Guo Xinjie, Lv Chenhao, Wang Yun, Wang Tengfei, Gan Xingyu, Li Liangjun, Lv Xiaoxia
Key Laboratory of Catalytic Conversion and Clean Energy in Universities of Shandong Province, School of Chemistry and Chemical Engineering, Qufu Normal University Qufu City, Shandong, 273165, P. R. China.
College of New Energy, China University of Petroleum (East China), Qingdao, Shandong Province, 266580, P. R. China.
Chemistry. 2023 Nov 24;29(66):e202302182. doi: 10.1002/chem.202302182. Epub 2023 Oct 17.
The design of non-noble metal bifunctional electrocatalysts with outstanding performance and remarkable stability for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is one of the most essential issues to the realization of rechargeable zinc-air battery, and transition metal phosphides (TMPs) have emerged as robust candidates for oxygen electrocatalysts. Herein, N-doped carbon-coated phosphorus-vacancies-rich Ni P particles (V -Ni P@NC) is proposed via simple carbonization and following Ar plasma treatment from a single nickel phosphonate metal-organic framework (MOF) without extra phosphine and nitrogen sources. The facile and rapid plasma treatment can achieve phosphorus vacancies which could modulate the electronic structure to enhance the inherent active and electrical conductivity. Meanwhile, the pyridine-N and graphitized-N produced during calcination also could provide more active sites and increase the electrical conductivity. The resultant V -Ni P@NC catalyst shows excellent bifunctional electrocatalytic activity (OER/ORR) based on synergistic effect of introducing P vacancies into Ni P and N-doped carbon. V -Ni P@NC catalyst shows more advantageous ΔE value (0.70 V) compared to Pt/C+RuO2 (0.73 V) and most reported catalysts. Additionally, the zinc-air bbatterie (ZAB) employing V -Ni P@NC as air cathode shows excellent performance. The maximum power density of 203.48 mW cm , the cycling stability of more than 150 h at 10 mA cm .
设计具有出色性能和卓越稳定性、用于氧还原反应（ORR）和析氧反应（OER）的非贵金属双功能电催化剂是实现可充电锌空气电池的最关键问题之一，过渡金属磷化物（TMPs）已成为氧电催化剂的有力候选材料。在此，通过简单的碳化以及随后对单一镍膦酸盐金属有机框架（MOF）进行氩等离子体处理，在无需额外膦源和氮源的情况下制备了氮掺杂碳包覆的富含磷空位的NiP颗粒（V -NiP@NC）。简便快速的等离子体处理能够实现磷空位，从而调节电子结构以增强固有活性和电导率。同时，煅烧过程中产生的吡啶-N和石墨化-N也能够提供更多活性位点并提高电导率。基于将磷空位引入NiP和氮掺杂碳的协同效应，所得的V -NiP@NC催化剂表现出优异的双功能电催化活性（OER/ORR）。与Pt/C+RuO2（0.73 V）和大多数已报道的催化剂相比，V -NiP@NC催化剂显示出更有利的ΔE值（0.70 V）。此外，采用V -NiP@NC作为空气阴极的锌空气电池（ZAB）表现出优异的性能。最大功率密度为203.48 mW cm ，在10 mA cm 下的循环稳定性超过150 h。
