通过合金化激活过渡金属二硫属化物基面用于CO2还原为CO

中文摘要 AI 辅助

过渡金属二硫属化物（TMDCs）已成为高度可调的电催化平台，特别是在CO2还原反应（CO2RR）中。虽然TMDC边缘位点表现出催化活性，但基面通常是惰性的，严重限制了整体活性位点密度。在本工作中，我们展示了硫空位激活1H-TMDCs的基面，同时固溶体合金化提供了一种广泛调节中间体吸附能的机制。我们评估了一个由V、Nb、Ta、Mo和W组成的准二元TMDC硫化物合金库，通过稳定性、缺陷能量学和竞争选择性进行筛选，以确定最有效的CO2RR催化剂。电子结构分析揭示，更接近费米能的d带中心通过使关键成键态在费米能以上保持未占据状态来削弱中间体结合。我们的计算确定(Nb,Ta)S2为有前景的催化剂，具有低硫空位形成能、接近最优的CO2RR中间体结合以及对析氢反应的选择性。总体而言，这项工作通过同时使用缺陷工程和合金化，为TMDC合金催化剂建立了合理设计框架。

英文摘要

Transition metal dichalcogenides (TMDCs) have emerged as highly tunable platforms for electrocatalysis, particularly for the CO2 reduction reaction (CO2RR). While TMDC edge sites exhibit catalytic activity, the basal plane is typically inert, severely limiting the overall active site density. In this work, we show that sulfur vacancies activate the basal plane of 1H-TMDCs, while concurrent solid-solution alloying provides a mechanism to broadly tune intermediate adsorption energies. We evaluate a library of quasi-binary TMDC sulfide alloys comprising V, Nb, Ta, Mo, and W, screening them by stability, defect energetics, and competitive selectivity to identify the most effective catalysts for CO2RR. Electronic-structure analysis reveals that a d-band center closer to the Fermi energy weakens intermediate binding by leaving key bonding states unoccupied above the Fermi energy. Our calculations identify (Nb,Ta)S2 as a promising catalyst with low sulfur vacancy formation energies, near-optimal CO2RR intermediate binding, and selectivity against the hydrogen evolution reaction. Overall, this work establishes a rational design framework for TMDC alloy catalysts through the simultaneous use of defect engineering and alloying.

发表机构

• Institute of Materials Science & Engineering, Washington University in St. Louis（华盛顿大学圣路易斯分校材料科学与工程研究所）
• Department of Computer Science & Engineering, Washington University in St. Louis（华盛顿大学圣路易斯分校计算机科学与工程系）
• Department of Mechanical Engineering & Materials Science, Washington University in St. Louis（华盛顿大学圣路易斯分校机械工程与材料科学系）
• Department of Chemistry, Incheon National University（仁川国立大学化学系）

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