1. 东北农业大学 工程学院,哈尔滨,150030
2. 城市水资源与水环境国家重点实验室(哈尔滨工业大学),哈尔滨,150090
纸质出版:2022
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公维佳, 张鸿宇, 杨柳, 等. 钴氮共掺杂碳基电催化剂的制备及性能调控[J]. 哈尔滨工业大学学报, 2022,54(2):40-49.
GONG Weijia, ZHANG Hongyu, YANG Liu, et al. Fabrication and performance optimization of cobalt/nitrogen co-doped carbon-based electrocatalyst[J]. 2022, 54(2): 40-49.
公维佳, 张鸿宇, 杨柳, 等. 钴氮共掺杂碳基电催化剂的制备及性能调控[J]. 哈尔滨工业大学学报, 2022,54(2):40-49. DOI: 10.11918/202106124.
GONG Weijia, ZHANG Hongyu, YANG Liu, et al. Fabrication and performance optimization of cobalt/nitrogen co-doped carbon-based electrocatalyst[J]. 2022, 54(2): 40-49. DOI: 10.11918/202106124.
贵金属基电催化剂是促进燃料电池及金属-空气电池技术发展的关键材料
然而
其单一的氧还原/氧析出催化功能及高昂的制备成本制约了其推广应用。为此
开发低成本、高效的非贵金属双功能电催化剂至关重要。以核壳金属有机框架(MOFs)为前驱体
通过高温煅烧法制备具有核壳结构、高催化活性、高导电性的钴/氮共掺杂碳基电催化剂(Co/Co3O4@NGC)。结果表明:煅烧温度是影响电催化剂微纳结构、物化组成和催化活性的关键因素
最佳烧结温度为900 ℃;制备的电催化剂(Co/Co3O4@NGC-900)具有清晰的核壳结构和3D十二面体形貌
微表面遍布Co/Co3O4纳米颗粒和Co-Nx位点。同时
Co/Co3O4@NGC-900有机地结合了多元活性成分(如活性Co/Co3O4纳米颗粒、Co-Nx及N掺杂)和高度石墨化碳基底的共同作用
具备高效的氧还原性(ORR
起始电位为0.89 V、半波电位为0.82 V、塔菲尔斜率为58.1 mV/dec、传荷电阻为26.6 Ω)和氧析出性(OER
过电势为410 mV、塔菲尔斜率为132 mV/dec、传荷电阻为24.5 Ω)
且具有与传统贵金属基电催化剂(Pt/C
RuO2/C)相匹配的电催化性能
在保障高效电催化活性的前提下实现了催化剂制造成本的大幅削减
为新型MOFs电催化材料的制备和应用提供了理论和技术支撑。
Noble metal-based electrocatalysts are the key materials to promote the technical development of fuel cells and metal-air batteries. However
the single catalytic function towards oxygen reduction/oxygen evolution and the prohibitive cost restrict their extensive application. Therefore
it is of great significance to develop non-noble metal-based bi-functional electrocatalysts with low-cost and high-efficiency. In this study
taking core-shell metal organic frameworks (MOFs) as precursors
cobalt/nitrogen co-doped carbon-based electrocatalyst (Co/Co3O4@NGC) was fabricated using high-temperature calcination technology
with a core-shell structure
high catalytic activity
and high conductivity. Results show that the calcination temperature was the key factor affecting the micro-nano structure
physicochemical composition
and catalytic activity of the electrocatalyst. The optimal temperature of calcination was 900 ℃. The fabricated electrocatalyst (Co/Co3O4@NGC-900) had a clear core-shell structure and 3D-dodecahedron morphology with Co/Co3O4 nanoparticles and Co-Nx sites on its micro-surface. In addition
Co/Co3O4@NGC-900 inherently combined the synergistic effects of both multiple active ingredients (e.g.
active Co/Co3O4 nanoparticles
Co-Nx
and N dopants) and highly graphitized carbon substrates
and thus exhibited efficient oxygen reduction performance (ORR
onset potential of 0.89 V
half-wave potential of 0.82 V
Tafel slope of 58.1 mV/dec
and charge transfer resistance of 26.6 Ω) and oxygen evolution performance (OER
overpotential of 410 mV
Tafel slope of 132 mV/dec
and charge transfer resistance of 24.5 Ω). Therefore
Co/Co3O4@NGC-900 exerted electrocatalytic performance comparable to that of typical noble metal-based electrocatalysts (e.g.
Pt/C
RuO2/C)
and achieved significant reduction of catalyst fabrication cost on the premise of ensuring its high-efficient electrocatalytic activity
providing theoretical and technical support for the fabrication and application of innovative MOFs derived electrocatalytic materials.
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