Yan Yibo, Li Kaixin, Chen Xiaoping, Yang Yanhui, Lee Jong-Min
School of Chemical and Biomedical Engineering, Nanyang Technological University, 62 Nanyang Drive, Singapore, 637459, Singapore.
Small. 2017 Dec;13(47). doi: 10.1002/smll.201701724. Epub 2017 Nov 7.
Expedition of electron transfer efficiency and optimization of surface reactant adsorption products desorption processes are two main challenges for developing non-noble catalysts in the oxygen reduction reaction (ORR) and CO reduction reaction (CRR). A heterojunction prototype on Co S @Co O core-shell octahedron structure is established via hydrothermal lattice anion exchange protocol to implement the electroreduction of oxygen and carbon dioxide with high performance. The synergistic bifunctional catalyst consists of p-type Co O core and n-type Co S shell, which afford high surface electron density along with high capacitance without sacrificing mechanical robustness. A four electron ORR process, identical to the Pt catalyzed ORR, is validated using the core-shell octahedron catalyst. The synergistic interaction between cobalt sulfide and cobalt oxide bicatalyst reduces the activation energy to convert CO into adsorbed intermediates and hereby enables CRR to run at a low overpotential, with formate as the highly selective main product at a high faraday efficiency of 85.3%. The remarkable performance can be ascribed to the synergistic coupling effect of the structured co-catalysts; heterojunction structure expedites the electron transfer efficiency and optimizes surface reactant adsorption product desorption processes, which also provide theoretical and pragmatic guideline for catalyst development and mechanism explorations.
提高电子转移效率以及优化表面反应物吸附和产物脱附过程是开发用于氧还原反应(ORR)和一氧化碳还原反应(CRR)的非贵金属催化剂面临的两个主要挑战。通过水热晶格阴离子交换协议建立了具有Co S@Co O核壳八面体结构的异质结原型,以实现高效的氧和二氧化碳电还原。这种协同双功能催化剂由p型Co O核和n型Co S壳组成,在不牺牲机械强度的情况下提供了高表面电子密度和高电容。使用核壳八面体催化剂验证了与Pt催化的ORR相同的四电子ORR过程。硫化钴和氧化钴双催化剂之间的协同相互作用降低了将CO转化为吸附中间体的活化能,从而使CRR能够在低过电位下运行,以甲酸盐作为高选择性的主要产物,法拉第效率高达85.3%。这种卓越的性能可归因于结构化助催化剂的协同耦合效应;异质结结构加快了电子转移效率,优化了表面反应物吸附和产物脱附过程,这也为催化剂开发和机理探索提供了理论和实际指导。