碳基单原子催化剂在电催化二氧化碳还原中的研究进展

doi:10.16085/j.issn.1000-6613.2023-1639

摘要/Abstract

摘要：

电催化CO₂还原技术是一种极富潜力的CO₂利用手段，开发具有高附加值产品选择性的电催化剂对该技术至关重要。近年来，碳基单原子材料作为一种原子利用率高、化学结构可调的新型催化剂在电催化CO₂还原反应中表现出极高的研究价值。本文介绍了电催化CO₂还原为不同产物的反应路径，总结了不同金属种类包括Fe、Cu、Ni、Co等的碳基单原子催化剂在电催化CO₂还原反应中的催化性能，分别阐述了单原子配位环境调节、电子结构调节、活性位点数量调控等调节策略对催化剂性能和反应过程等的影响。最后针对电催化CO₂还原反应碳基单原子催化剂的设计合成，从如何提高生成多碳产物的选择性以及鉴别反应过程中活性位点的真实状态等方面进行了展望。

关键词: 二氧化碳, 电化学, 催化剂, 碳基材料, 单原子

Abstract:

Electrochemical reduction is considered as a promising means of CO₂ utilization. It is crucial to develop an electrocatalyst that can increase the selectivity for high value-added products. Recently, carbon-based single-atom catalysts have shown great research value in electrocatalytic CO₂reduction reaction due to their high atom utilization and tunable chemical structure. This review introduces the reaction pathways of electrocatalytic CO₂ reduction to various products. The catalytic performance for electrocatalytic CO₂ reduction reaction over carbon-based single-atom catalysts with different metal species including Fe, Cu, Ni, Co, respectively is summarized. The effects of tuning strategies such as coordination environment tuning, electronic structure tuning, and active site number tuning on the catalytic performance and the reaction process are illustrated. In order to achieve better design and synthesis of carbon-based single-atom catalysts for the electrocatalytic CO₂ reduction reaction, the strategies to improve the selectivity of the generated multi-carbon products and identify the true state of the active sites are discussed.

Key words: carbon dioxide, electrochemistry, catalyst, carbon based material, single atom

中图分类号:

TQ426

李永恒, 王文波, 辛靖, 吴冲冲, 苏梦军, 杨国明. 碳基单原子催化剂在电催化二氧化碳还原中的研究进展[J]. 化工进展, 2024, 43(10): 5486-5497.

LI Yongheng, WANG Wenbo, XIN Jing, WU Chongchong, SU Mengjun, YANG Guoming. Research progress of carbon based single atom catalysts for electrocatalytic reduction of carbon dioxide[J]. Chemical Industry and Engineering Progress, 2024, 43(10): 5486-5497.

图/表 9

表1 不同反应路径对应的反应平衡电位和产物（pH=7，电解液浓度1mol/L，25℃，0.1MPa）[6,11-13]

反应路径	反应平衡电位（vs. RHE）/V	产物
$C O 2 + 2 H + + 2 e - → C O + H 2 O$	-0.1	一氧化碳（CO）
$C O 2 + 6 H + + 6 e - → C H 3 O H + 2 H 2 O$	+0.03	甲醇（CH₃OH）
$C O 2 + 2 H + + 2 e - → H C O O H$	-0.12	甲酸（HCOOH）
$C O 2 + 8 H + + 8 e - → C H 4 + 2 H 2 O$	+0.17	甲烷（CH₄）
$2 C O 2 + 12 H + + 12 e - → C 2 H 4 + 4 H 2 O$	+0.08	乙烯（C₂H₄）
$2 C O 2 + 8 H + + 8 e - → C H 3 C O O H + 2 H 2 O$	+0.11	乙酸（CH₃COOH）
$2 C O 2 + 10 H + + 10 e - → C H 3 C H O + 3 H 2 O$	+0.06	乙醛（CH₃CHO）
$2 C O 2 + 12 H + + 12 e - → C 2 H 5 O H + 3 H 2 O$	+0.09	乙醇（C₂H₅OH）
$2 C O 2 + 14 H + + 14 e - → C 2 H 6 + 4 H 2 O$	+0.14	乙烷（C₂H₆）
$3 C O 2 + 18 H + + 18 e - → C 3 H 7 O H + 5 H 2 O$	+0.1	丙醇（C₃H₇OH）

表1 不同反应路径对应的反应平衡电位和产物（pH=7，电解液浓度1mol/L，25℃，0.1MPa）[6,11-13]

