Zhang Chaoqi, Lu Ruihu, Liu Chao, Lu Jingyi, Zou Yingying, Yuan Ling, Wang Jing, Wang Guozhong, Zhao Yan, Yu Chengzhong
School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, 200241, P. R. China.
State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan, 430070, China.
Adv Sci (Weinh). 2022 Apr;9(12):e2104768. doi: 10.1002/advs.202104768. Epub 2022 Mar 1.
High-performance transition metal chalcogenides (TMCs) as electrocatalysts for two-electron oxygen reduction reaction (2e-ORR) in alkaline medium are promising for hydrogen peroxide (H O ) production, but their synthesis remains challenging. In this work, a titanium-doped zinc-cobalt sulfide hollow superstructure (Ti-ZnCoS HSS) is rationally designed as an efficient electrocatalyst for H O electrosynthesis. Synthesized by using hybrid metal-organic frameworks (MOFs) as precursors after sulfidation treatment, the resultant Ti-ZnCoS HSS exhibits a hollow-on-hollow superstructure with small nanocages assembled around a large cake-like cavity. Both experimental and simulation results demonstrate that the polymetallic composition tailors the d-band center and binding energy with oxygen species. Moreover, the hollow superstructure provides abundant active sites and promotes mass and electron transfer. The synergistic d-band center and superstructure engineering at both atomic and nanoscale levels lead to the remarkable 2e-ORR performance of Ti-ZnCoS HSS with a high selectivity of 98%, activity (potential at 1 mA cm of 0.774 V vs reversible hydrogen electrode (RHE)), a H O production rate of 675 mmol h g , and long-term stability in alkaline condition, among the best 2e-ORR electrocatalysts reported to date. This strategy paves the way toward the rational design of polymetallic TMCs as advanced 2e-ORR catalysts.
高性能过渡金属硫族化合物（TMCs）作为碱性介质中两电子氧还原反应（2e-ORR）的电催化剂，在过氧化氢（H₂O₂）生产方面具有广阔前景，但其合成仍具有挑战性。在这项工作中，合理设计了一种钛掺杂的硫化锌钴空心超结构（Ti-ZnCoS HSS）作为H₂O₂电合成的高效电催化剂。通过使用混合金属有机框架（MOFs）作为前驱体，经硫化处理后合成，所得的Ti-ZnCoS HSS呈现出一种空心套空心的超结构，其中小纳米笼围绕着一个大的饼状空腔组装而成。实验和模拟结果均表明，多金属组成调整了d带中心以及与氧物种的结合能。此外，空心超结构提供了丰富的活性位点，并促进了质量和电子转移。在原子和纳米尺度上协同进行的d带中心和超结构工程，导致Ti-ZnCoS HSS具有卓越的2e-ORR性能，选择性高达98%，活性（在1 mA cm⁻²时相对于可逆氢电极（RHE）的电位为0.774 V），H₂O₂产率为675 mmol h⁻¹ g⁻¹，并且在碱性条件下具有长期稳定性，是迄今为止报道的最佳2e-ORR电催化剂之一。该策略为合理设计多金属TMCs作为先进的2e-ORR催化剂铺平了道路。
