College of Engineering, Mathematics and Physical Sciences, University of Exeter, Exeter EX4 4QF, UK.
Nanoscale. 2015 Dec 28;7(48):20674-84. doi: 10.1039/c5nr07429k. Epub 2015 Nov 24.
Exploring highly-efficient and low-cost bifunctional electrocatalysts for both oxygen reduction reaction (ORR) and oxygen evolution reactions (OER) in the renewable energy area has gained momentum but still remains a significant challenge. Here we present a simple but efficient method that utilizes ZIF-67 as the precursor and template for the one-step generation of homogeneous dispersed cobalt sulfide/N,S-codoped porous carbon nanocomposites as high-performance electrocatalysts. Due to the favourable molecular-like structural features and uniform dispersed active sites in the precursor, the resulting nanocomposites, possessing a unique core-shell structure, high porosity, homogeneous dispersion of active components together with N and S-doping effects, not only show excellent electrocatalytic activity towards ORR with the high onset potential (around -0.04 V vs.-0.02 V for the benchmark Pt/C catalyst) and four-electron pathway and OER with a small overpotential of 0.47 V for 10 mA cm(-2) current density, but also exhibit superior stability (92%) to the commercial Pt/C catalyst (74%) in ORR and promising OER stability (80%) with good methanol tolerance. Our findings suggest that the transition metal sulfide-porous carbon nanocomposites derived from the one-step simultaneous sulfurization and carbonization of zeolitic imidazolate frameworks are excellent alternative bifunctional electrocatalysts towards ORR and OER in the next generation of energy storage and conversion technologies.
在可再生能源领域,探索高效且低成本的氧还原反应 (ORR) 和氧析出反应 (OER) 双功能电催化剂已经成为一个热点,但仍然是一个重大挑战。在这里,我们提出了一种简单但有效的方法,利用 ZIF-67 作为前驱体和模板,通过一步法生成均匀分散的硫化钴/N,S 共掺杂多孔碳纳米复合材料作为高性能电催化剂。由于前驱体具有有利的分子样结构特征和均匀分散的活性位,所得纳米复合材料具有独特的核壳结构、高孔隙率、活性成分的均匀分散以及 N 和 S 掺杂效应,不仅对 ORR 表现出优异的电催化活性,具有较高的起始电位(约-0.04 V 相对于基准 Pt/C 催化剂为-0.02 V)和四电子途径,而且在 10 mA cm(-2) 电流密度下,OER 的过电位仅为 0.47 V,对商业 Pt/C 催化剂(74%)的稳定性(92%)也更高,在 ORR 中具有良好的甲醇耐受性,并且对 OER 具有良好的稳定性(80%)。我们的研究结果表明,由沸石咪唑酯骨架的一步同时硫化和碳化衍生的过渡金属硫化物-多孔碳纳米复合材料是下一代储能和转换技术中 ORR 和 OER 的优秀双功能电催化剂。