Thiosemicarbazone based materials as electrocatalysts for the hydrogen evolution reaction

氢是工业和农业过程的重要组成部分，也是一种有前途的替代无碳燃料。目前，95%的工业氢气来自不可持续的化石燃料裂解。随着全球对廉价能源需求的增长，我们需要可持续的替代能源。该领域的主要挑战之一是开发基于固态和分子材料的高效催化剂，利用电力通过分解水产生氢。铂是从酸性溶液中产生氢的最有效的催化剂。然而，由于其稀缺性和高昂的成本，它的实际应用受到严重限制。在这个项目中，路易斯维尔大学的罗伯特·m·布坎南教授和高塔姆·古普塔教授正在开发一种新型催化剂，这种催化剂基于廉价的、富含地球资源的金属，如锌、铜和镍。催化剂的灵感来自于天然存在的氢化酶中的蛋白质环境。布坎南和古普塔教授积极参与推广活动，促进本科生参与科学、技术、工程和数学（STEM）学科，重点是少数族裔和第一代大学生。古普塔教授每年都会参加由纽约大学康恩可再生能源中心赞助的高中生“研究夏令营”。在化学部化学催化项目的资助下，dr。路易斯维尔大学（UofL）的Robert Buchanan和Gautam Gupta研究了基于氧化还原非无害硫氨基脲配体的析氢反应（HER）催化剂的制备和表面修饰分析。该研究解决了这种很大程度上未被开发的新型HER催化剂的结构-功能关系。它包括通过物理吸附和共价/增强的非共价附着方法对碳电极表面进行修饰，以提高耐久性并促进电子和质子转移。一个小分子催化剂库的HER活性被作为基准，与3D纳米结构催化剂载体结合在一起，以促进易反应物和产物的运输，高电子导电性和增强活性。该项目的广泛影响包括多个层面的利益。该项目有助于开发具有实际应用价值的水裂解析氢可持续材料。在大学层面，该项目加强了研究人员与UofL康涅狄格州可再生能源中心之间的联系，该中心是一个由科学家、工程师和行业领袖组成的网络，专注于复杂的、大规模的能源相关问题的跨学科解决方案。在参与者层面，两名研究生作为研究助理学习各种技能，本科生在许多年轻的受训科学家感兴趣和关注的主题上做出贡献。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

Hydrogen is an essential building block for industrial and agricultural processes and a promising alternative carbon-free fuel. Currently, 95% of industrial hydrogen derives from unsustainable fossil-fuel cracking. As global demand for cheap energy grows, there is a need for sustainable alternative sources. One of the major challenges in this area is the development of efficient catalysts based on solid state and molecular materials that use electricity to produce hydrogen by splitting water. Platinum is the most efficient catalyst for producing hydrogen from acidic solutions. However, its practical use is severely limited by its scarcity and prohibitive cost. In this project, Professors Robert M. Buchanan and Gautam Gupta of the University of Louisville are developing new catalysts based on inexpensive, earth-abundant metals, such as zinc, copper, and nickel. The catalysts are inspired by the protein environment in the naturally occurring hydrogenase enzymes. Professors Buchanan and Gupta are actively engaged in outreach activities that promote engagement of undergraduate students in the science, technology, engineering and mathematics (STEM) disciplines with an emphasis on under-represented minorities and first generation college students. Professor Gupta participates annually in 'Research Summer Camps' for high school students sponsored by the Conn Center for Renewable Energy at UofL.With funding from the Chemical Catalysis Program of the Chemistry Division, Drs. Robert Buchanan and Gautam Gupta of the University of Louisville (UofL) investigate the fabrication and analysis of modified surfaces with hydrogen evolution reaction (HER) catalysts based on redox non-innocent thiosemicarbazone ligands. The study addresses the structure-function relationship of this largely underexplored approach to new HER catalysts. It includes modification of carbon electrode surfaces through physisorption and covalent/enhanced non-covalent attachment methods to improve durability and facilitate electron and proton transfer. The HER activity of a library of small molecule catalysts is being benchmarked with the best performing catalysts incorporated in 3D nanostructured catalyst supports to promote facile reactant and product transport, high electronic conductivity and enhanced activity. The broader impacts of this project include benefits at multiple levels. The project facilitates the development of sustainable materials for hydrogen evolution from water splitting with practical applications. At the university level, the project strengthens connections between the investigators and the Conn Renewable Energy Center at UofL, a network comprised of scientists, engineers, and industry leaders focused on interdisciplinary solutions to complex, large scale energy-related issues. At the participant level, two graduate students supported as research assistants learn a diverse combination of skills and undergraduate research students make contributions on a topic of interest and concern to many younger scientists-in-training.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.