Review of Copper⁃Based Catalysts for Electrocatalytic Reduction of Carbon Dioxide

doi:10.3969/j.issn.1672-6952.2021.04.001

Abstract

Abstract:

With the rapid economic development, the demand for energy continues to increase, and the emission of CO₂ gas keep growing. The electrochemical reduction of carbon dioxide (ERC) to fuel and chemicals is an effective way to realize the conversion and utilization of CO₂ as well as the storage of renewable energy. Cu?based catalysts are one of the materials which can directly reduce CO₂ to high value?added chemicals(such as hydrocarbons) with high efficiency. Thus, the Cu?based catalysts have been one of the research focus of ERC technology research. The main research progress of Cu?based catalysts for ERC technology in recent years is reviewed. Firstly, reaction principle of ERC and the technology challenge are summarized, and then the cooperative control strategy for the structure and composition of copper?based catalysts is discussed for monometallic copper?based catalysts, polymetallic copper?based catalysts, copper oxide and oxide?derived copper catalysts, and copper?organic composite catalysts. In addition, research progress and unsolved problems of Cu?based catalysts are also summarized. Finally, the future trend these catalysts is also prospected.

Key words: Electrochemical reduction of carbon dioxide (ERC), Electrocatalysts, Copper?based catalysts, Research progress

摘要：

随着经济高速发展，对能源的需求持续增加，二氧化碳(CO₂)气体的排放量也日益增长。CO₂电化学还原(ERC)制备燃料和化学品技术是实现CO₂转化利用及可再生能源储存的有效途径。铜(Cu)基催化剂是一类能够以较高效率将CO₂直接还原为高附加值化学品（如碳氢化合物）的催化剂，因而是ERC技术的研究重点之一。重点综述了近几年ERC技术用Cu基催化剂的主要研究进展。首先概述了ERC的反应原理及其存在的技术挑战，然后从铜金属催化剂、多金属铜基催化剂、铜氧化物及其衍生催化剂和铜?有机物复合催化剂方面，讨论了Cu催化剂结构、组成的协同调控策略。此外，还分析了Cu基催化剂的研究进展和仍待解决的问题，最后对该类催化剂的发展方向进行了展望。

关键词: 二氧化碳电化学还原, 电催化剂, 铜基催化剂, 研究进展

CLC Number:

TE08

Guohua Diao, Liwei Pan, Lin Fan, Xinyu Han, Hexiang Zhong. Review of Copper⁃Based Catalysts for Electrocatalytic Reduction of Carbon Dioxide[J]. Journal of Liaoning Petrochemical University, 2021, 41(4): 1-8.

刁国华, 潘立卫, 范琳, 韩新宇, 钟和香. 二氧化碳电化学还原用铜基催化剂研究进展[J]. 辽宁石油化工大学学报, 2021, 41(4): 1-8.

