单原子Ni、N共掺杂碳材料基催化剂电还原CO2制CO研究进展

doi:10.16085/j.issn.1000-6613.2023-0857

摘要/Abstract

摘要：

单原子Ni、N共掺杂碳材料基催化剂（Ni-N-C）电催化CO₂制CO，因其在较大的电流密度和较大的过电势下仍具有超高的CO选择性，引起了广泛关注。本文综述了Ni-N-C电催化CO₂制CO研究进展，包括氮掺杂碳材料基催化剂和Ni-N-C电催化CO₂制CO。总结了氮掺杂碳材料基催化剂中不同形态N的催化活性，目前为止，N在该类催化剂电化学还原CO₂中的确切作用没有达成共识。此外，还总结了Ni-N-C的催化性能、催化机理及催化性能改性方法，探讨了与Ni配位的N原子和缺陷位对催化活性的影响规律，分析了各类碳载体的优缺点。Ni-N-C电化学还原CO₂制CO研究已取得一定的进展，如电流密度可达工业级要求，但是其实现大规模工业化应用还需解决一些关键问题，如开发高活性和高稳定性Ni-N-C的定向制备技术；研发制备简易温和、成本低廉、具有抗腐蚀性、耐高温的先进碳载体材料。

关键词: 单原子Ni, 富氮碳材料, 电催化, CO₂制CO

Abstract:

Study of single-atom Ni and N co-doped carbon-material based catalysts (Ni-N-C) for CO₂ electrochemical reduction (CO₂ER) to CO began in the past decade. It has received a lot of attentions because it possessed ultra-high CO selectivity even under high current density and high overpotential. This article reviewed recent advances in Ni-N-C for CO₂ER to CO, including nitrogen doped carbon-material based catalysts and Ni-N-C for CO₂ER to CO. The catalytic activities of different forms of N in carbon-material based catalysts were summarized, and so far, the exact role of N in carbon-material based catalysts for CO₂ER was controversial. Moreover, the catalytic performance, catalytic mechanism and catalytic performance modification for Ni-N-C were also summarized. The effects of N atoms and defect sites coordinated with Ni on catalytic activity, and the advantages and disadvantages of various carbon-carriers were analyzed. Although research on CO₂ER to CO using Ni-N-C has made certain progress, such as the current density reaching industrial grade requirements, some key issues still needed to be solved to achieve its large-scale industrial applications, such as developing directional preparation technologies for high activity and high stability Ni-N-C and developing advanced carbon-material carriers, which were simple and mild preparation, low cost, corrosion-resistant high-temperature resistant.

Key words: single atom Ni, nitrogen rich carbon materials, electrocatalytic, CO₂ to CO

中图分类号:

TQ138.1

蔚德磊, 韩康顺, 陈瑶, 刘祥春, 崔平. 单原子Ni、N共掺杂碳材料基催化剂电还原CO₂制CO研究进展[J]. 化工进展, 2024, 43(6): 3174-3186.

YU Delei, HAN Kangshun, CHEN Yao, LIU Xiangchun, CUI Ping. Recent advances in electroreduction of CO₂ to CO using single atom Ni, N co-doped carbon-material based catalysts[J]. Chemical Industry and Engineering Progress, 2024, 43(6): 3174-3186.

