二氧化碳电化学还原用铜基催化剂研究进展

doi:10.3969/j.issn.1672-6952.2021.04.001

摘要/Abstract

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

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

中图分类号:

TE08

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.

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.

图/表 4

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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]