Construction of three-dimensional cobalt sulfide/multi-heteroatom co-doped porous carbon as an efficient trifunctional electrocatalyst

Abstract

Exploring cost-effective non-precious metal electrocatalysts is vital for the large-scale application of clean energy conversion devices (i.e., fuel cells, metal–air batteries and water electrolysers). Herein, we present the construction of a three-dimensional cobalt sulfide/multi-heteroatom co-doped carbon composite as a trifunctional electrocatalyst for the oxygen reduction reaction (ORR), oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) through one-step sulfidation of zeolitic-imidazolate frameworks (ZIFs) using sulfur powder as a sulfur source. By virtue of the distinct periodic metal–nitrogen coordination structure and the abundant micropores within the ZIF precursor, sub-10 nm Co₉S₈ nanoparticles (NPs) are homogenously anchored on a Co, S and N multi-heteroatom co-doped carbon framework with a large specific surface area that exposes sufficient reactive sites for these electrocatalytic reactions. The optimized Co₉S₈/CoNSC exhibits outstanding ORR, OER and HER performance, comparable or even superior to those of commercial Pt/C and RuO₂. The small Co₉S₈ NPs and Co–N_x species embedded in the carbon matrix cooperatively catalyze the OER and ORR, while the HER catalysis is mainly contributed by Co₉S₈ NPs. Furthermore, the Co₉S₈/CoNSC shows outstanding anti-poisoning capability towards sulfur species during ORR catalysis with no obvious activity degradation observed in 0.1 M KOH containing 50 μM SO₃²⁻ species, significantly outperforming commercial Pt/C. The assembled rechargeable Zn–air battery using the Co₉S₈/CoNSC as a cathode shows a high power density (150 mW cm⁻²) and the assembled water electrolyzer only requires 1.585 V at a current density of 10 mA cm⁻² when using this material as an anode and a cathode. This work provides an effective strategy to design and synthesize efficient, durable and anti-poisoning cobalt chalcogenide-based trifunctional electrocatalysts for the large-scale application of clean energy conversion devices.