Modulating Coordination of Iron Atom Clusters on N,P,S Triply-Doped Hollow Carbon Support towards Enhanced Electrocatalytic Oxygen Reduction |
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Authors: | Dr. Xingmei Guo Jing Shi Ming Li Prof. Junhao Zhang Xiangjun Zheng Yuanjun Liu Prof. Baojuan Xi Dr. Xuguang An Zhongyao Duan Qianqian Fan Fei Gao Prof. Shenglin Xiong |
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Affiliation: | 1. School of Environmental and Chemical Engineering, Jiangsu University of Science and Technology, Zhenjiang, Jiangsu, 212003 P. R. China;2. School of Environmental and Chemical Engineering, Jiangsu University of Science and Technology, Zhenjiang, Jiangsu, 212003 P. R. China Contribution: Writing - review & editing (supporting);3. School of Chemistry and Chemical Engineering, Shandong University, Jinan, Shandong, 250100 P. R. China Contribution: Writing - review & editing (supporting);4. School of Mechanical Engineering, Chengdu University, Chengdu, Sichuan, 610106 P. R. China Contribution: Writing - review & editing (supporting);5. School of Chemistry and Chemical Engineering, Shandong University, Jinan, Shandong, 250100 P. R. China |
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Abstract: | Constructing atom-clusters (ACs) with in situ modulation of coordination environment and simultaneously hollowing carbon support are critical yet challenging for improving electrocatalytic efficiency of atomically dispersed catalysts (ADCs). Herein, a general diffusion-controlled strategy based on spatial confining and Kirkendall effect is proposed to construct metallic ACs in N,P,S triply-doped hollow carbon matrix (MACs/NPS−HC, M=Mn, Fe, Co, Ni, Cu). Thereinto, FeACs/NPS−HC with the best catalytic activity for oxygen reduction reaction (ORR) is thoroughly investigated. Unlike the benchmark sample of symmetrical N-surrounded iron single-atoms in N-doped carbon (FeSAs/N−C), FeACs/NPS−HC comprises bi-/tri-atomic Fe centers with engineered S/N coordination. Theoretical calculation reveals that proper Fe gathering and coordination modulation could mildly delocalize the electron distribution and optimize the free energy pathways of ORR. In addition, the triple doping and hollow structure of carbon matrix could further regulate the local environment and allow sufficient exposure of active sites, resulting in more enhanced ORR kinetics on FeACs/NPS−HC. The zinc-air battery assembled with FeACs/NPS−HC as cathodic catalyst exhibits all-round superiority to Pt/C and most Fe-based ADCs. This work provides an exemplary method for establishing atomic-cluster catalysts with engineered S-dominated coordination and hollowed carbon matrix, which paves a new avenue for the fabrication and optimization of advanced ADCs. |
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Keywords: | Atom Clusters Coordination Engineering Matrix Hollowing Oxygen Reduction Electrocatalysis |
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