College of Science, Sichuan Agricultural University, Xin Kang Road, Yucheng District, Ya'an, 625014, P.R. China.
School of Chemistry and Chemical Engineering, Key Laboratory of Fuel Cell Technology of Guangdong Province, South China University of Technology, Guangzhou, 510641, P.R. China.
Small. 2021 May;17(19):e2007326. doi: 10.1002/smll.202007326. Epub 2021 Mar 30.
A valid strategy for amplifying the oxygen reduction reaction (ORR) efficiency of non-noble electrocatalyst in both alkaline and acid electrolytes by decorated with a layer of biomass derivative nitrogen-doped carbon (NPC) is proposed. Herein, a top-down strategy for the generally fabricating NPC matrix decorated with trace of metal oxides nanoparticles (FeO NPs) by a dual-template assisted high-temperature pyrolysis process is reported. A high-activity FeO /FeNC (namely Hemin/NPC-900) ORR electrocatalyst is prepared via simply carbonizing the admixture of Mg (OH) (CO ) and NaCl as dual-templates, melamine and acorn shells as nitrogen and carbon source, hemin as a natural iron and nitrogen source, respectively. Owing to its unique 3D porous construction, large BET areas (819.1 m ∙g ), and evenly dispersed active sites (FeN , CN, and FeO parts), the optimized Hemin/NPC-900 catalyst displays comparable ORR catalytic activities, remarkable survivability to methanol, and preferable long-term stability in both alkali and acid electrolyte compared with benchmark Pt/C. More importantly, density function theory computations certify that the interaction between Fe O nanoparticles and arm-GN (graphitic N at armchair edge) active sites can effectually promote ORR electrocatalytic performance by a lower overpotential of 0.81 eV. Accordingly, the research provides some insight into design of low-cost non-precious metal ORR catalysts in theory and practice.
提出了一种通过在生物质衍生的氮掺杂碳(NPC)层上修饰来提高非贵金属电催化剂在碱性和酸性电解质中氧还原反应(ORR)效率的有效策略。在此,报道了一种通过双模板辅助高温热解过程来普遍制备 NPC 基质上负载痕量金属氧化物纳米颗粒(FeO NPs)的自上而下策略。通过简单地碳化 Mg(OH)(CO )和 NaCl 的混合物作为双模板,三聚氰胺和橡子壳作为氮源和碳源,以及分别以血红素和 NPC-900 作为天然铁和氮源,制备了高活性的 FeO/Fe-N-C(即血红素/NPC-900)ORR 电催化剂。由于其独特的 3D 多孔结构、大 BET 面积(819.1 m ∙g )和均匀分散的活性位点(Fe-N、C-N 和 Fe-O 部分),优化后的 Hemin/NPC-900 催化剂在碱性和酸性电解质中表现出相当的 ORR 催化活性、对甲醇的优异耐腐蚀性和较好的长期稳定性,优于基准 Pt/C。更重要的是,密度泛函理论计算证明,Fe O 纳米颗粒与 arm-GN(扶手边缘的石墨 N)活性位点之间的相互作用可以通过 0.81 eV 的更低过电位有效地促进 ORR 电催化性能。因此,该研究从理论和实践上为设计低成本非贵金属 ORR 催化剂提供了一些见解。