结构化铜基催化剂电化学还原CO2为多碳产物研究进展

doi:10.16085/j.issn.1000-6613.2020-1649

化工进展 ›› 2021, Vol. 40 ›› Issue (7): 3736-3746.DOI: 10.16085/j.issn.1000-6613.2020-1649

结构化铜基催化剂电化学还原CO₂为多碳产物研究进展

张轩¹(), 黄耀桢¹, 邵秀丽¹, 李晶¹(), 李丰¹, 岳秦², 王政¹()

^1.宁夏大学化学化工学院，省部共建煤炭高效利用与绿色化工国家重点实验室，宁夏银川 750021
^2.电子科技大学基础与前沿研究院，四川成都 610051

收稿日期:2020-08-18 修回日期:2020-11-30 出版日期:2021-07-06 发布日期:2021-07-19
通讯作者: 李晶,王政
作者简介:张轩（1985—），男，博士研究生，研究方向为能源催化材料。E-mail：anguszhang@yeah.net。
基金资助:
国家自然科学基金(21766026);宁夏科技领军人才项目(KJT2016001);宁夏回族自治区国内一流学科建设项目(NXYLXK2017A04)

Recent progress in structured Cu-based catalysts for electrochemical CO₂ reduction to C₂₊ products

ZHANG Xuan¹(), HUANG Yaozhen¹, SHAO Xiuli¹, LI Jing¹(), LI Feng¹, YUE Qin², WANG Zheng¹()

^1.State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering, College of Chemistry and Chemical Engineering, Ningxia University, Yinchuan 750021, Ningxia, China
^2.Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, Chengdu 610051, Sichuan, China

Received:2020-08-18 Revised:2020-11-30 Online:2021-07-06 Published:2021-07-19
Contact: LI Jing,WANG Zheng

摘要/Abstract

摘要：

近年来，随着有关铜基催化剂价态、晶面、微观形态等结构化因素对其催化性能影响的研究不断深入，铜基催化剂电化学还原CO₂高选择性制备高附加值多碳（C₂₊）产物取得长足进展。本文系统综述了近五年来结构化铜基催化剂电化学还原CO₂生成C₂₊产物的研究报道，并分析总结了铜基催化剂表面混合价态、高活性晶面和丰富晶界的存在，以及富含限域空间的形态学结构（纳米线阵列、纳米树突和纳米多孔结构等）的构建与其电化学还原CO₂生成C₂₊产物的活性和选择性之间的构效关系。进一步提出了CO₂电化学还原领域发展的新趋势，即充分发挥各个结构化因素的协同作用，原位制备具有混合价态和丰富晶界的纳米多孔结构铜基催化剂，并在流通池中高效还原CO₂持续生成C₂₊产物。

关键词: 铜, 催化剂, 二氧化碳, 还原, 价态, 晶面, 形态学

Abstract:

In recent years, the influence of structural properties such as valence, facet and micromorphology on the catalytic performance of Cu-based catalysts has been extensively studied, and highly selective electrochemical reduction of CO₂ to high value-added multi-carbon (C₂₊) products over Cu-based catalysts has achieved great progress. This review provides an overview of the research progress in structured Cu-based catalysts for electrochemical reduction of CO₂ to C₂₊ products in the past five years, and analyzes the structure-activity relationship among the catalytic activity and reaction selectivity and the presence of mixed valence states, high-active facets and rich grain boundaries on the catalyst surface, as well as the structures with abundant confine spaces such as nanowire arrays, nanodendrites and nanoporous structures. The new trend in CO₂ electrochemical reduction is further proposed, that is, to take full advantage of the synergistic effect of various structural factors, to in situ prepare nanoporous Cu-based catalysts with mixed valence states and rich grain boundaries, and to apply flow cell to efficiently and continuously reduce CO₂ to C₂₊ products.

Key words: copper, catalyst, carbon dioxide, reduction, valence, facet, morphology

中图分类号:

O646

张轩, 黄耀桢, 邵秀丽, 李晶, 李丰, 岳秦, 王政. 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, LI Jing, LI Feng, YUE Qin, WANG Zheng. 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.