Figures/Tables 4

References 54

1	赵晨辰，何向明，王莉，等.电化学还原CO₂阴极材料研究进展［J］. 化工进展， 2013， 32（2）： 373⁃380.
2	Spinner N S， Vega J A， Mustain W E. Recent progress in the electrochemical conversion and utilization of CO₂［J］. Catalysis Science & Technology， 2012， 2（1）： 19⁃28.
3	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.
4	Wang Y X， Niu C L， Wang D W. Metallic nanocatalysts for electrochemical CO₂ reduction in aqueous solutions［J］. Journal of Colloid and Interface Science， 2018， 527： 95⁃106.
5	Schlögl R. Heterogeneous catalysis［J］. Angewandte Chemie International Edition， 2015， 54（11）： 3465⁃3520.
6	张现萍，黄海燕，靳红利，等.水溶液中电化学还原CO₂的研究进展［J］. 化工进展， 2015， 34（12）： 4139⁃4144.
7	Yang W F， Dastafkan K， Jia C， et al. Design of electrocatalysts and electrochemical cells for carbon dioxide reduction reactions［J］. Advanced Materials Technologies， 2018， 3（9）： 1700377.
8	Centi G， Quadrelli E A， Perathoner S. Catalysis for CO₂conversion： A key technology for rapid introduction of renewable energy in the value chain of chemical industries［J］. Energy & Environmental Science， 2013， 6（6）： 1711⁃1731.
9	Kuhl K P， Cave E R， Abram D N， et al. New insights into the electrochemical reduction of carbon dioxide on metallic copper surfaces［J］. Energy & Environmental Science， 2012， 5（5）： 7050⁃7059.
10	Hori Y， Murata A， Takahashi R. Formation of hydrocarbons in the electrochemical reduction of carbon dioxide at a copper electrode in aqueous solution［J］. Journal of the Chemical Society， Faraday Transactions 1： Physical Chemistry in Condensed Phases， 1989， 85（8）： 2309⁃2326.
11	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.
12	Rasul S， Anjum D H， Jedidi A， 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.
13	Raciti D， Livi K J， Wang C. Highly dense Cu nanowires for low⁃overpotential CO₂ reduction［J］. Nano Letters， 2015， 15（10）： 6829⁃6835.
14	Xie M S， Xia B Y， Li Y W， et al. Amino acid modified copper electrodes for the enhanced selective electroreduction of carbon dioxide towards hydrocarbons［J］. Energy & Environmental Science， 2016， 9（5）： 1687⁃1695.
15	Chen C S， Handoko A D， Wan J H， et al. Stable and selective electrochemical reduction of carbon dioxide to ethylene on copper mesocrystals［J］. Catalysis Science & Technology， 2015， 5（1）： 161⁃168.
16	Ma M， Djanashvili K， Smith W A. Controllable hydrocarbon formation from the electrochemical reduction of CO₂ over Cu nanowire arrays［J］. Angewandte Chemie International Edition， 2016， 55（23）： 6680⁃6684.
17	Tang W， Peterson A A， Varela A S， et al. The importance of surface morphology in controlling the selectivity of polycrystalline copper for CO₂ electroreduction［J］. Physical Chemistry Chemical Physics， 2012， 14（1）： 76⁃81.
18	Manthiram K， Beberwyck B J， Alivisatos A P. Enhanced electrochemical methanation of carbon dioxide with a dlispersible nanoscale copper catalyst［J］. Journal of the American Chemical Society， 2014， 136（38）： 13319⁃13325.
19	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.
20	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.
21	Loiudice A， Lobaccaro P， Kamali E A， et al. Tailoring copper nanocrystals towards C₂ products in electrochemical CO₂ reduction［J］. Angewandte Chemie， 2016， 128（19）： 5883⁃5886.
22	Roberts F S， Kuhl K P， Nilsson A. High selectivity for ethylene from carbon dioxide reduction over copper nanocube electrocatalysts［J］. Angewandte Chemie International Edition， 2015， 54（17）： 5179⁃5182.
23	Choi C， Cheng T， Flores Espinosa M， et al. A highly active star decahedron Cu nanocatalyst for hydrocarbon production at low overpotentials［J］. Advanced Materials， 2019， 31（6）： 1805405.
24	Reller C， Krause R， Volkova E， et al. Selective electroreduction of CO₂ toward ethylene on nano dendritic copper catalysts at high current density［J］. Advanced Energy Materials， 2017， 7（12）： 1602114.
25	Sen S， Liu D， Palmore G T R. Electrochemical reduction of CO₂ at copper nanofoams［J］. ACS Catalysis， 2014， 4（9）： 3091⁃3095.
26	Chung J， Won D H， Koh J， et al. Hierarchical Cu pillar electrodes for electrochemical CO₂ reduction to formic acid with low overpotential［J］. Physical Chemistry Chemical Physics， 2016， 18（8）： 6252⁃6258.
27	Kim D， Kley C S， Li Y， et al. Copper nanoparticle ensembles for selective electroreduction of CO₂ to C₂-C₃ products［J］. Proceedings of the National Academy of Sciences， 2017， 114（40）： 10560⁃10565.
28	Lv J J， Jouny M， Luc W， et al. A highly porous copper electrocatalyst for carbon dioxide reduction［J］. Advanced Materials， 2018， 30（49）： 1803111.
29	Weng Z， Jiang J B， Wu Y S， et al. Electrochemical CO₂ reduction to hydrocarbons on a heterogeneous molecular Cu catalyst in aqueous solution［J］. Journal of the American Chemical Society， 2016， 138（26）： 8076⁃8079.
