Yilmaz Gamze, Yang Tong, Du Yonghua, Yu Xiaojiang, Feng Yuan Ping, Shen Lei, Ho Ghim Wei
Department of Electrical and Computer Engineering National University of Singapore 4 Engineering Drive 3 Singapore 117583 Singapore.
Department of Physics National University of Singapore Singapore 117551 Singapore.
Adv Sci (Weinh). 2019 May 29;6(15):1900140. doi: 10.1002/advs.201900140. eCollection 2019 Aug 7.
The design of MoS-based electrocatalysts with exceptional reactivity and robustness remains a challenge due to thermodynamic instability of active phases and catalytic passiveness of basal planes. This study details a viable in situ reconstruction of zinc-nitrogen coordinated cobalt-molybdenum disulfide from structure directing metal-organic framework (MOF) to constitute specific heteroatomic coordination and surface ligand functionalization. Comprehensive experimental spectroscopic studies and first-principle calculations reveal that the rationally designed electron-rich centers warrant efficient charge injection to the inert MoS basal planes and augment the electronic structure of the inactive sites. The zinc-nitrogen coordinated cobalt-molybdenum disulfide shows exceptional catalytic activity and stability toward the hydrogen evolution reaction with a low overpotential of 72.6 mV at -10 mA cm and a small Tafel slope of 37.6 mV dec. The present study opens up a new opportunity to stimulate catalytic activity of the in-plane MoS basal domains for enhanced electrochemistry and redox reactivity through a "molecular reassembly-to-heteroatomic coordination and surface ligand functionalization" based on highly adaptable MOF template.
由于活性相的热力学不稳定性和基面的催化惰性，设计具有卓越反应活性和稳定性的基于二硫化钼的电催化剂仍然是一项挑战。本研究详细介绍了一种可行的原位重构方法，即从结构导向金属有机框架（MOF）构建锌-氮配位的二硫化钴钼，以形成特定的杂原子配位和表面配体功能化。全面的实验光谱研究和第一性原理计算表明，合理设计的富电子中心保证了向惰性二硫化钼基面的有效电荷注入，并增强了非活性位点的电子结构。锌-氮配位的二硫化钴钼对析氢反应表现出卓越的催化活性和稳定性，在-10 mA cm时过电位低至72.6 mV，塔菲尔斜率小至37.6 mV dec。本研究通过基于高度适应性MOF模板的“分子重组-杂原子配位和表面配体功能化”，为激发面内二硫化钼基域的催化活性以增强电化学和氧化还原反应性开辟了新机会。
