Quasi-Two-Dimensional Intermetallic Electride CeRuSi for Efficient Alkaline Hydrogen Evolution
Quasi-Two-Dimensional Intermetallic Electride CeRuSi for Efficient Alkaline Hydrogen Evolution
复制标题
DOI：
10.1021/acscatal.2c06382
复制
发表时间：
2023-03
期刊：
影响因子：
12.9
通讯作者：
Weizheng Cai;Chuan Zhou-;Xinmeng Hu;Tiwen Jiao;Yijia Liu;Lei Li;Jiang-Bin Li;M. Kitano;Hideo Hosono;Jiazhen Wu
中科院分区：
文献类型：
--
作者：
Weizheng Cai;Chuan Zhou-;Xinmeng Hu;Tiwen Jiao;Yijia Liu;Lei Li;Jiang-Bin Li;M. Kitano;Hideo Hosono;Jiazhen Wu
电子化合物是新兴的催化剂材料，其中过量的电子充当周期性阴离子。尽管它们已成功用于各种氢化反应，但由于化学稳定性较弱，它们在水性体系中的应用仍然具有挑战性。在此，我们开发了一种准二维（2D）金属间化合物CeRuSi作为高性能碱性析氢电催化剂，在10 mA/cm2的电流密度下实现了28 mV的超低过电势，并在1.0 M KOH中实现了长期稳定性。速率决定步骤被推断为具有加速动力学的塔菲尔步骤。我们证明 CeRuSi 是迄今为止最好的基于电子化合物的析氢电催化剂。我们进一步证明，高活性主要归因于独特的电子化物特征和配位不饱和Ru位点，通过选择性化学蚀刻暴露和激活。最后，我们使用密度泛函理论计算确认了优异的催化性能，并找到了 Ru 活性中心的优化 H 吸附能。这项工作将刺激更多关于电子化合物的电催化研究，并为电催化剂的设计提供指导。
Electrides are emerging catalyst materials, in which excess electrons serve as periodic anions. Although they have been successfully used for various hydrogenation reactions, due to weak chemical stabilities, their applications in aqueous systems remain challenging. Herein, we develop a quasi-two-dimensional (2D) intermetallic electride CeRuSi as a high-performance alkaline hydrogen evolution electrocatalyst, realizing an ultralow overpotential of 28 mV at a current density of 10 mA/cm2and long-term stability in 1.0 M KOH. The rate-determining step is deduced to be the Tafel step with accelerated kinetics. We show that CeRuSi is so far the best electride-based electrocatalyst for hydrogen evolution. We further demonstrate that high activity is mainly ascribed to the unique electride features and the coordinatively unsaturated Ru sites, exposed and activated via selective chemical etching. Finally, we confirm the superior catalytic performance using density functional theory calculations and find an optimized H adsorption energy over the Ru active centers. This work will stimulate more electrocatalytic studies on electrides and provide guidance for the design of electrocatalysts.