活性炭负载Ni-N-C催化剂提升电解碳酸氢盐法拉第效率

doi:10.11949/0438-1157.20230813

化工学报 ›› 2023, Vol. 74 ›› Issue (11): 4570-4577.DOI: 10.11949/0438-1157.20230813

• 催化、动力学与反应器 • 上一篇下一篇

活性炭负载Ni-N-C催化剂提升电解碳酸氢盐法拉第效率

王正峰¹(), 谢雨杭²^,³, 范永春¹, 李伟科¹, 付乾²^,³()

^1.中国能源建设集团广东省电力设计研究院有限公司，广东广州 510633
^2.重庆大学低品位能源利用及系统教育部重点实验室，重庆 400030
^3.重庆大学能源与动力工程学院，工程热物理研究所，重庆 400030

收稿日期:2023-08-08 修回日期:2023-10-31 出版日期:2023-11-25 发布日期:2024-01-22
通讯作者: 付乾
作者简介:王正峰（1983—），男，高级工程师，wangzhengfeng@gedi.com.cn
基金资助:
重庆市杰出青年科学基金项目(cstc2019jcyjjqX0020)

Active carbons supported Ni-N-C catalysts for enhanced Faraday efficiency of electrolytic bicarbonate

Zhengfeng WANG¹(), Yuhang XIE²^,³, Yongchun FAN¹, Weike LI¹, Qian FU²^,³()

^1.China Energy Engineering Group Guangdong Electric Power Design Institute, Guangzhou 510633, Guangdong, China
^2.Key Laboratory of Low-grade Energy Utilization Technologies and Systems (Chongqing University), Ministry of Education, Chongqing 400030, China
^3.Institute of Engineering Thermophysics, School of Energy and Power Engineering, Chongqing University, Chongqing 400030, China

Received:2023-08-08 Revised:2023-10-31 Online:2023-11-25 Published:2024-01-22
Contact: Qian FU

摘要/Abstract

摘要：

直接电解碳酸氢盐可避免CO₂解吸的高耗能步骤，为将CO₂转化为增值化学品提供了一条具有商业前景的路径。寻找廉价、高效的电解碳酸氢盐催化剂以替代贵金属催化剂（如Ag），是一项重要的工作。本研究将Ni-N-C催化剂引入电解碳酸氢盐体系，以活性炭为碳载体制备了具有发达孔隙结构的Ni-N-C催化剂，为电解碳酸氢盐提供了丰富的催化活性位点和充足的物质传输通道。在N₂饱和的3.0 mol·L^-1 KHCO₃溶液中，Ni-N-C催化剂在100 mA·cm^-2的电流密度时CO法拉第效率（FE_CO）为57.2%，相同条件下Ag催化剂的FE_CO仅为42%。本研究证明了Ni-N-C催化剂在电解碳酸氢盐体系中可以取代Ag将碳酸氢盐转化为CO。

关键词: 电化学还原CO₂, 直接电解碳酸氢盐, 催化剂, 活性炭, 法拉第效率

Abstract:

Direct electrolytic bicarbonate can avoid the energy-intensive step of CO₂ desorption, thus offering a promising route to convert CO₂ into value-added chemicals. It is an important task to find cheap and efficient electrolytic bicarbonate catalysts to replace noble metal catalysts (e.g., Ag). In this study, nickel-nitrogen-carbon (Ni-N-C) catalysts were introduced into the electrolytic bicarbonate system. Ni-N-C catalysts with abundant pore structure were prepared by anchoring Ni single atoms on active carbons, which provided abundant catalytic active sites and sufficient material transport channels for electrolytic bicarbonate. When operated in the N₂-saturated 3.0 mol·L^-1 KHCO₃ solution, the Ni-N-C catalyst obtained a Faraday efficiency for CO production (FE_CO) of 57.2% at 100 mA·cm^-2, while the Ag catalyst only obtained a FE_CO of 42% under the same condition. This study proves that Ni-N-C catalyst can replace Ag in the electrolysis of bicarbonate system to convert bicarbonate into CO.

Key words: electrochemical reduction of CO₂, direct electrolytic bicarbonate, catalyst, active carbon, Faraday efficiency

中图分类号:

TM 911.4

王正峰, 谢雨杭, 范永春, 李伟科, 付乾. 活性炭负载Ni-N-C催化剂提升电解碳酸氢盐法拉第效率[J]. 化工学报, 2023, 74(11): 4570-4577.

