Research progress and tendency of CO2 electrocatalytic reduction to syngas

doi:10.11949/0438-1157.20221268

Abstract

Abstract:

Renewable electric energy drives CO₂ electrocatalytic synthesis of chemicals or fuels, which has the advantages of mild reaction conditions, adjustable product selectivity and the use of distributed renewable energy. Syngas, as an important chemical raw gas, can be used to produce methanol, ethanol, olefins and other bulk chemicals, thus CO₂ electrocatalytic reduction to syngas is one of important ways to CO₂ utilization. However, accurately controlling the CO/H₂ ratio with high current density and high selectivity is one of the key scientific problems. In this paper, from the perspective of improving current density and efficiency, and widening the proportion of syngas, we reviewed the latest research progress of CO₂ electrocatalytic reduction to syngas, including electrode design, electrolyte development, and electrolyzer structure innovation, and so on. Then, the research progress on the electrocatalytic reduction mechanism of CO₂ electrocatalytic reduction to syngas by in-situ characterization and theoretical simulation (DFT, MD) is discussed. Furthermore, it was concluded that the efficiency of CO₂ electrocatalytic reduction to syngas can be improved through multi-stage morphology regulation of catalyst, multi-active site design, integration of CO₂ capture and conversion system, and the coupling of CO₂ reduction and anodic reaction. Finally, the challenges of the industrialization of CO₂ electrocatalytic reduction to syngas are discussed and prospected.

Key words: CO₂, syngas, electrocatalytic reduction, catalyst, electrolytes, mechanism

摘要：

可再生电能驱动CO₂电催化合成化学品或燃料，具有反应条件温和、产物选择性可调且可利用分布式可再生能源优势。合成气作为一类重要的化工原料气，可制备甲醇、乙醇、烯烃等大宗化学品，是CO₂电催化转化的重要途径，如何高电流密度、高选择性且精准调控碳氢比例(CO/H₂)是需要解决的关键科学技术难题。本文从提升电流密度和效率、拓宽合成气比例角度出发，综述了CO₂电催化还原制合成气的最新研究进展，包括电极材料设计、电解液开发、电解槽结构创新等；论述了利用原位表征和理论模拟(DFT、MD)方法对CO₂电催化还原制合成气反应机理的研究进展。在此基础上，提出可通过催化剂多级形貌调控、多活性位点设计、CO₂捕集与转化系统集成、CO₂还原与阳极反应耦合等途径，提升CO₂电催化还原制合成气效率的策略。最后，探讨和展望了实现CO₂电催化还原制合成气工业化的挑战和问题。

关键词: 二氧化碳, 合成气, 电催化还原, 催化剂, 电解液, 机理

CLC Number:

TQ 151.5⁺2

Xin LI, Shaojuan ZENG, Kuilin PENG, Lei YUAN, Xiangping ZHANG. Research progress and tendency of CO₂ electrocatalytic reduction to syngas[J]. CIESC Journal, 2023, 74(1): 313-329.

李鑫, 曾少娟, 彭奎霖, 袁磊, 张香平. CO₂电催化还原制合成气研究进展及趋势[J]. 化工学报, 2023, 74(1): 313-329.

Figures/Tables 10

Table 1 Electrode potential for semi-reaction of CO2 electrocatalytic reduction ［17-20］

反应	标准电极电势（vs RHE）/V
2H⁺+2e^- $→$ H₂	-0.42
CO₂ + 8H⁺+ 8e^- $→$ CH₄ + 2H₂O	-0.24
CO₂ + 6H⁺+ 6e^- $→$ CH₃OH + H₂O	-0.38
CO₂ + 4H⁺+ 4e^- $→$ HCHO + H₂O	-0.51
CO₂ + 2H⁺+ 2e- $→$ CO + H₂O	-0.52
CO₂ + 2H⁺+ 2e^- $→$ HCOOH	-0.61
2CO₂ + 12H⁺+ 12e^- $→$ C₂H₄ + 4H₂O	0.064
2CO₂ + 12H⁺+ 12e^- $→$ C₂H₅OH + 3H₂O	0.084

Table 1 Electrode potential for semi-reaction of CO2 electrocatalytic reduction ［17-20］

