金属基材料电催化CO2还原的研究进展

doi:10.16085/j.issn.1000-6613.2020-0889

摘要/Abstract

摘要：

电催化CO₂还原为具有附加价值的燃料和化学品，在缓解全球气候变暖和有效储存可再生能源方面极具潜力，近年来受到了广泛的关注。本文首先简述了水溶液中CO₂电化学还原为不同产物反应途径的研究成果，当前简单C₁产物的生成路径较为清晰，但生成多碳烃类和醇类的反应途径尚缺乏明确的证据，需要进一步探索。然后综述了用于CO₂电化学还原的金属基电催化材料的研究进展，聚焦于产物选择性、催化活性和稳定性，分别对金属纳米类、金属合金类、金属氧化物类、金属基复合物以及最近出现的单原子金属催化材料的研究现状进行了介绍。最后，展望了电催化CO₂还原的研究前景，指出不断优化电催化材料的性能是将来研究的主要方向之一，特别是有望取代Au、Ag等贵金属的单原子催化剂以及能高效生成多碳产物的铜基材料；同时，更精确的理论计算结合原位光谱表征，深入探究CO₂电化学还原反应的机理，将极大地促进高效电催化材料的开发。

关键词: 二氧化碳, 电化学, 还原, 金属基材料, 反应途径

Abstract:

The electrocatalytic reduction of CO₂ to valuable fuels and chemicals has great potential in mitigating global warming and effectively storing renewable energy, which has received extensive attention in recent years. Herein, first of all, this review briefly describes the research results of the reaction pathways of CO₂electrochemical reduction to different products in aqueous solutions. Currently, the generation pathways of simple C₁products are relatively clear, but the reaction pathways for multi-carbon hydrocarbons and alcohols generation are still unclear, which needs further exploration. Then, the recent advances of metal-based electrocatalytic materials for CO₂ electrochemical reduction is described. Focusing on product selectivity, catalytic activity and stability, this review presents the research status of nanostructured metals, metal alloys, metal oxides, metal complexes, and single atomic metal materials. Finally, the prospect of electrocatalytic CO₂ reduction is proposed. It points out that continuously optimizing the performance of electrocatalytic materials is one of the main directions in future research, especially the single atomic catalysts, which are expected to replace Au, Ag and other precious metals, as well as the copper-based materials that can efficiently produce multi-carbon products. Meanwhile, the in-depth exploration of the mechanism of CO₂ electrochemical reduction reactions based on more accurate theoretical calculations combined with in-situ spectral characterizations will greatly promote the development of highly efficient electrocatalytic materials.

Key words: carbon dioxide, electrochemistry, reduction, metal-based material, reaction pathway

中图分类号:

O646

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.

图/表 4

表1 电化学还原CO2半反应的电极电位（标准试验条件）[4]

电化学半反应	电极电位（vs. SHE）/V
2H⁺+2e^- $→$ H₂	-0.42
CO₂+2H⁺+2e^- $→$ CO+H₂O	-0.52
CO₂+2H⁺+2e^- $→$ HCOOH	-0.61
CO₂+4H⁺+4e^- $→$ HCHO+H₂O	-0.51
CO₂+6H⁺+6e^- $→$ CH₃OH+H₂O	-0.38
CO₂+8H⁺+8e^- $→$ CH₄+2H₂O	-0.24
2CO₂+12H⁺+12e^- $→$ C₂H₄+4H₂O	0.064
2CO₂+12H⁺+12e^- $→$ C₂H₅OH+3H₂O	0.084

表1 电化学还原CO2半反应的电极电位（标准试验条件）[4]

电化学半反应	电极电位（vs. SHE）/V
2H⁺+2e^- $→$ H₂	-0.42
CO₂+2H⁺+2e^- $→$ CO+H₂O	-0.52
CO₂+2H⁺+2e^- $→$ HCOOH	-0.61
CO₂+4H⁺+4e^- $→$ HCHO+H₂O	-0.51
CO₂+6H⁺+6e^- $→$ CH₃OH+H₂O	-0.38
CO₂+8H⁺+8e^- $→$ CH₄+2H₂O	-0.24
2CO₂+12H⁺+12e^- $→$ C₂H₄+4H₂O	0.064
2CO₂+12H⁺+12e^- $→$ C₂H₅OH+3H₂O	0.084