Zhengfeng WANG, Yuhang XIE, Yongchun FAN, Weike LI, Qian FU. Active carbons supported Ni-N-C catalysts for enhanced Faraday efficiency of electrolytic bicarbonate[J]. CIESC Journal, 2023, 74(11): 4570-4577.

图/表 6

图1 Ni-N-C@AC催化剂制备流程

Fig.1 Schematic for the preparation of Ni-N-C@AC

图2 Ni-N-C@AC催化剂STEM-HAADF图及元素分布

Fig.2 STEM-HAADF image and elemental mapping of Ni-N-C@AC

图3 Ni-N-C@AC催化剂物理表征结果

Fig.3 Physical characterization of Ni-N-C@AC

表1 Ni-N-C@AC和Ni-N-C@CB电极BET比表面积

Table 1 BET specific surface area of Ni-N-C@AC and Ni-N-C@CB

电极	微孔BET 比表面积/(m²·g^-1)	介孔BET 比表面积/(m²·g^-1)	总BET 比表面积/(m²·g^-1)
Ni-N-C@AC	135.15	286.96	422.11
Ni-N-C@CB	39.43	169.57	209.00

图4 H型反应器CO2RR性能测试

Fig.4 CO2RR performance in the H type cell

图5 MEA反应器电解碳酸氢盐性能测试

Fig.5 The catalytic performance of electrolytic bicarbonate in a MEA-based reactor

