Abstract
The development of carbon materials with high electrochemical performance for next-generation energy device is emerging, especially N, S co-doped carbon materials have sparked intensive attention. However, the exploration of N, S co-doped carbon with well-defined active sites and hierarchical porous structures are still limited. In this study, we prepared a series of edge-enriched N, S co-doped carbon materials through pyrolysis of thiourea (TU) encapsulated in zeolitic imidazolate frameworks (TU@ZIF) composites, which delivered very good oxygen reduction reaction (ORR) performance in alkaline medium with onset potential of 0.94 V vs. reversible hydrogen electrode (RHE), good stability and methanol tolerance. Density functional theory (DFT) calculations suggested that carbon atoms adjacent to N and S are probable active sites for ORR intermediates in edge-enriched N, S co-doped carbon materials because higher electron density can enhance O2 adsorption, lower formation barriers of intermediates, improving the ORR performance comparing to intact N, S co-doped carbon materials. This study might provide a new pathway for improving ORR activity by the integration engineering of edge sites, and electronic structure of heteroatom doped carbon electrocatalysts.
Edge-enriched N, S co-doped carbon materials, derived from encapsulation of thiourea within ZIF-8 and subsequent pyrolysis, exhibit enhanced oxygen reduction reaction (ORR) performance in alkaline medium. [Display omitted]