反应路径	反应平衡电位（vs. RHE）/V	产物
$C O 2 + 2 H + + 2 e - → C O + H 2 O$	-0.1	一氧化碳（CO）
$C O 2 + 6 H + + 6 e - → C H 3 O H + 2 H 2 O$	+0.03	甲醇（CH₃OH）
$C O 2 + 2 H + + 2 e - → H C O O H$	-0.12	甲酸（HCOOH）
$C O 2 + 8 H + + 8 e - → C H 4 + 2 H 2 O$	+0.17	甲烷（CH₄）
$2 C O 2 + 12 H + + 12 e - → C 2 H 4 + 4 H 2 O$	+0.08	乙烯（C₂H₄）
$2 C O 2 + 8 H + + 8 e - → C H 3 C O O H + 2 H 2 O$	+0.11	乙酸（CH₃COOH）
$2 C O 2 + 10 H + + 10 e - → C H 3 C H O + 3 H 2 O$	+0.06	乙醛（CH₃CHO）
$2 C O 2 + 12 H + + 12 e - → C 2 H 5 O H + 3 H 2 O$	+0.09	乙醇（C₂H₅OH）
$2 C O 2 + 14 H + + 14 e - → C 2 H 6 + 4 H 2 O$	+0.14	乙烷（C₂H₆）
$3 C O 2 + 18 H + + 18 e - → C 3 H 7 O H + 5 H 2 O$	+0.1	丙醇（C₃H₇OH）

图1 CO2还原反应路径[29-30]

图2 石墨烯基不同空间位置Fe单原子在电催化CO2还原反应中的自由能变化[38]

图3 不同配位环境Cu单原子催化剂进行电催化CO2还原反应的路径和自由能变化[45]

图4 不同Cu活性位点上进行电催化CO2还原反应以及析氢反应的自由能变化[46]

图5 Ni—N2(NH2)和Ni—N3位点上进行电催化CO2还原反应的自由能变化[47]

图6 不同Ni催化剂上发生CO2还原反应的自由能变化以及与析氢反应的极限电位差[49]

图7 CoPor和COF@CoPor催化剂上进行电催化CO2还原反应的自由能变化[25]