图1 电催化还原CO2为C1产物的反应途径

图2 铜电极上电化学还原CO2为C2H4和C2H5OH的反应途径

表2 代表性金属基材料电催化剂CO2还原的性能比较

催化剂	电解质	电位（vs. RHE）/V	电流密度/mA·cm^-2	主要产物（FE）	稳定性/h	参考文献
Cu NCs	0.1mol·L^-1 KHCO₃	-1.1	5.6	C₂H₄(41%)	—	[45]
Cu基 NP/C	0.1mol·L^-1 KHCO₃	-1.1	约60mA·mg_Cu^-1	C₂H₄(57.3%)	10	[46]
CuO_x颗粒	0.1mol·L^-1 CsHCO₃	-0.9	11	C₂₊(80%)	3	[47]
Au NWs	0.5mol·L^-1 KHCO₃	-0.35	1.84A·g_Au^-1	CO(94%)	6	[48]
Cu NWs	0.1mol·L^-1 KHCO₃	-1.25	约15	CH₄(55%)	—	[49]
2D Cu纳米片	2mol·L^-1 KOH	-0.74	约272	C₂₊(70%),其中CH₃COO^-(48%)	3	[50]
3D Cu NFs	0.1mol·L^-1 KHCO₃	-1.0~-1.6	18.7~21	HCOOH(45%)	9	[51]
3D hp-In	0.1mol·L^-1 KHCO₃	-1.2	65.7	HCOOH(90%)	24	[52]
Cu-In合金	0.1mol·L^-1 KHCO₃	-0.7	约1.6	CO(95%)	7	[53]
CuPd合金	0.5mol·L^-1 KHCO₃	-0.87	约4.5	CO(88%)	20	[54]
Sn-Cu合金	0.5mol·L^-1 KCl	-1.14	约100	HCOOH(82.3%)	11	[55]
In-Zn NCs	0.5mol·L^-1 KHCO₃	-1.2	22	HCOOH(95%)	24	[56]
Cu-Ag合金	1mol·L^-1 KOH	-0.7	约300	C₂H₄(60%),C₂H₅OH(25%)	—	[57]
AuCu/Cu-SCA	0.5mol·L^-1 KHCO₃	-1.0	约19	C₂H₅OH(29%),C₂H₄(16%)	24	[58]
OD-Au	0.5mol·L^-1 NaHCO₃	-0.35	2~4	CO(96%)	8	[59]
Cu₂O薄膜	0.1mol·L^-1 KHCO₃	-0.99	30~35	C₂H₄(34%~39%),C₂H₅OH(9%~16%)	—	[60]
OD-Cu	0.1mol·L^-1 KHCO₃	-0.9	11	C₂H₄(60%)	—	[61]
等离子体处理的Cu	0.1mol·L^-1 KHCO₃	-1.0	约34	C₂H₄(45%),C₂H₅OH(22%)	—	[62]
Cu/CNS	0.1mol·L^-1 KHCO₃	-1.2	2	C₂H₅OH(63%)	6	[63]
In₂O₃-rGO	0.1mol·L^-1 KHCO₃	-1.2	26	HCOOH(84.6%)	10	[64]
Ag-G-NCF	0.1mol·L^-1 KHCO₃	-0.6	0.31	C₂H₅OH (85.2%)	10	[65]
Cu Ps/BCF	0.1mol·L^-1 KHCO₃	-1.0	50	C₂H₄(63.7%)	24	[66]
Ni SAs/N-C	0.5mol·L^-1 KHCO₃	-1.0	10.48	CO(71%)	60	[67]
Ni-N-C	0.1mol·L^-1 KHCO₃	-0.75	7.51	CO(96%)	10	[68]
Co-N₂	0.5mol·L^-1 KHCO₃	-0.68	18.1	CO(95%)	60	[69]
Ni-NG	0.5mol·L^-1 KHCO₃	-0.65	约11	CO(95%)	20	[70]
SANi-GO	0.5mol·L^-1 KHCO₃	-0.63	约21	CO(96.5%)	50	[71]

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金属基材料电催化CO₂还原的研究进展

Progress of electrocatalytic reduction of CO₂ on metal-based materials

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