图/表 8

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催化剂	主要结构化调控因素	电解池	C₂₊产物法拉第效率	电位（vs.RHE）/V	电流密度/mA·cm^-2	参考文献
Cu-Cu₃N	价态 Cu⁺/Cu⁰	H型电解池	C₂H₄(39%±2%) C₂H₅OH(19%±1%) C₃H₇OH(6%±1%)	-0.95	14	［18］
Cu（B）	价态 Cu^δ⁺/Cu⁰	H型电解池	C₂H₄(52%±2%) C₂H₅OH(27%±1%)	-1.1	70	［19］
Cu-SCP	价态 Cu⁺	H型电解池	C₂H₄(19.7%) C₂H₅OH(33.5%)	-1.34	—	［20］
Cu	价态 Cu⁺/Cu⁰	H型电解池	C₂H₄(38%)	-1.2	22.2	［25］
Cu₂O	价态 Cu⁺	流通池	C₂H₄(38.0%±1.4%) CH₃COOH(4.8%±1.1%) C₂H₅OH(26.9%±2.0%) C₃H₇OH(5.5%±1.1%)	-0.61	267±13	［27］
Cu₂O	晶面 Cu₂O（111）	H型电解池	C₂H₄(51%)	-0.76	15.7	［35］
Cu	晶面 Cu（111）	流通池	C₂₊(73.1%)	-1.2	96.62	［37］
Cu	晶面 Cu（100）/Cu（110）	流通池	C₂H₄(31.22%) C₂H₅OH(35.73%) CH₃COO^-(1.59%)	-1.05	240.8	［38］
Cu₂O	晶面 Cu₂O｛100｝/｛111｝	H型电解池	C₂H₄(59%)	-1.1	22	［39］
Cu₂O/Cu	晶面 Cu₂O（110）/Cu（111）	H型电解池	C₂₊(64.5%)	-0.9	26.2	［40］
Cu	晶面 Cu（100）/Cu（111）	H型电解池	C₂₊(72.1%)	-1.1	25.2	［41］
Cu	形态：纳米线阵列	隔膜电解池	C₂H₄(17.4%) C₂H₆(2.4%) C₂H₅OH(3.8%) C₃H₇OH(7.8%)	-1.1	—	［45］
Cu	形态：纳米线阵列	隔膜电解池	C₂H₄(3.0%) C₂H₆(6.8%) C₂H₅OH(15.2%)	-0.695	—	［47］
Cu₃Au	形态：纳米线阵列	H型电解池	C₂H₅OH(48%)	-0.5	0.4	［48］
Cu₂O	形态：纳米线阵列	气密反应器	C₂H₄(65%)	-0.8	—	［23］
Cu	形态：纳米树突	流通池	C₂H₄(57%)	—	170	［54］
Cu	形态：纳米树突	隔膜电解池	C₂H₄(56%) C₂H₅OH(17%)	-1.4	30	［55］
Cu	形态：纳米树突	常规电解池	C₂H₄(22.3%) n-C₃H₇OH(3.1%) C₂H₅CHO(2.9%)	-1.2	—	［56］
Cu-Cu₂O/Cu	形态：纳米树突	H型电解池	CH₃COOH(48%) C₂H₅OH(32%)	-0.4	11.5	［57］
Cu	形态：多孔结构	H型电解池	C₂H₄(35%)	-1.3	—	［61］
Cu	形态：多孔结构	H型电解池	C₂H₄(38%)	-1.7(vs.NHE)	—	［62］
Cu	形态：多孔结构	H型电解池	C₂H₄(30%) C₂H₅OH(10%)	-0.81	4.3+1.43	［63］
Cu₄O	形态：多孔结构	H型电解池	C₂H₄(45%)	-1.0	44.7	［70］
Cu	形态：多孔结构	微流电解池	C₂₊(62%)	-0.67	411	［75］

