Collectively exhaustive electrochemical hydrogen evolution reaction of polymorphic cobalt selenides derived from organic surfactants modified Co-MOFs
Collectively exhaustive electrochemical hydrogen evolution reaction of polymorphic cobalt selenides derived from organic surfactants modified Co-MOFs
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有机表面活性剂改性 Co-MOF 衍生的多晶型硒化钴的全面详尽的电化学析氢反应
DOI：
10.1016/j.apcatb.2023.122367
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发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Zhou, Meng
中科院分区：
文献类型：
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作者：
Thangasamy, Pitchai;He, Rong;Randriamahazaka, Hyacinthe;Chen, Xinqi;Zhang, Yizhi;Luo, Hongmei;Wang, Haiyan;Zhou, Meng
寻找和探索非贵金属基电催化剂，通过水裂解反应的有前途的电力到氢燃料技术是非常新兴的。在此，我们报告了使用油胺（奥拉）和1-十二烷硫醇（DDT）改性的均苯三甲酸（TMA）和钴前体制备钴基金属有机框架（Co-MOFs）。然后，通过水-有机溶剂混合物辅助的单步硒化过程，从Co-MOFs衍生出具有电催化活性的硒化钴。有趣的是，由于硒化钴的相混合特性和协同相互作用，从DDT改性的Co-MOF获得的硒化钴显示出共同的彻底析氢反应（HER）性能，具有非常小的过电位，分别为10和50 mA cm-2，分别为1.161和1.206 mV，达到10和50 mA cm-2。在DDT-Co硒化物电极表面的快速反应动力学被确定为确认通过观察较低的电荷传输/界面电阻和塔菲尔斜率值，由于吸附的氢（Hads）原子的高表面覆盖率，证明了高界面化学电容值，作为高电导率和大的电化学可访问的活性位点的结果。计算的HER的活化能（Ea）进一步揭示了DDT-Co硒化物上HER中的低动能势垒，表明由于Hads的快速表面扩散速率而具有高的固有催化活性。阴极转移系数（αc）值表明，DDT-Co硒化物（αc= 2）表面的HER反应遵循Langmuir-Hinshelwood反应机理，遵循Volmer-Tafel途径.本工作为Co-MOFs的修饰及其对硒化钴HER催化活性的影响以及基于电化学阻抗谱分析的HER机理研究提供了有价值的见解。
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.