30	Lysgaard S， Mýrdal J S G， Hansen H A， et al. A DFT⁃based genetic algorithm search for AuCu nanoalloy electrocatalysts for CO₂ reduction［J］. Physical Chemistry Chemical Physics， 2015， 17（42）： 28270⁃28276.
31	Zhu W J， Zhang L， Yang P P， et al. Morphological and compositional design of Pd⁃Cu bimetallic nanocatalysts with controllable product selectivity toward CO₂ electroreduction［J］. Small， 2018， 14（7）： 1703314.
32	Hoang T T H， Verma S， Ma S， et al. Nano porous copper⁃silver alloys by additive⁃controlled electrodeposition for the selective electroreduction of CO₂ to ethylene and ethanol［J］. Journal of the American Chemical Society， 2018， 140（17）： 5791⁃5797.
33	Ma S， Sadakiyo M， Heima M， et al. Electroreduction of carbon dioxide to hydrocarbons using bimetallic Cu⁃Pd catalysts with different mixing patterns［J］. Journal of the American Chemical Society， 2016， 139（1）： 47⁃50.
34	Zhuang T T， Liang Z Q， Seifitokaldani A， et al. Steering post⁃C-C coupling selectivity enables high efficiency electroreduction of carbon dioxide to multi⁃carbon alcohols［J］. Nature Catalysis， 2018， 1（6）： 421⁃428.
35	Chang Z Y， Huo S J， Zhang W， et al. The tunable and highly selective reduction products on Ag@Cu bimetallic catalysts toward CO₂ electrochemical reduction reaction［J］. The Journal of Physical Chemistry C， 2017， 121（21）： 11368⁃11379.
36	Ren D， Ang B S H， Yeo B S. Tuning the selectivity of carbon dioxide electroreduction toward ethanol onoxidederived CuxZn catalysts［J］. ACS Catalysis， 2016， 6（12）： 8239⁃8247.
37	Li Q， Fu J J， Zhu W L， et al. Tuning Sn⁃catalysis for electrochemical reduction of CO₂ to CO via the core/shell Cu/SnO₂ structure［J］. Journal of the American Chemical Society， 2017， 139（12）： 4290⁃4293.
38	Hu H J， Wang Y T， Du N， et al. Thermal treatment induced Cu⁃Sn core/shell nanowire array catalysts for highly efficient CO₂ electroreduction［J］. ChemElectroChem， 2018， 5（24）： 3854⁃3858.
39	Hou Y H， Erni R， Widmer R， et al. Synthesis and characterization of degradation⁃resistant Cu@CuPd nanowire catalysts for the efficient production of formate and CO from CO₂［J］. ChemElectroChem， 2019， 6（12）： 3189⁃3198.
40	Yang H， Hu Y W， Chen J J， et al. Intermediates adsorption engineering of CO₂ electroreduction reaction in highly selective heterostructure Cu⁃based electrocatalysts for CO production［J］. Advanced Energy Materials， 2019， 9（27）： 1901396.
41	Yin Z， Gao D F， Yao S Y， et al. Highly selective palladium⁃copper bimetallic electrocatalysts for the electrochemical reduction of CO₂ to CO［J］. Nano Energy， 2016， 27： 35⁃43.
42	Dai C C， Sun L B， Song J J， et al. Selective electroreduction of carbon dioxide to formic acid on cobalt⁃decorated copper thin films［J］. Small Methods， 2019， 3（11）： 1900362.
43	Le M， Ren M， Zhang Z， et al. Electrochemical reduction of CO₂ to CH₃OH at copper oxide surfaces［J］. Journal of the Electrochemical Society， 2011， 158（5）： 45⁃49.
44	Li C W， Ciston J， Kanan M W. Electroreduction of carbon monoxide to liquid fuel on oxide⁃derived nanocrystalline copper［J］. Nature， 2014， 508（7497）： 504⁃507.
45	Gu Z X， Yang N， Han P， et al. Oxygen vacancy tuning toward efficient electrocatalytic CO₂ reduction to C₂H₄［J］. Small Methods， 2019， 3（2）： 1800449.
46	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（1）： 3851.
47	Ren D， Deng Y， Handoko A D， et al. Selective electrochemical reduction of carbon dioxide to ethylene and ethanol on copper（I） oxide catalysts［J］. ACS Catalysis， 2015， 5（5）： 2814⁃2821.
48	Sarfraz S， Garcia⁃Esparza A T， Jedidi A， et al. Cu⁃Sn bimetallic catalyst for selective aqueous electroreduction of CO₂ to CO［J］. ACS Catalysis， 2016， 6（5）： 2842⁃2851.
49	Kas R， Kortlever R， Milbrat A， et al. Electrochemical CO₂ reduction on Cu₂O⁃derived copper nanoparticles： Controlling the catalytic selectivity of hydrocarbons［J］. Physical Chemistry Chemical Physics， 2014， 16（24）： 12194⁃12201.
50	Wang S B， Wang X C. Multifunctional metal⁃organic frameworks for photocatalysis［J］. Small， 2015， 11（26）： 3097⁃3112.
51	Qiu Y L， Zhong H X， Zhang T T， et al. Selective electrochemical reduction of carbon dioxide using Cu based metal organic framework for CO₂ capture［J］. ACS Applied Materials & Interfaces， 2018， 10（3）： 2480⁃2489.
52	Tan X Y， Yu C， Zhao C T， et al. Restructuring of Cu₂O to Cu₂O@Cu⁃metal–organic frameworks for selective electrochemical reduction of CO₂［J］. ACS Applied Materials & Interfaces， 2019， 11（10）： 9904⁃9910.
53	Qiu Y L， Zhong H X， Xu W B， et al. Tuning the electrocatalytic properties of a Cu electrode with organic additives containing amine group for CO₂ reduction［J］. Journal of Materials Chemistry A， 2019， 7（10）： 5453⁃5462.
54	Liu H， Xiang K S， Liu Y C， et al. Polydopamine functionalized Cu nanowires for enhanced CO₂ electroreduction towards methane［J］. ChemElectroChem， 2018， 5（24）： 3991⁃3999.