催化剂	主要结构化调控因素	电解池	C₂₊产物法拉第效率	电位（vs.RHE）/V	电流密度/mA·cm^-2	参考文献
Cu-Cu₃N	价态 Cu⁺/Cu⁰	H型电解池	C₂H₄(39%±2%) C₂H₅OH(19%±1%) C₃H₇OH(6%±1%)	-0.95	14	［18］
Cu（B）	价态 Cu^δ⁺/Cu⁰	H型电解池	C₂H₄(52%±2%) C₂H₅OH(27%±1%)	-1.1	70	［19］
Cu-SCP	价态 Cu⁺	H型电解池	C₂H₄(19.7%) C₂H₅OH(33.5%)	-1.34	—	［20］
Cu	价态 Cu⁺/Cu⁰	H型电解池	C₂H₄(38%)	-1.2	22.2	［25］
Cu₂O	价态 Cu⁺	流通池	C₂H₄(38.0%±1.4%) CH₃COOH(4.8%±1.1%) C₂H₅OH(26.9%±2.0%) C₃H₇OH(5.5%±1.1%)	-0.61	267±13	［27］
Cu₂O	晶面 Cu₂O（111）	H型电解池	C₂H₄(51%)	-0.76	15.7	［35］
Cu	晶面 Cu（111）	流通池	C₂₊(73.1%)	-1.2	96.62	［37］
Cu	晶面 Cu（100）/Cu（110）	流通池	C₂H₄(31.22%) C₂H₅OH(35.73%) CH₃COO^-(1.59%)	-1.05	240.8	［38］
Cu₂O	晶面 Cu₂O｛100｝/｛111｝	H型电解池	C₂H₄(59%)	-1.1	22	［39］
Cu₂O/Cu	晶面 Cu₂O（110）/Cu（111）	H型电解池	C₂₊(64.5%)	-0.9	26.2	［40］
Cu	晶面 Cu（100）/Cu（111）	H型电解池	C₂₊(72.1%)	-1.1	25.2	［41］
Cu	形态：纳米线阵列	隔膜电解池	C₂H₄(17.4%) C₂H₆(2.4%) C₂H₅OH(3.8%) C₃H₇OH(7.8%)	-1.1	—	［45］
Cu	形态：纳米线阵列	隔膜电解池	C₂H₄(3.0%) C₂H₆(6.8%) C₂H₅OH(15.2%)	-0.695	—	［47］
Cu₃Au	形态：纳米线阵列	H型电解池	C₂H₅OH(48%)	-0.5	0.4	［48］
Cu₂O	形态：纳米线阵列	气密反应器	C₂H₄(65%)	-0.8	—	［23］
Cu	形态：纳米树突	流通池	C₂H₄(57%)	—	170	［54］
Cu	形态：纳米树突	隔膜电解池	C₂H₄(56%) C₂H₅OH(17%)	-1.4	30	［55］
Cu	形态：纳米树突	常规电解池	C₂H₄(22.3%) n-C₃H₇OH(3.1%) C₂H₅CHO(2.9%)	-1.2	—	［56］
Cu-Cu₂O/Cu	形态：纳米树突	H型电解池	CH₃COOH(48%) C₂H₅OH(32%)	-0.4	11.5	［57］
Cu	形态：多孔结构	H型电解池	C₂H₄(35%)	-1.3	—	［61］
Cu	形态：多孔结构	H型电解池	C₂H₄(38%)	-1.7(vs.NHE)	—	［62］
Cu	形态：多孔结构	H型电解池	C₂H₄(30%) C₂H₅OH(10%)	-0.81	4.3+1.43	［63］
Cu₄O	形态：多孔结构	H型电解池	C₂H₄(45%)	-1.0	44.7	［70］
Cu	形态：多孔结构	微流电解池	C₂₊(62%)	-0.67	411	［75］

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结构化铜基催化剂电化学还原CO₂为多碳产物研究进展

Recent progress in structured Cu-based catalysts for electrochemical CO₂ reduction to C₂₊ products

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