图/表 11

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制备方法	碳材料载体或其前体	电化学性能		参考文献
制备方法	碳材料载体或其前体	电解液	性能参数	参考文献
900℃煅烧	改性石墨烯	0.1mol/L KHCO₃	FE_CO=90% @ -0.7~-0.9V(vs.RHE)；TOF=2700h^-1 @ -0.7V(vs.RHE)；稳定运行时长> 5h @ -0.65V(vs.RHE)；塔菲尔斜率=126mV/dec	[90]
750℃煅烧	石墨烯纳米片	0.5mol/L KHCO₃	FE_CO=95%、电流密度=11mA/cm² @ 620 mV；TOF = 6.8s^-1 @ 0.57V；稳定运行时长> 20h @ 12mA/cm²；塔菲尔斜率=110mV/dec	[91]
分子工程法引入甲氧基、1000℃煅烧	碳纳米管	1mol/L KHCO₃	FE_CO=99.5% @ 电流密度=10~300mA/cm²； TOF = 2.9s^-1 @ -0.64V(vs.RHE)；稳定运行时长> 40h @ 150mA/cm²	[92]
微波诱导等离子体法引入S原子	氧化石墨烯	0.5mol/L KHCO₃	FE_CO=97%、电流密度=40mA/cm²@ -0.8~-0.9V(vs.RHE)； TOF = 3965h^-1 @ -0.79V(vs.RHE)；稳定运行时长> 20h @ -0.8V	[93]
氰基修饰碳基底、670℃煅烧	C₃N₄	0.5mol/L KHCO₃	FE_CO≥90% @ -0.58~-1.18V(vs.RHE)；电流密度=46.8mA/cm²、 TOF = 22000h^-1 @ -1.18V；稳定运行时长> 12h @ -0.88V(vs.RHE)	[42]
800~1000℃煅烧、模板法	多巴胺	0.5mol/L KHCO₃	FE_CO=96%、电流密度=35mA/cm²@ -1V(vs.RHE)；稳定运行时长>12h @ 2.4V	[94]
400~1000℃煅烧	ZIF-8	0.5mol/L KHCO₃	FE_CO=92%、电流密度=92.1mA/cm²、TOF = 5500h^-1 @ -0.9V(vs.RHE)；稳定运行时长> 70h @ -0.6V(vs.RHE)	[95]
1000℃煅烧	ZIF-8	0.5mol/L KHCO₃	FE_CO=71.9%、电流密=10.48mA/cm²、TOF = 5273h^-1 @ -0.89V；稳定运行时长>60h @ -1.0V(vs.RHE)；塔菲尔斜率=249mV/dec	[98]
静电纺丝法、750℃煅烧	石墨壳	0.1mol/L KHCO₃	FE_CO=93.2%、电流密度=4mA/cm²、稳定运行时长>20h @ -0.7V；塔菲尔斜率=138.5mV/dec	[32]
拓扑化学转化法	葡萄糖、C₃N₄	0.5mol/L KHCO₃	FE_CO>90% @ -0.5~-0.9V；电流密度=28.6mA/cm²@ -0.81V；塔菲尔斜率=103mV/dec	[44]
850℃煅烧	碳纳米管	0.5mol/L KHCO₃	FE_CO=97% @ -0.83V(vs.RHE)；TOF =13860h^-1、电流密度=17.5mA/cm²@ -0.94 V(vs.RHE)；稳定运行时长>16h @ -0.79V(vs.RHE)	[99]
后离子交换法、900℃煅烧	ZIF-8	0.5mol/L KHCO₃	FE_CO=95.6%、TOF=1425 h^-1、电流密度=6.64mA/cm²、稳定运行时长>10h @ -0.65V；塔菲尔斜率=99mV/dec	[100]
950℃煅烧	三（4-氨苯基）胺为原料制备酶	0.5mol/L KHCO₃	FE_CO=99.6%、电流密度=1.23A/cm²、TOF =69.7s^-1 @ -2.4V(vs.RHE)；稳定运行时长>100h @ -2.2 V(vs.RHE)	[101]
静电纺丝法、1000℃煅烧	聚丙烯腈、聚苯乙烯	0.5mol/L KHCO₃	FE_CO=96.6% @ -0.8 V(vs.RHE)；电流密度=15.5mA/cm²、 TOF=4606.5h^-1 @ -1.0V；塔菲尔斜率=124.6mV/dec	[102]
600~800℃煅烧	苯代三聚氰胺、氰尿酸	0.5mol/L KHCO₃	FE_CO>90%、电流密度=65mA/cm²、TOF=135000h^-1 @ -0.9V(vs.RHE)；稳定运行时长>14h @ -0.7V(vs.RHE)；塔菲尔斜率=124mV/dec	[103]
900℃煅烧、引入S原子	石墨烯	0.5mol/L KHCO₃	FE_CO=97%、电流密度=350A/g_catalyst、TOF = 14800h^-1、稳定运行时长>100h @ 0.61V；塔菲尔斜率=114mV/dec	[105]
600℃、1000℃煅烧	炭黑	0.5mol/L KHCO₃	FE_CO >95% @ -0.6~-0.84V(vs.RHE)；电流密度=21mA/cm² @ -0. 9V (vs.RHE)；稳定运行时长>24h @ 0.55V；塔菲尔斜率=101mV/dec	[110]
静电纺丝法、900℃煅烧	多孔碳纤维薄膜	0.5mol/L KHCO₃	FE_CO=96%、电流密度=56.1mA/cm² @ -0.7V(vs.RHE)；塔菲尔斜率=117mV/dec	[111]