催化剂	E(vs. RHE)/V	电解液	法拉第效率/%						文献
催化剂	E(vs. RHE)/V	电解液	CH₄	C₂H₄	C₂H₅OH	C₂₊	CO	HCOOH	文献
电抛光Cu箔	-1.05	0.1 mol/L KHCO₃				40.6			[9]
Cu纳米颗粒	-1.10	0.1 mol/L KClO₄	1.0	36.0		37.0	<35.0		[17]
n⁃Cu/C	-1.35	0.1 mol/L NaHCO₃	76.0						[18]
Cu⁃P⁃ED	-2.13	0.5 mol/L NaHCO₃	85.0						[19]
Cu箔	-1.10	0.1 mol/L KHCO₃	57.0	20.0			<5.0		[20]
44 nm Cu纳米立方体	-1.10	0.1 mol/L KHCO₃		41.0		46.4			[21]
Cu纳米泡沫	-1.50(vs. Ag/AgCl)	0.1 mol/L KHCO₃						37.0	[25]
Cu纳米柱	-0.50	0.1 mol/L KHCO₃						28.7	[26]
Cu纳米颗粒集合	-0.75	0.1 mol/L KHCO₃				50.0			[27]
多孔纳米Cu	-0.67	1.0 mol/L KOH		38.6	16.6	62.0			[28]

催化剂	E(vs. RHE)/V	电解液	法拉第效率/%						文献
催化剂	E(vs. RHE)/V	电解液	CH₄	C₂H₄	C₂H₅OH	C₂₊	CO	HCOOH	文献
电抛光Cu箔	-1.05	0.1 mol/L KHCO₃				40.6			[9]
Cu纳米颗粒	-1.10	0.1 mol/L KClO₄	1.0	36.0		37.0	<35.0		[17]
n⁃Cu/C	-1.35	0.1 mol/L NaHCO₃	76.0						[18]
Cu⁃P⁃ED	-2.13	0.5 mol/L NaHCO₃	85.0						[19]
Cu箔	-1.10	0.1 mol/L KHCO₃	57.0	20.0			<5.0		[20]
44 nm Cu纳米立方体	-1.10	0.1 mol/L KHCO₃		41.0		46.4			[21]
Cu纳米泡沫	-1.50(vs. Ag/AgCl)	0.1 mol/L KHCO₃						37.0	[25]
Cu纳米柱	-0.50	0.1 mol/L KHCO₃						28.7	[26]
Cu纳米颗粒集合	-0.75	0.1 mol/L KHCO₃				50.0			[27]
多孔纳米Cu	-0.67	1.0 mol/L KOH		38.6	16.6	62.0			[28]