表2 不同碳基单原子催化剂的电催化CO2还原反应表现

催化剂	电解液	产物	电压（vs. RHE） /V	法拉第效率 /%	最大电流密度 /mA∙cm^-2	稳定性 /h	转化频率 /h^-1	参考文献
Fe-SA/ZIF	0.1mol/L KHCO₃	CO	-1.0~-0.4	98	18	40	—	[35]
FeN₄Cl/NC	0.5mol/L KHCO₃	CO	-0.7~-0.3	90.5	40	18	1566	[36]
Fe-N/P-C	0.5mol/L KHCO₃	CO	-0.7~-0.4（>90%）	98	20	24	508.8	[37]
FeN₄/石墨烯边缘	0.1mol/L KHCO₃	CO	-0.6~-0.4	94	—	9	1630	[38]
Fe₂—N-C	0.5mol/L KHCO₃	CO	-0.9~-0.5	80	45	20	26,637	[40]
Fe-n-f-CNTs（碳纳米管）	0.5mol/L KHCO₃	CH₃CH₂OH	-1.2~-0.6	45	60	—	—	[41]
Cu SAs/NC	0.1mol/L KHCO₃	CO	-0.9~-0.5（>70%）	92	8.9	30	—	[54]
Cu—N₄—C/1100	0.1mol/L KHCO₃	CO	-1.1~-0.6（>90%）	98	14	40	1012	[45]
2Bn-Cu@UiO-67	1.0mol/L KOH	CH₄	-1.6~-1.1（>70%）	81	420	—	58680	[55]
Cu-C（石墨炔）	0.1mol/L KHCO₃	CH₄	—	66	40	10	2311	[56]
CuSAs/TCNFs （贯通孔碳纳米纤维）	0.1mol/L KHCO₃	CH₃OH	-0.9~-0.4	44	93	50	—	[57]
Cu₃(2，3，7，8，12， B-六羟基三环喹唑啉)₂	0.1mol/L KHCO₃	CH₃OH	-0.8~-0.2	53.6	45	—	—	[58]
CuNi-DSA（双单原子）/ CNFs（碳纳米纤维）	0.1mol/L KHCO₃	CO	-1.18~-0.78	99.60	42	25	2870	[59]
Cu/C	0.1mol/L KHCO₃	CH₃CH₂OH	-1.2~-0.4	91	25	16	—	[44]
Cu-SA/NPC（氮磷共掺杂碳）	0.1mol/L KHCO₃	CH₃COCH₃	-0.96~-0.16	36.7	15	—	—	[42]
Ni-SAs-NC	0.5mol/L KHCO₃	CO	-1.0~-0.6（>90%)	98	31	30	—	[60]
MeNiPc（甲酯化酞菁镍）/ （石墨烯）	0.5mol/L KHCO₃	CO	-0.93~-0.58（>90%)	99.40	28	12	8310	[61]
Ni-N-MEGO	0.5mol/L KHCO₃	CO	-0.7~-0.55（>90%)	92.10	28.6	21	864	[47]
Ni-SAs@BNC	0.5mol/L KHCO₃	CO	-1.2~-0.6（>97%)	99	67.91	40	—	[49]
SACs Co—N₂C₃	0.1mol/L KHCO₃	CO	-1.1~-0.4（>90%)	92	8.3	40	1451	[50]
CoSA/HCNFs （非自支撑碳纳米纤维）	0.1mol/L KHCO₃	CO	-0.9~-0.4（>90%)	97	67	50	—	[62]
Co-HNC（空心氮掺杂碳）	0.1mol/L KHCO₃	合成气	-1.0~-0.7	100	—	24	—	[63]
CoPc（酞菁钴）/石墨烯	0.5mol/L KHCO₃	CO	-1.6~-0.6	85.40	—	30	—	[64]
CoPc/MWCNT（多壁碳纳米管）	0.5mol/L K₂HPO₄	CH₃OH	—	65	100	8	—	[65]
CoPor-N₃/CNTs	0.1mol/L KHCO₃	CO	-0.7~-0.35（>46%)	96	20.3	24	550	[66]
COF@CoPor	0.5mol/L KHCO₃	CO	-1.0~-0.5（>84.2%)	73.8	12.5	10	4578	[25]
SACs Co-ZIF	0.5mol/L KHCO₃	CO	-0.7~-0.5（>45%)	60	12	10	—	[67]
2D-Co-COF₅₀₀	0.5mol/L KHCO₃	CO	-1.0~-0.5（>80.2%)	96.50	17.9	15	336	[51]
CoN₄/石墨烯	0.1mol/L KHCO₃	CO	-0.96~-0.26	95	19	15	—	[68]
Co—N₅/HNPCSs （空心氮掺杂多孔碳球）	0.2mol/L NaHCO₃	CO	-0.88~-0.57（>90%）	99	17.5	10	480.2	[69]
Sb SA/NC	0.5mol/L KHCO₃	HCOOH	-1.0~-0.7	94	25	10	—	[15]
Pd₂ DAC（双原子催化剂）	0.5mol/L KHCO₃	CO	-0.9~-0.7	98.20	38	12	—	[23]
Bi SA	0.5mol/L KHCO₃	CO	-1.2~-0.8	>90	29.3	40	9504	[10]
Bi SAs/NC	0.1mol/L NaHCO₃	CO	-0.625~-0.375	97	—	—	10118	[16]
Cd-NC SACs	0.5mol/L KHCO₃	CO	-0.90~-0.65	91.40	17.5	10	—	[24]
Ga—N₃S-PC	0.5mol/L KHCO₃	CO	-0.30~-0.20	92	175	24	—	[4]
SnPc（酞菁锡）/CNT-OH	1mol/L KOH	HCOOH	-1.2~-0.7	89.40	135	9	—	[53]
ZnN₄S₁/P-HC（空心碳）	0.1mol/L KHCO₃	CO	-0.9~-0.4	约100	35	30	1241	[52]
InCe/CN	0.1mol/L KHCO₃	HCOOH	-1.4~-1.2	77	—	6	—	[70]

