Zhang Jiakun, Cui Bolan, Jiang Shang, Liu Haitao, Dou Meiling
Beijing Key Laboratory of Electrochemical Process and Technology for Materials, Beijing University of Chemical Technology, Beijing, China.
Nanoscale. 2022 Jul 14;14(27):9849-9859. doi: 10.1039/d2nr01704k.
Exploring cost-effective non-precious metal electrocatalysts is vital for the large-scale application of clean energy conversion devices (, 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 CoS 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 CoS/CoNSC exhibits outstanding ORR, OER and HER performance, comparable or even superior to those of commercial Pt/C and RuO. The small CoS NPs and Co-N species embedded in the carbon matrix cooperatively catalyze the OER and ORR, while the HER catalysis is mainly contributed by CoS NPs. Furthermore, the CoS/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 SO species, significantly outperforming commercial Pt/C. The assembled rechargeable Zn-air battery using the CoS/CoNSC as a cathode shows a high power density (150 mW cm) and the assembled water electrolyzer only requires 1.585 V at a current density of 10 mA cm 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.
探索具有成本效益的非贵金属电催化剂对于清洁能源转换装置（如燃料电池、金属空气电池和水电解槽）的大规模应用至关重要。在此，我们展示了通过使用硫粉作为硫源对沸石咪唑酯骨架（ZIFs）进行一步硫化，构建三维硫化钴/多杂原子共掺杂碳复合材料作为氧还原反应（ORR）、析氧反应（OER）和析氢反应（HER）的三功能电催化剂。凭借ZIF前驱体中独特的周期性金属 - 氮配位结构和丰富的微孔，亚10纳米的硫化钴纳米颗粒（NPs）均匀地锚定在具有大比表面积的钴、硫和氮多杂原子共掺杂碳骨架上，为这些电催化反应暴露了足够的活性位点。优化后的CoS/CoNSC表现出出色的ORR、OER和HER性能，与商业Pt/C和RuO的性能相当甚至更优。嵌入碳基质中的小尺寸CoS NPs和Co - N物种协同催化OER和ORR，而HER催化主要由CoS NPs贡献。此外，CoS/CoNSC在ORR催化过程中对硫物种表现出出色的抗中毒能力，在含有50 μM SO物种的0.1 M KOH中未观察到明显的活性降解，显著优于商业Pt/C。使用CoS/CoNSC作为阴极组装的可充电锌空气电池显示出高功率密度（150 mW cm），并且当使用这种材料作为阳极和阴极时，组装的水电解槽在电流密度为10 mA cm时仅需要1.585 V。这项工作为设计和合成用于清洁能源转换装置大规模应用的高效、耐用和抗中毒的钴硫族化物基三功能电催化剂提供了一种有效策略。