反应	标准电极电势（vs RHE）/V
2H⁺+2e^- $→$ H₂	-0.42
CO₂ + 8H⁺+ 8e^- $→$ CH₄ + 2H₂O	-0.24
CO₂ + 6H⁺+ 6e^- $→$ CH₃OH + H₂O	-0.38
CO₂ + 4H⁺+ 4e^- $→$ HCHO + H₂O	-0.51
CO₂ + 2H⁺+ 2e- $→$ CO + H₂O	-0.52
CO₂ + 2H⁺+ 2e^- $→$ HCOOH	-0.61
2CO₂ + 12H⁺+ 12e^- $→$ C₂H₄ + 4H₂O	0.064
2CO₂ + 12H⁺+ 12e^- $→$ C₂H₅OH + 3H₂O	0.084

Table 2 CO/H2 ratios and corresponding downstream chemical products［19，21-24］

CO/H₂	下游产物
纯CO	CO电子特气
约1	氢甲酰化产品
0.5~1.0	费托合成品
约0.5	甲醇
0.3~0.5	甲烷

Table 3 Different system of CO2 electrocatalytic reduction to syngas

电极	电解液	电解槽	电势（vs RHE）/V	电流密度/（mA/cm²）	CO/H₂	文献
Cu-In	0.1 mol/L KHCO₃	H	-1.1	20	2~9	[29]
CuZnAl	0.5 mol/L NaHCO₃	H	-2.4	90	0.14~0.5	[30]
PdAg	0.5 mol/L NaHCO₃	H	-0.9	—	2.7	[31]
PdCu	0.5 mol/L NaHCO₃	H	-0.9	—	1.2	[31]
Zn-1P	0.5 mol/L NaHCO₃	H	-1.27	90.4	0.09~11.4	[32]
Co₃O₄-CDots-C₃N₄	0.5 mol/L KHCO₃	H	-1.0	15	0.25~14.2	[33]
3D N-CNTs/SS	0.1 mol/L KHCO₃	H	-1.1	2	0.3~3	[34]
ZnO-C	0.5 mol/L KHCO₃	H	-1.2	27.07	0.73~2	[35]
4.3Pd-SnO₂	0.5 mol/L KHCO₃	H	-0.6	10	0.28~4.2	[36]
Zn/Cu	0.5 mol/L KHCO₃	H	-1.53	20.4	0.25~0.84	[37]
HPC-Co/CoPc	1.0 mol/L KHCO₃	H	-0.86	225	0.26~0.95	[38]
CF-120	0.1 mol/L KHCO₃	H	-0.6	~8.5	0.33~2	[39]
Ag	18%(mol)[Emim][BF₄]	H	—	—	—	[40]
Ru	Bu₄NH₂PO₄ /MeCN	H	-1.2	—	0.45~49	[41]
MoO₂	MeCN/0.3 mol/L [Bmim][PF₄]	H	-2.45	20	2~5	[42]
In₂Se₃/CP	[Bmim]PF₆	H	-2.3	90.1	0.33~24	[43]
Ag/TiO₂	1 mol/L NaOH	GDE	-0.56	~-83	0.5~1.5	[44]
Cu-In	1 mol/L KOH	GDE	-1.17	∼200	1.49~14.77	[45]
4.3Pd-SnO₂	0.5 mol/L KHCO₃	GDE	-0.9	100	0.26~9.2	[36]
HPC-Co/CoPc	1.0 mol/L KOH	GDE	-0.6	880	—	[38]
PdH	0.5 mol/L NaHCO₃	MEA	-0.9	200	0.25~1	[31]
BiO _x /[Bmim]OTf	—	MEA	-3.8 V(full cell)	200	—	[46]
Ni SA	—	MEA	-2.78 V(full cell)	~50	—	[47]
NiO	—	SOEC	-1.3	620	0.5~2	[48]

Fig.1 (a) Wall breaking and ring opening of carbon nanotube[31]; (b) Effect of different sizes nano Zn on CO/H2[50]; (c) Preparation of oxygen vacancy N-ZnO by rapid flame method[35]; (d) Construction of Pd-SnO2 interface[36]; (e) Dual single-cobalt atom-based carbon electrocatalyst for CO2RR and HER[38]

Fig.2 (a) Relationship between cation and pKa[64]; (b) Effect of halogen ion on product selectivity[66]; (c) Effect of different ionic liquids on current density[42]; (d) Adjust IL concentration and H2O content to regulate CO/H2 ratio[43]

Fig.3 Different types of electrolytic cell structure

Fig.4 The reaction pathway of CO2RR and HER [80]

Fig.5 CO2RR pathways towards different products[83]

Fig.6 (a) Overpotential reduced in [Emim][BF4][40]; (b) CO2 transfer pathways in ionic liquids[88]

Fig.7 Different CO2 capture and conversion routes[102]

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Research progress and tendency of CO₂ electrocatalytic reduction to syngas

CO₂电催化还原制合成气研究进展及趋势

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