014, 136(32): 11355-11361.
72	HE J F, DETTELBACH K E, SALVATORE D A, et al. High-throughput synthesis of mixed-metal electrocatalysts for CO₂ reduction[J]. Angewandte Chemie International Edition, 2017, 56(22): 6068-6072.
73	CLARK E L, HAHN C, JARAMILLO T F, et al. Electrochemical CO₂ reduction over compressively strained CuAg surface alloys with enhanced multi-carbon oxygenate selectivity[J]. Journal of the American Chemical Society, 2017, 139(44): 15848-15857.
74	SUN K, CHENG T, WU L N, et al. Ultrahigh mass activity for carbon dioxide reduction enabled by gold-iron core-shell nanoparticles[J]. Journal of the American Chemical Society, 2017, 139(44): 15608-15611.
75	MISTRY H, CHOI Y W, BAGGER A, et al. Enhanced carbon dioxide electroreduction to carbon monoxide over defect-rich plasma-activated silver catalysts[J]. Angewandte Chemie International Edition, 2017, 56(38): 11394-11398.
76	MISTRY H, VARELA A S, BONIFACIO C S, et al. Highly selective plasma-activated copper catalysts for carbon dioxide reduction to ethylene[J]. Nature Communications, 2016, 7: 12123.
77	GAO W, LI S, HE H C, et al. Vacancy-defect modulated pathway of photoreduction of CO₂ on single atomically thin AgInP₂S₆ sheets into olefiant gas[J]. Nature Communications, 2021, 12: 4747.

[1]	张明焱, 刘燕, 张雪婷, 刘亚科, 李从举, 张秀玲. 非贵金属双功能催化剂在锌空气电池研究进展[J]. 化工进展, 2023, 42(S1): 276-286.
[2]	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.
[3]	谢璐垚, 陈崧哲, 王来军, 张平. 用于SO₂去极化电解制氢的铂基催化剂[J]. 化工进展, 2023, 42(S1): 299-309.
[4]	杨霞珍, 彭伊凡, 刘化章, 霍超. 熔铁催化剂活性相的调控及其费托反应性能[J]. 化工进展, 2023, 42(S1): 310-318.
[5]	郑谦, 官修帅, 靳山彪, 张长明, 张小超. 铈锆固溶体Ce_0.25Zr_0.75O₂光热协同催化CO₂与甲醇合成DMC[J]. 化工进展, 2023, 42(S1): 319-327.
[6]	王家庆, 宋广伟, 李强, 郭帅成, DAI Qingli. 橡胶混凝土界面改性方法及性能提升路径[J]. 化工进展, 2023, 42(S1): 328-343.
[7]	戴欢涛, 曹苓玉, 游新秀, 徐浩亮, 汪涛, 项玮, 张学杨. 木质素浸渍柚子皮生物炭吸附CO₂特性[J]. 化工进展, 2023, 42(S1): 356-363.
[8]	陈崇明, 陈秋, 宫云茜, 车凯, 郁金星, 孙楠楠. 分子筛基CO₂吸附剂研究进展[J]. 化工进展, 2023, 42(S1): 411-419.
[9]	王乐乐, 杨万荣, 姚燕, 刘涛, 何川, 刘逍, 苏胜, 孔凡海, 朱仓海, 向军. SCR脱硝催化剂掺废特性及性能影响[J]. 化工进展, 2023, 42(S1): 489-497.
[10]	顾永正, 张永生. HBr改性飞灰对Hg⁰的动态吸附及动力学模型[J]. 化工进展, 2023, 42(S1): 498-509.
[11]	邓丽萍, 时好雨, 刘霄龙, 陈瑶姬, 严晶颖. 非贵金属改性钒钛基催化剂NH₃-SCR脱硝协同控制VOCs[J]. 化工进展, 2023, 42(S1): 542-548.
[12]	孙玉玉, 蔡鑫磊, 汤吉海, 黄晶晶, 黄益平, 刘杰. 反应精馏合成甲基丙烯酸甲酯工艺优化及节能[J]. 化工进展, 2023, 42(S1): 56-63.
[13]	杨寒月, 孔令真, 陈家庆, 孙欢, 宋家恺, 王思诚, 孔标. 微气泡型下向流管式气液接触器脱碳性能[J]. 化工进展, 2023, 42(S1): 197-204.
[14]	王胜岩, 邓帅, 赵睿恺. 变电吸附二氧化碳捕集技术研究进展[J]. 化工进展, 2023, 42(S1): 233-245.
[15]	程涛, 崔瑞利, 宋俊男, 张天琪, 张耘赫, 梁世杰, 朴实. 渣油加氢装置杂质沉积规律与压降升高机理分析[J]. 化工进展, 2023, 42(9): 4616-4627.

电催化还原CO₂生成多种产物催化剂研究进展

Research progress of catalysts for electrocatalytic reduction of CO₂ to various products

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 9

参考文献 77

相关文章 15

编辑推荐

Metrics

本文评价