参考文献 31

1	Lees E W, Mowbray B A W, Salvatore D A, et al. Linking gas diffusion electrode composition to CO₂ reduction in a flow cell[J]. Journal of Materials Chemistry A, 2020, 8(37): 19493-19501.
2	Kuhl K P, Cave E R, Abram D N, et al. New insights into the electrochemical reduction of carbon dioxide on metallic copper surfaces[J]. Energy & Environmental Science, 2012, 5(5): 7050-7059.
3	Stephanie N, Erlend B, Scott Soren B, et al. Progress and perspectives of electrochemical CO₂ reduction on copper in aqueous electrolyte[J]. Chemical Reviews, 2019, 119(12): 7610-7672.
4	Ren S X, Joulié D, Salvatore D A, et al. Molecular electrocatalysts can mediate fast, selective CO₂ reduction in a flow cell[J]. Science, 2019, 365: 367-369.
5	Kim B, Hillman F, Ariyoshi M, et al. Effects of composition of the micro porous layer and the substrate on performance in the electrochemical reduction of CO₂ to CO[J]. Journal of Power Sources, 2016, 312: 192-198.
6	Del Castillo A, Alvarez-Guerra M, Solla-Gullón J, et al. Sn nanoparticles on gas diffusion electrodes: synthesis, characterization and use for continuous CO₂ electroreduction to formate[J]. Journal of CO₂ Utilization, 2017, 18: 222-228.
7	Weekes D M, Salvatore D A, Reyes A, et al. Electrolytic CO₂ reduction in a flow cell[J]. Accounts of Chemical Research, 2018, 51(4): 910-918.
8	Welch A J, Dunn E, DuChene J S, et al. Bicarbonate or carbonate processes for coupling carbon dioxide capture and electrochemical conversion[J]. ACS Energy Letters, 2020, 5(3): 940-945.
9	Boot-Handford M E, Abanades J C, Anthony E J, et al. Carbon capture and storage update[J]. Energy & Environmental Science, 2014, 7(1): 130-189.
10	Wang Y, Zhao L, Otto A, et al. A review of post-combustion CO₂ capture technologies from coal-fired power plants[J]. Energy Procedia, 2017, 114: 650-665.
11	Li T F, Lees E W, Goldman M, et al. Electrolytic conversion of bicarbonate into CO in a flow cell[J]. Joule, 2019, 3(6): 1487-1497.
12	Lee G, Li Y C, Kim J Y, et al. Electrochemical upgrade of CO₂ from amine capture solution[J]. Nature Energy, 2021, 6(1): 46-53.
13	Lees E W, Goldman M, Fink A G, et al. Electrodes designed for converting bicarbonate into CO[J]. ACS Energy Letters, 2020, 5(7): 2165-2173.
14	Mahyoub S A, Qaraah F A, Chen C Z, et al. An overview on the recent developments of Ag-based electrodes in the electrochemical reduction of CO₂ to CO[J]. Sustainable Energy & Fuels, 2020, 4(1): 50-67.
15	Zhang Z, Wen G B, Luo D, et al. “Two ships in a bottle” design for Zn-Ag-O catalyst enabling selective and long-lasting CO₂ electroreduction[J]. Journal of the American Chemical Society, 2021, 143(18): 6855-6864.
16	Qin L B, Sun F, Ma X S, et al. Homoleptic alkynyl-protected Ag₁₅ nanocluster with atomic precision: structural analysis and electrocatalytic performance toward CO₂ reduction[J]. Angewandte Chemie (International Ed. in English), 2021, 60(50): 26136-26141.
17	Zhang M L, Wu T S, Hong S, et al. Efficient electrochemical reduction of CO₂ by Ni-N catalysts with tunable performance[J]. ACS Sustainable Chemistry & Engineering, 2019, 7(17): 15030-15035.
18	Yang H Z, Shang L, Zhang Q H, et al. A universal ligand mediated method for large scale synthesis of transition metal single atom catalysts[J]. Nature Communications, 2019, 10: 4585.
19	Jia M W, Choi C, Wu T S, et al. Carbon-supported Ni nanoparticles for efficient CO₂ electroreduction[J]. Chemical Science, 2018, 9(47): 8775-8780.
20	Pan F P, Deng W, Justiniano C, et al. Identification of champion transition metals centers in metal and nitrogen-codoped carbon catalysts for CO₂ reduction[J]. Applied Catalysis B: Environmental, 2018, 226: 463-472.
21	Ma S S, Su P P, Huang W J, et al. Atomic Ni species anchored N-doped carbon hollow spheres as nanoreactors for efficient electrochemical CO₂ reduction[J]. ChemCatChem, 2019, 11(24): 6092-6098.
22	Liang S Y, Huang L, Gao Y S, et al. Electrochemical reduction of CO₂ to CO over transition metal/N-doped carbon catalysts: the active sites and reaction mechanism[J]. Advanced Science, 2021, 8(24): 2102886
23	Sun Z, Liu Z, Han B, et al. Fabrication of ruthenium-carbon nanotube nanocomposites in supercritical water[J]. Advanced Materials, 2005, 17(7): 928-932.
24	Yang H B, Hung S F, Liu S, et al. Atomically dispersed Ni(Ⅰ) as the active site for electrochemical CO₂ reduction[J]. Nature Energy, 2018, 3(2): 140-147.
25	Junge Puring K, Siegmund D, Timm J, et al. Electrochemical CO₂ reduction: tailoring catalyst layers in gas diffusion electrodes[J]. Advanced Sustainable Systems, 2021, 5(1): 2000088.
26	Zhang Z S, Lees E W, Habibzadeh F, et al. Porous metal electrodes enable efficient electrolysis of carbon capture solutions[J]. Energy & Environmental Science, 2022, 15(2): 705-713.
27	Yue P T, Xiong K R, Ma L, et al. MOF-derived Ni single-atom catalyst with abundant mesopores for efficient mass transport in electrolytic bicarbonate conversion[J]. ACS Applied Materials & Interfaces, 2022, 14(49): 54840-54847.
28	Larrea C, Torres D, Avilés-Moreno J R, et al. Multi-parameter study of CO₂ electrochemical reduction from concentrated bicarbonate feed[J]. Journal of CO₂ Utilization, 2022, 57: 101878.
29	Zhang W, Huang C Q, Xiao Q, et al. Atypical oxygen-bearing copper boosts ethylene selectivity toward electrocatalytic CO₂ reduction[J]. Journal of the American Chemical Society, 2020, 142(26): 11417-11427.
30	Wang Q N, Dong H, Yu H, et al. Enhanced performance of gas diffusion electrode for electrochemical reduction of carbon dioxide to formate by adding polytetrafluoroethylene into catalyst layer[J]. Journal of Power Sources, 2015, 279: 1-5.
31	Burdyny T, Smith W A. CO₂ reduction on gas-diffusion electrodes and why catalytic performance must be assessed at commercially-relevant conditions[J]. Energy & Environmental Science, 2019, 12(5): 1442-1453.

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活性炭负载Ni-N-C催化剂提升电解碳酸氢盐法拉第效率

Active carbons supported Ni-N-C catalysts for enhanced Faraday efficiency of electrolytic bicarbonate

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