标题：N-, P-, and S-Doped Graphene-Like Carbon Catalysts Derived from Onium Salts with Enhanced Oxygen Chemisorption for Zn-Air Battery Cathodes
作者：Xiangjun Zhenga, Jiao Wua, Xuecheng Caoa, Janel Abbottb, Chao Jina, Haibo Wanga, Peter Strasserd, Ruizhi Yanga, Xin Chenc, Gang Wub
单位：a College of Energy, Soochow Institute for Energy and Materials Innovations, Key Laboratory of Advanced Carbon Materials and Wearable Energy Technologies of Jiangsu Province, Soochow University, Suzhou 215006, China
b Department of Chemical and Biological Engineering, University at Buffalo, The State University of New York, Buffalo, New York 14260, United States
c The Center of New Energy Materials and Technology, College of Chemistry and Chemical Engineering, Southwest Petroleum University, Chengdu 610500, China
摘要：Compared to currently studied metal-based catalysts, metal-free heteroatom-doped carbon catalysts have many advantages including no issues of degradation and contamination from metal dissolution. Relying on single type of doping usually cannot yield optimal electronic and geometric structures favorable for the oxygen reduction reaction (ORR). Herein, heteroatom N, P, and S simultaneously doped graphene-like carbon (NPS-G) was successfully synthesized from onium salts by a facile one-step pyrolysis method. The resulting metal-free NPS-G catalyst with optimized N, P, and S contents exhibits enhanced catalytic activity towards the ORR in alkaline media, relative to any single doping. In particular, this metal-free catalyst shows an encouraging half-wave potential (E1/2 = 0.857 V) comparable to that of metal-based catalysts. It also demonstrates excellent electrochemical stability and methanol tolerance. This catalyst was further studied as a cathode in a primary Zn-air battery, showing exceptional open-circuit voltage (1.372 V) and power density (0.151 W cm−2). The NPS-G cathode delivers a specific capacity of 686 mA h gZn-1 at a current density of 10 mA cm−2 while utilizing 82.2% of the theoretical capacity (835 mA h gZn-1). The origin of high activity associated with various heteroatom doping is elucidated through X-ray photoelectron spectroscopy analysis and density functional theory studies. The enhanced chemisorption of oxygen species (*OOH, *O and *OH) onto the dopants of the NPS-G catalysts reduces charge transfer resistance and facilitate the ORR. The porous 2D structure also contributes to the increase of active site density and facile mass transport.