塔菲尔方程
钴
电化学
硒化物
催化作用
氢
活化能
过电位
偏苯三甲酸
金属有机骨架
化学
化学工程
无机化学
吸附
电极
有机化学
物理化学
分子
工程类
硒
作者
Pitchai Thangasamy,Rong He,Hyacinthe Randriamahazaka,Xinqi Chen,Yizhi Zhang,Hongmei Luo,Haiyan Wang,Meng Zhou
标识
DOI:10.1016/j.apcatb.2023.122367
摘要
Finding and exploring non-noble metal-based electrocatalysts for the promising power-to-hydrogen fuel technology through water splitting reactions is highly emerging. Herein, we report the preparation of cobalt-based metal-organic frameworks (Co-MOFs) using an oleylamine (OLA) and 1-dodecanethiol (DDT)-modified trimesic acid (TMA), and cobalt precursor. Then, the electrocatalytically active cobalt selenides were derived from the Co-MOFs by a water-organic solvent mixture-assisted single-step selenization process. Interestingly, the cobalt selenide obtained from the DDT-modified Co-MOF shows collectively exhaustive hydrogen evolution reaction (HER) performance with very small overpotentials of ~161 and ~206 mV to achieve 10 and 50 mA cm-2, respectively, due to the phase mixing characteristics of cobalt selenide and the synergistic interaction. The fast reaction kinetics were identified at the DDT-Co selenide electrode surface as confirmed by observing the lower charge-transport/interfacial resistance and Tafel slope value due to the high surface coverage of adsorbed hydrogen (Hads) atoms, evidenced by high interfacial chemical capacitance value, as a result of the high electrical conductivity and large electrochemically accessible active sites. The calculated activation energy (Ea) of HER further reveals a low kinetic energy barrier in the HER on the DDT-Co selenide, indicating high intrinsic catalytic activity due to the fast surface diffusion rate of Hads. Furthermore, the obtained cathodic transfer coefficient (αc) value strongly suggested that the HER on the surface of DDT-Co selenide (αc = 2) proceeds in the Langmuir-Hinshelwood reaction mechanism and follows the Volmer-Tafel pathway. The present work provides valuable insights into the modification of Co-MOFs and their impact on HER catalytic activity of cobalt selenide, and also the mechanistic investigation of HER based on electrochemical impedance spectroscopy analysis.
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