制备方法	碳材料载体或其前体	电化学性能		参考文献
制备方法	碳材料载体或其前体	电解液	性能参数	参考文献
900℃煅烧	改性石墨烯	0.1mol/L KHCO₃	FE_CO=90% @ -0.7~-0.9V(vs.RHE)；TOF=2700h^-1 @ -0.7V(vs.RHE)；稳定运行时长> 5h @ -0.65V(vs.RHE)；塔菲尔斜率=126mV/dec	[90]
750℃煅烧	石墨烯纳米片	0.5mol/L KHCO₃	FE_CO=95%、电流密度=11mA/cm² @ 620 mV；TOF = 6.8s^-1 @ 0.57V；稳定运行时长> 20h @ 12mA/cm²；塔菲尔斜率=110mV/dec	[91]
分子工程法引入甲氧基、1000℃煅烧	碳纳米管	1mol/L KHCO₃	FE_CO=99.5% @ 电流密度=10~300mA/cm²； TOF = 2.9s^-1 @ -0.64V(vs.RHE)；稳定运行时长> 40h @ 150mA/cm²	[92]
微波诱导等离子体法引入S原子	氧化石墨烯	0.5mol/L KHCO₃	FE_CO=97%、电流密度=40mA/cm²@ -0.8~-0.9V(vs.RHE)； TOF = 3965h^-1 @ -0.79V(vs.RHE)；稳定运行时长> 20h @ -0.8V	[93]
氰基修饰碳基底、670℃煅烧	C₃N₄	0.5mol/L KHCO₃	FE_CO≥90% @ -0.58~-1.18V(vs.RHE)；电流密度=46.8mA/cm²、 TOF = 22000h^-1 @ -1.18V；稳定运行时长> 12h @ -0.88V(vs.RHE)	[42]
800~1000℃煅烧、模板法	多巴胺	0.5mol/L KHCO₃	FE_CO=96%、电流密度=35mA/cm²@ -1V(vs.RHE)；稳定运行时长>12h @ 2.4V	[94]
400~1000℃煅烧	ZIF-8	0.5mol/L KHCO₃	FE_CO=92%、电流密度=92.1mA/cm²、TOF = 5500h^-1 @ -0.9V(vs.RHE)；稳定运行时长> 70h @ -0.6V(vs.RHE)	[95]
1000℃煅烧	ZIF-8	0.5mol/L KHCO₃	FE_CO=71.9%、电流密=10.48mA/cm²、TOF = 5273h^-1 @ -0.89V；稳定运行时长>60h @ -1.0V(vs.RHE)；塔菲尔斜率=249mV/dec	[98]
静电纺丝法、750℃煅烧	石墨壳	0.1mol/L KHCO₃	FE_CO=93.2%、电流密度=4mA/cm²、稳定运行时长>20h @ -0.7V；塔菲尔斜率=138.5mV/dec	[32]
拓扑化学转化法	葡萄糖、C₃N₄	0.5mol/L KHCO₃	FE_CO>90% @ -0.5~-0.9V；电流密度=28.6mA/cm²@ -0.81V；塔菲尔斜率=103mV/dec	[44]
850℃煅烧	碳纳米管	0.5mol/L KHCO₃	FE_CO=97% @ -0.83V(vs.RHE)；TOF =13860h^-1、电流密度=17.5mA/cm²@ -0.94 V(vs.RHE)；稳定运行时长>16h @ -0.79V(vs.RHE)	[99]
后离子交换法、900℃煅烧	ZIF-8	0.5mol/L KHCO₃	FE_CO=95.6%、TOF=1425 h^-1、电流密度=6.64mA/cm²、稳定运行时长>10h @ -0.65V；塔菲尔斜率=99mV/dec	[100]
950℃煅烧	三（4-氨苯基）胺为原料制备酶	0.5mol/L KHCO₃	FE_CO=99.6%、电流密度=1.23A/cm²、TOF =69.7s^-1 @ -2.4V(vs.RHE)；稳定运行时长>100h @ -2.2 V(vs.RHE)	[101]
静电纺丝法、1000℃煅烧	聚丙烯腈、聚苯乙烯	0.5mol/L KHCO₃	FE_CO=96.6% @ -0.8 V(vs.RHE)；电流密度=15.5mA/cm²、 TOF=4606.5h^-1 @ -1.0V；塔菲尔斜率=124.6mV/dec	[102]
600~800℃煅烧	苯代三聚氰胺、氰尿酸	0.5mol/L KHCO₃	FE_CO>90%、电流密度=65mA/cm²、TOF=135000h^-1 @ -0.9V(vs.RHE)；稳定运行时长>14h @ -0.7V(vs.RHE)；塔菲尔斜率=124mV/dec	[103]
900℃煅烧、引入S原子	石墨烯	0.5mol/L KHCO₃	FE_CO=97%、电流密度=350A/g_catalyst、TOF = 14800h^-1、稳定运行时长>100h @ 0.61V；塔菲尔斜率=114mV/dec	[105]
600℃、1000℃煅烧	炭黑	0.5mol/L KHCO₃	FE_CO >95% @ -0.6~-0.84V(vs.RHE)；电流密度=21mA/cm² @ -0. 9V (vs.RHE)；稳定运行时长>24h @ 0.55V；塔菲尔斜率=101mV/dec	[110]
静电纺丝法、900℃煅烧	多孔碳纤维薄膜	0.5mol/L KHCO₃	FE_CO=96%、电流密度=56.1mA/cm² @ -0.7V(vs.RHE)；塔菲尔斜率=117mV/dec	[111]

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单原子Ni、N共掺杂碳材料基催化剂电还原CO₂制CO研究进展

Recent advances in electroreduction of CO₂ to CO using single atom Ni, N co-doped carbon-material based catalysts

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