催化剂	E(vs. RHE)/V	电解液	法拉第效率/%						文献
催化剂	E(vs. RHE)/V	电解液	CH₄	C₂H₄	C₂H₅OH	C₂₊	CO	HCOOH	文献
CRD⁃Cu₃Pd	-1.20	0.1 mol/L KHCO₃	40.6						[31]
FL⁃Pd₃Cu	-0.90	0.1 mol/L KHCO₃					82.1		[31]
CuAg 纳米线	-0.70	1.0 mol/L KOH		60.0	25.0	85.0			[32]
相分离CuPd	-0.74	1.0 mol/L KOH		48.0	15.0	63.0			[33]
Ag@Cu⁃20	-1.06	0.1 mol/L KHCO₃		28.6					[35]
氧化物衍生Cu₄Zn层	-1.05	0.1 mol/L KHCO₃	0.4	10.8	29.1		10.4	0.3	[36]
Cu@CuPd纳米线	-0.30	0.5 mol/L KHCO₃						80.0	[39]
Cu@CuPd纳米线	-0.80	0.5 mol/L KHCO₃					86.0		[39]
Cu₂O/CuO@Ni	-1.20	0.5 mol/L KHCO₃					95.0		[40]
Pd₈₅Cu₁₅/C	-0.89	0.1 mol/L KHCO₃					86.0		[41]
Cu/Co纳米线	-0.65	0.1 mol/L KHCO₃						80.0	[42]

催化剂	E(vs. RHE)/V	电解液	法拉第效率/%						文献
催化剂	E(vs. RHE)/V	电解液	CH₄	C₂H₄	C₂H₅OH	C₂₊	CO	HCOOH	文献
CRD⁃Cu₃Pd	-1.20	0.1 mol/L KHCO₃	40.6						[31]
FL⁃Pd₃Cu	-0.90	0.1 mol/L KHCO₃					82.1		[31]
CuAg 纳米线	-0.70	1.0 mol/L KOH		60.0	25.0	85.0			[32]
相分离CuPd	-0.74	1.0 mol/L KOH		48.0	15.0	63.0			[33]
Ag@Cu⁃20	-1.06	0.1 mol/L KHCO₃		28.6					[35]
氧化物衍生Cu₄Zn层	-1.05	0.1 mol/L KHCO₃	0.4	10.8	29.1		10.4	0.3	[36]
Cu@CuPd纳米线	-0.30	0.5 mol/L KHCO₃						80.0	[39]
Cu@CuPd纳米线	-0.80	0.5 mol/L KHCO₃					86.0		[39]
Cu₂O/CuO@Ni	-1.20	0.5 mol/L KHCO₃					95.0		[40]
Pd₈₅Cu₁₅/C	-0.89	0.1 mol/L KHCO₃					86.0		[41]
Cu/Co纳米线	-0.65	0.1 mol/L KHCO₃						80.0	[42]

催化剂	E(vs. RHE)/V	c(KHCO₃)/(mol·L^-1)	法拉第效率/%						文献
催化剂	E(vs. RHE)/V	c(KHCO₃)/(mol·L^-1)	CH₄	C₂H₄	C₂H₅OH	C₂₊	CO	HCOOH	文献
CuO_x⁃Vo	-1.40	0.1		63.00		63.00			[45]
3.6 µm Cu₂O薄层	-0.99	0.1	0.32	34.26	16.37	50.78	0.43	3.94	[47]
Cu_xO⁃Sn	-0.80	0.1					90.00		[48]
Cu₂O衍生的Cu纳米颗粒	-1.10	0.1	4.00	33.00			2.50	22.50	[49]