Research progress of electrocatalysts towards electrocatalytic reduction reaction of carbon dioxide to syngas

doi:10.16085/j.issn.1000-6613.2024-0098

Abstract

Abstract:

The conversion of carbon dioxide (CO₂) to valuable syngas (CO/H₂) by electrocatalytic carbon dioxide reduction reaction (CRR) has attracted widespread attention. The development of electrocatalysts for CRR is crucial for efficient and accurate synthesis of syngas. This article reviews the research progress on the reaction process, reaction mechanism, and the electrocatalysts of CRR to syngas. The types, advantages, existing problems, and development directions of existing CRR catalysts were introduced. The influence of the types and proportions of doping elements in catalysts on the reaction intermediates were analyzed in detail. The effects of the edge and active site of the metal atom doped with non-metallic elements on CRR were pointed out. The precise regulation CO and H₂ by catalyst design and reaction condition adjustment were discussed. The article also discusses the ways to promote CRR and regulate the hydrocarbon ratio of syngas such as increasing reaction active sites and reducing the reaction energy barrier of intermediates. Furthermore, it was concluded that the efficiency of CRR to syngas could be improved through multi-stage regulation of catalyst morphology, multi-active site design, and the coupling of CO₂ reduction and anodic reaction. Finally, the challenges and issues in future industrial production of syngas through CRR were discussed.

Key words: syngas, carbon dioxide, electrochemistry, catalyst

摘要：

利用电催化二氧化碳还原反应（CRR）将CO₂转变为有价值的合成气（CO/H₂）受到广泛关注。CRR电催化剂的开发对于高效、精确制备合成气至关重要。本文综述了CRR制备合成气的反应过程、反应机理以及催化剂等方面的研究进展，介绍了现有CRR催化剂的种类、优点、存在的问题以及发展方向，具体分析了催化剂的掺杂元素种类和比例对反应中间体的影响，指出了掺杂非金属元素的金属原子边缘和活性位对CRR的作用，探讨了催化剂设计和反应条件调节对CO和H₂比例的精确调控。本文也讨论了增加反应活性位点、降低中间体的反应能垒等促进CRR以及调节合成气碳氢比的方式。此外，提出了可通过催化剂多级形貌调控、多活性位点设计、CO₂还原与阳极反应耦合等途径，提升CRR制合成气效率的策略。最后，探讨和展望了CRR制合成气在未来工业化生产中存在的挑战和问题。

关键词: 合成气, 二氧化碳, 电化学, 催化剂

CLC Number:

TQ151

HUANG Peng, ZOU Ying, WANG Baohuan, WANG Xiaoyan, ZHAO Yong, LAING Xin, HU Di. Research progress of electrocatalysts towards electrocatalytic reduction reaction of carbon dioxide to syngas[J]. Chemical Industry and Engineering Progress, 2024, 43(5): 2760-2775.

黄澎, 邹颖, 王宝焕, 王逍妍, 赵勇, 梁鑫, 胡迪. 二氧化碳电催化还原反应制合成气催化剂研究进展[J]. 化工进展, 2024, 43(5): 2760-2775.

Figures/Tables 14

电化学半反应	电极电位（vs. SHE）/ V
2H⁺ + 2e^- $→$ H₂	-0.420
CO₂(g) + 2H⁺ + 2e^- $→$ HCOOH (l)	-0.250
CO₂(g) + H₂O (l) + e^- $→$ HCOO (aq) + OH^-	-1.078
CO₂(g) + 2H⁺ + 2e^- $→$ CO (g) + H₂O (l)	-0.106
CO₂(g) + H₂O (l) + 2e^- $→$ CO (g) + 2OH^-	-0.934

电化学半反应	电极电位（vs. SHE）/ V
2H⁺ + 2e^- $→$ H₂	-0.420
CO₂(g) + 2H⁺ + 2e^- $→$ HCOOH (l)	-0.250
CO₂(g) + H₂O (l) + e^- $→$ HCOO (aq) + OH^-	-1.078
CO₂(g) + 2H⁺ + 2e^- $→$ CO (g) + H₂O (l)	-0.106
CO₂(g) + H₂O (l) + 2e^- $→$ CO (g) + 2OH^-	-0.934

催化剂名称	过电位(vs. RHE)/V	电流密度/mA·cm^-2	电解质	法拉第效率/%	参考文献
Fe³⁺-N-C	-0.45	15	0.5mol/L KHCO₃	90	[40]
Mn-NO/CNs	-0.46	8	0.5mol/L KHCO₃	96	[41]
Ni-N₄-C	-0.4	8	0.5mol/L KHCO₃	90.2	[42]
P/Ni-0@Ni-N-C	-0.8	20	0.5mol/L KHCO₃	91	[43]
ZnN/CNO	-0.47	5.5	0.5mol/L KHCO₃	97	[44]
Fe₁-Ni₁-N-C	-0.5	7	0.5mol/L KHCO₃	96.2	[7]
Au NWs	-0.35	8	0.5mol/L KHCO₃	94	[47]
DDT-Au	-1.1	2.4	0.1mol/L KHCO₃+3.4μmol/L EDTA	40	[48]
ID-Ag	-0.7	18	0.5mol/L KHCO₃	94.5	[49]
Ag	-0.49	3	0.1mol/L KHCO₃	80	[34]
AuCu/CNT	-0.4	2	0.5mol/L KHCO₃	95.2	[51]
Cu/Ni(OH)₂	-0.39	4.3	0.5mol/L NaHCO₃	92	[53]
ZnCa-MOF74	-1.9V (vs.SCE)	4	0.1mol/L KHCO₃	93	[55]
Zn _x Cd_1-_x @S-胺	-1.16	25	0.5mol/L NaHCO₃	60	[57]
p-Cu@Zn（101）	-0.39	11.36	0.1mol/L KHCO₃	85	[58]
FeNPCN	-0.5	3	0.1mol/L KHCO₃	94	[81]
Ni SAs/NCNTs	-0.75	22	0.5mol/L KHCO₃	95	[82]
CoPc/CNT	-0.52	15	0.1mol/L KHCO₃	96	[83]
NC-900	-0.35	5	0.5mol/L NaHCO₃	90	[84]
1D/2D NR/CS-900	-0.45	16	0.5mol/L KHCO₃	94.2	[76]
NSHPC	-0.6	5.58	0.1mol/L KHCO₃	87.8	[85]
SD-AgPMRs	-0.38	2.3	0.1mol/L KHCO₃	80	[86]
NP-C	-0.59	5.5	0.1mol/L KHCO₃	81	[87]
BPNC	-0.5	3	0.1mol/L KHCO₃	81.8	[88]

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