双金属⁃氮掺杂炭催化剂的制备及其电催化CO2性能

doi:10.12422/j.issn.1006-396X.2023.03.001

摘要/Abstract

摘要：

金属?氮掺杂炭是一类新兴的应用于CO₂还原反应(CO₂RR)的非贵金属电催化剂。目前的制备方法主要采用浸渍法为主的后处理方式，通常涉及较多的步骤，且金属种类单一。以4,4′?联吡啶为配体、硝酸铁和氯化铜为金属节点，通过配位竞争的策略合成FeCu配位聚合物，后经原位热处理得到FeCu?N?C系列催化剂。分别采用SEM、TEM、XRD、N₂吸附?脱附等技术对催化剂形貌结构、金属物种状态、孔隙结构等进行了表征。采用三电极体系评价了FeCu?N?C系列催化剂在电催化CO₂RR产合成气（CO/H₂）中的性能。结果表明，通过调控Fe、Cu的物质的量比、炭化温度、金属组合等条件可调控合成气中n(CO)/n(H₂)的比例。在较宽电位范围内（-0.7~-1.3 V）生成的合成气中n(CO)/n(H₂)可在0.15~3.33调控，可满足甲醇合成、费托反应及合成气发酵等重要反应的供给气配比。

关键词: 多孔炭, 金属?氮掺杂炭, 双金属催化剂, 电催化CO₂还原, 合成气

Abstract:

Metal?nitrogen doped carbon is an emerging class of non?precious metal electrocatalysts used in carbon dioxide reduction reactions(CO₂RR).Metal?nitrogen doped carbon is an emerging class of non?precious metal electrocatalysts in carbon dioxide reduction reactions(CO₂RR).Current preparation methods mainly use impregnation?based post?processing,which often involves multiple preparation steps and limited types of metals.In this work,an iron?copper(FeCu) and nitrogen doped carbon catalyst was prepared through a coordination competition strategy.In the preparation,4,4?bipyridine served as ligand and iron nitrate and copper chloride as metal sites to form FeCu coordination polymers,which was directly transformed into FeCu?nitrogen doped porous carbon catalysts.The physicochemical properties such as morphological structure,metal species state and pore structure were characterized by SEM,TEM,XRD and N₂ adsorption?desorption,respectively.The performance of different FeCu?nitrogen doped carbon catalysts in electrocatalytic CO₂RR to syngas was examined in a three?electrode system.The regulation of n(CO)/n(H₂) in syngas was studied by adjusting the metal composition,metal combination and pyrolysis temperature,etc.The n(CO)/n(H₂) generated in the wide potential range of -0.7 V to -1.3 V can be regulated in the range of 0.15~3.33,which can meet the supply gas ratios for important reactions such as methanol synthesis,Fischer?Tropsch reaction and syngas fermentation.

Key words: Porous carbon, Metal?nitrogen doped carbon, Bimetallic catalysts, Electrocatalytic CO₂reduction, Syngas

中图分类号:

TQ127.1

武玉泰, 王佳琦, 李丹, 胡旭, 王永胜, 郝广平. 双金属⁃氮掺杂炭催化剂的制备及其电催化CO₂性能[J]. 石油化工高等学校学报, 2023, 36(3): 1-10.

Yutai Wu, Jiaqi Wang, Dan Li, Xu Hu, Yongsheng Wang, Guangping Hao. Preparation of Bimetallic⁃Nitrogen Doped Carbon Catalysts and Electrocatalytic CO₂ Performance[J]. Journal of Petrochemical Universities, 2023, 36(3): 1-10.

图/表 14

图1 FeCu?N?C系列催化剂的合成示意图

Fig.1 Schematic illustration of the synthesis of FeCu?N?C series catalysts

图2 双金属配位聚合物和单金属Cu的配位聚合物的光学图片（a) Cu （b） Fe0.5Cu （c） FeCu （d） Fe2.0Cu （e） Cu?N?C

Fig.2 Optical images of bimetal coordinated polymer monolith and Cu coordinated polymer

图3 Fe x Cu?N?C催化剂的SEM图

Fig.3 SEM images of Fe x Cu?N?C

图4 Fe x Cu?N?C?900催化剂的XRD和拉曼图谱

Fig.4 XRD patterns and Raman spectra of Fe x Cu?N?C?900 catalysts

图5 Fe x Cu?N?C?900催化剂的N2吸附?脱附等温线、CO2吸附?脱附等温线

Fig.5 N2 adsorption?desorption isotherm and CO2 adsorption?desorption isotherm of Fe x Cu?N?C?900 catalysts

表1 Fe x Cu?N?C?t催化剂的孔结构数据

Table 1 Pore structure parameters of Fe x Cu?N?C?t catalysts

催化剂	比表面积/（m²·g^-1）	总孔容/(cm³·g^-1)	微孔孔容/(cm³·g^-1)
Cu⁃N⁃C⁃900	1 036	0.85	0.38
Fe_0.5Cu⁃N⁃C⁃900	821	0.69	0.30
FeCu⁃N⁃C⁃900	761	0.75	0.27
Fe_1.5Cu⁃N⁃C⁃900	707	0.70	0.26
Fe_2.0Cu⁃N⁃C⁃900	602	0.84	0.19
Fe_2.0Cu⁃N⁃C⁃700	568	0.80	0.18
Fe_2.0Cu⁃N⁃C⁃400	562	0.59	0.18

图6 Fe0.5Cu?N?C?900和Fe2.0Cu?N?C?900的TEM、HRTEM、STEM和EDS映射图

Fig.6 TEM,HRTEM,STEM and EDS mapping images of Fe0.5Cu?N?C?900 and Fe2.0Cu?N?C?900

图7 Fe2.0Cu?N?C?t催化剂的XRD谱图和N2吸附?脱附等温线

Fig.7 XRD patterns and nitrogen adsorption?desorption isotherms of Fe2.0Cu?N?C?t catalysts

图8 M2.0Cu?N?C?900催化剂的N2吸附?脱附等温线和孔径分布

Fig.8 Nitrogen adsorption?desorption isotherms and corresponding pore size distribution of M2.0Cu?N?C?900 catalysts

表2 M2.0Cu?N?C?900催化剂的孔结构数据

Table 2 Pore structure parameters of M2.0Cu?N?C?900 catalysts

催化剂	比表面积/（m²·g^-1）	总孔容/(cm³·g^-1)	微孔孔容/(cm³·g^-1)
Zn_2.0Cu⁃N⁃C⁃900	367	0.18	0.14
Ni_2.0Cu⁃N⁃C⁃900	184	0.56	0.05

图9 Zn2.0Cu?N?C?900和Ni2.0Cu?N?C?900的SEM图

Fig.9 SEM images of Zn2.0Cu?N?C?900 and Ni2.0Cu? N?C?900

图10 Fe x Cu?N?C?900催化剂的CO2RR性能测试图

Fig.10 Performance testing chart of CO2RR for Fe x Cu?N?C?900 catalysts

图11 Fe2.0Cu?N?C?t催化剂的CO2RR性能测试图

Fig.11 Performance testing chart of CO2RR for Fe2.0Cu?N?C?t catalysts

图12 M2.0Cu?N?C?900催化剂的CO2RR性能测试图

Fig.12 Performance testing chart of CO2RR for catalysts with M2.0Cu?N?C?900

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双金属⁃氮掺杂炭催化剂的制备及其电催化CO₂性能

Preparation of Bimetallic⁃Nitrogen Doped Carbon Catalysts and Electrocatalytic CO₂ Performance

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