表2 不同碳基单原子催化剂的电催化CO2还原反应表现

催化剂	电解液	产物	电压（vs. RHE） /V	法拉第效率 /%	最大电流密度 /mA∙cm^-2	稳定性 /h	转化频率 /h^-1	参考文献
Fe-SA/ZIF	0.1mol/L KHCO₃	CO	-1.0~-0.4	98	18	40	—	[35]
FeN₄Cl/NC	0.5mol/L KHCO₃	CO	-0.7~-0.3	90.5	40	18	1566	[36]
Fe-N/P-C	0.5mol/L KHCO₃	CO	-0.7~-0.4（>90%）	98	20	24	508.8	[37]
FeN₄/石墨烯边缘	0.1mol/L KHCO₃	CO	-0.6~-0.4	94	—	9	1630	[38]
Fe₂—N-C	0.5mol/L KHCO₃	CO	-0.9~-0.5	80	45	20	26,637	[40]
Fe-n-f-CNTs（碳纳米管）	0.5mol/L KHCO₃	CH₃CH₂OH	-1.2~-0.6	45	60	—	—	[41]
Cu SAs/NC	0.1mol/L KHCO₃	CO	-0.9~-0.5（>70%）	92	8.9	30	—	[54]
Cu—N₄—C/1100	0.1mol/L KHCO₃	CO	-1.1~-0.6（>90%）	98	14	40	1012	[45]
2Bn-Cu@UiO-67	1.0mol/L KOH	CH₄	-1.6~-1.1（>70%）	81	420	—	58680	[55]
Cu-C（石墨炔）	0.1mol/L KHCO₃	CH₄	—	66	40	10	2311	[56]
CuSAs/TCNFs （贯通孔碳纳米纤维）	0.1mol/L KHCO₃	CH₃OH	-0.9~-0.4	44	93	50	—	[57]
Cu₃(2，3，7，8，12， B-六羟基三环喹唑啉)₂	0.1mol/L KHCO₃	CH₃OH	-0.8~-0.2	53.6	45	—	—	[58]
CuNi-DSA（双单原子）/ CNFs（碳纳米纤维）	0.1mol/L KHCO₃	CO	-1.18~-0.78	99.60	42	25	2870	[59]
Cu/C	0.1mol/L KHCO₃	CH₃CH₂OH	-1.2~-0.4	91	25	16	—	[44]
Cu-SA/NPC（氮磷共掺杂碳）	0.1mol/L KHCO₃	CH₃COCH₃	-0.96~-0.16	36.7	15	—	—	[42]
Ni-SAs-NC	0.5mol/L KHCO₃	CO	-1.0~-0.6（>90%)	98	31	30	—	[60]
MeNiPc（甲酯化酞菁镍）/ （石墨烯）	0.5mol/L KHCO₃	CO	-0.93~-0.58（>90%)	99.40	28	12	8310	[61]
Ni-N-MEGO	0.5mol/L KHCO₃	CO	-0.7~-0.55（>90%)	92.10	28.6	21	864	[47]
Ni-SAs@BNC	0.5mol/L KHCO₃	CO	-1.2~-0.6（>97%)	99	67.91	40	—	[49]
SACs Co—N₂C₃	0.1mol/L KHCO₃	CO	-1.1~-0.4（>90%)	92	8.3	40	1451	[50]
CoSA/HCNFs （非自支撑碳纳米纤维）	0.1mol/L KHCO₃	CO	-0.9~-0.4（>90%)	97	67	50	—	[62]
Co-HNC（空心氮掺杂碳）	0.1mol/L KHCO₃	合成气	-1.0~-0.7	100	—	24	—	[63]
CoPc（酞菁钴）/石墨烯	0.5mol/L KHCO₃	CO	-1.6~-0.6	85.40	—	30	—	[64]
CoPc/MWCNT（多壁碳纳米管）	0.5mol/L K₂HPO₄	CH₃OH	—	65	100	8	—	[65]
CoPor-N₃/CNTs	0.1mol/L KHCO₃	CO	-0.7~-0.35（>46%)	96	20.3	24	550	[66]
COF@CoPor	0.5mol/L KHCO₃	CO	-1.0~-0.5（>84.2%)	73.8	12.5	10	4578	[25]
SACs Co-ZIF	0.5mol/L KHCO₃	CO	-0.7~-0.5（>45%)	60	12	10	—	[67]
2D-Co-COF₅₀₀	0.5mol/L KHCO₃	CO	-1.0~-0.5（>80.2%)	96.50	17.9	15	336	[51]
CoN₄/石墨烯	0.1mol/L KHCO₃	CO	-0.96~-0.26	95	19	15	—	[68]
Co—N₅/HNPCSs （空心氮掺杂多孔碳球）	0.2mol/L NaHCO₃	CO	-0.88~-0.57（>90%）	99	17.5	10	480.2	[69]
Sb SA/NC	0.5mol/L KHCO₃	HCOOH	-1.0~-0.7	94	25	10	—	[15]
Pd₂ DAC（双原子催化剂）	0.5mol/L KHCO₃	CO	-0.9~-0.7	98.20	38	12	—	[23]
Bi SA	0.5mol/L KHCO₃	CO	-1.2~-0.8	>90	29.3	40	9504	[10]
Bi SAs/NC	0.1mol/L NaHCO₃	CO	-0.625~-0.375	97	—	—	10118	[16]
Cd-NC SACs	0.5mol/L KHCO₃	CO	-0.90~-0.65	91.40	17.5	10	—	[24]
Ga—N₃S-PC	0.5mol/L KHCO₃	CO	-0.30~-0.20	92	175	24	—	[4]
SnPc（酞菁锡）/CNT-OH	1mol/L KOH	HCOOH	-1.2~-0.7	89.40	135	9	—	[53]
ZnN₄S₁/P-HC（空心碳）	0.1mol/L KHCO₃	CO	-0.9~-0.4	约100	35	30	1241	[52]
InCe/CN	0.1mol/L KHCO₃	HCOOH	-1.4~-1.2	77	—	6	—	[70]

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