Yifan Li, Xueying Wan, Zhigang Chen, Ding Ding, Hao Li, Ning Zhang, Dong Liu, Yi Cui
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The performance evaluations demonstrate that the minimal oxygen-modified Mo<sub>2</sub>C exhibits the best alkaline HER activity among all model electrocatalysts. In situ XPS combined with quasi in situ XPS under different applied negative potentials reveals that tailoring the Mo<sub>2</sub>C surface decorated with oxygen-containing species can facilitate the desorption of produced OH* intermediates from water activation, thus avoiding the deep oxidation issue of the catalyst surface and accelerating the regeneration of active sites in the alkaline HER process. Moreover, a comparable trend of HER performance is also observed on the synthetically practical Mo<sub>2</sub>C powder catalysts, which further proves our hypothesis deduced from the model system. Our strategy of oxygen-terminated Mo<sub>2</sub>C model electrocatalysts and the utilization of advanced spectroscopy characterizations may pave an interesting route for the rational design of low-cost but highly efficient oxygen-modified molybdenum carbide catalysts for practical water electrolysis.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":11.3000,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Activity Enhancement of Molybdenum Carbide in Alkaline Hydrogen Evolution Reaction through Oxidation-Gradient Modulation\",\"authors\":\"Yifan Li, Xueying Wan, Zhigang Chen, Ding Ding, Hao Li, Ning Zhang, Dong Liu, Yi Cui\",\"doi\":\"10.1021/acscatal.4c01779\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Featured by their Pt-like electronic structure, molybdenum carbides have been widely developed for efficiently catalyzing the hydrogen evolution reaction (HER). 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引用次数: 0
摘要
碳化钼具有类似铂的电子结构,已被广泛开发用于高效催化氢进化反应(HER)。值得注意的是,过渡金属原子的亲氧化性会导致碳化钼不可避免地发生表面氧化,从而对其氢进化反应活性产生明显影响。然而,这样一个重要的细节通常是在理论模拟中记录下来的,很少通过控制良好的实验进行探索。本文利用真空连接装置,采用先进的表面科学技术,特意制备了氧化梯度碳化钼模型电催化剂,并评估了其相应的碱性 HER 性能。性能评估结果表明,在所有模型电催化剂中,最小氧修饰的 Mo2C 表现出最佳的碱性 HER 活性。原位 XPS 结合不同应用负电位下的准原位 XPS 发现,用含氧物种修饰的 Mo2C 表面可促进水活化产生的 OH* 中间产物的解吸,从而避免催化剂表面的深度氧化问题,并加速碱性 HER 过程中活性位点的再生。此外,在合成实用的 Mo2C 粉末催化剂上也观察到了类似的 HER 性能趋势,这进一步证明了我们从模型系统中推导出的假设。我们的氧封端 Mo2C 模型电催化剂策略以及对先进光谱特性的利用,可能会为合理设计用于实用水电解的低成本但高效的氧修饰碳化钼催化剂铺平一条有趣的道路。
Activity Enhancement of Molybdenum Carbide in Alkaline Hydrogen Evolution Reaction through Oxidation-Gradient Modulation
Featured by their Pt-like electronic structure, molybdenum carbides have been widely developed for efficiently catalyzing the hydrogen evolution reaction (HER). It is noteworthy that the oxophilicity of transition-metal atoms can give rise to the inevitable surface oxidation of molybdenum carbides, which has a noticeable impact on their HER activities. However, such a significant detail was usually documented in theory simulations and rarely explored by well-controlled experiments. Herein, advanced surface-science techniques using vacuum-connected setups are performed to deliberately prepare oxidation-gradient molybdenum carbide-oxide model electrocatalysts and evaluate the corresponding alkaline HER performance. The performance evaluations demonstrate that the minimal oxygen-modified Mo2C exhibits the best alkaline HER activity among all model electrocatalysts. In situ XPS combined with quasi in situ XPS under different applied negative potentials reveals that tailoring the Mo2C surface decorated with oxygen-containing species can facilitate the desorption of produced OH* intermediates from water activation, thus avoiding the deep oxidation issue of the catalyst surface and accelerating the regeneration of active sites in the alkaline HER process. Moreover, a comparable trend of HER performance is also observed on the synthetically practical Mo2C powder catalysts, which further proves our hypothesis deduced from the model system. Our strategy of oxygen-terminated Mo2C model electrocatalysts and the utilization of advanced spectroscopy characterizations may pave an interesting route for the rational design of low-cost but highly efficient oxygen-modified molybdenum carbide catalysts for practical water electrolysis.
期刊介绍:
ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels.
The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.