Thiosemicarbazone based materials as electrocatalysts for the hydrogen evolution reaction

缩氨基硫脲基材料作为析氢反应的电催化剂

• 批准号: 1800245
• 负责人: Robert Buchanan
• 金额: $ 47.45万
• 依托单位: University of Louisville Research Foundation Inc
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-07-01 至 2023-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1800245&HistoricalAwards=false
• 关键词: Thiosemicarbazone; based; materials; electrocatalysts; hydrogen

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.

氢气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，需要可持续的替代能源。这一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，这些催化剂利用电力通过分解水来产生氢气。铂是从酸性溶液中生产氢气的最有效的催化剂。然而，它的实际使用受到其稀缺性和高昂成本的严重限制。在这个项目中，罗伯特M。路易斯维尔大学的Buchanan和Gautam Gupta正在开发新的催化剂，这些催化剂基于廉价的、地球上丰富的金属，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。教授布坎南和古普塔积极参与推广活动，促进本科生在科学，技术，工程和数学（干）学科的参与，重点是代表性不足的少数民族和第一代大学生。古普塔教授每年参加由UofL康恩可再生能源中心赞助的高中生“研究夏令营”。在化学系化学催化项目的资助下，路易斯维尔大学（UofL）的Robert Buchanan和Gautam Gupta博士研究了基于氧化还原非金属的析氢反应（HER）催化剂的改性表面的制造和分析。无辜的缩氨基硫脲配体。这项研究解决了这种在很大程度上未被探索的新HER催化剂的结构-功能关系。它包括通过物理吸附和共价/增强非共价附着方法对碳电极表面进行改性，以提高耐久性并促进电子和质子转移。小分子催化剂库的HER活性正在以3D纳米结构催化剂载体中掺入的性能最佳的催化剂为基准，以促进反应物和产物的容易运输、高电子电导率和增强的活性。该项目更广泛的影响包括多个层面的好处。该项目促进了可持续材料的开发，用于从实际应用中分解水析氢。在大学层面，该项目加强了研究人员与UofL的Conn可再生能源中心之间的联系，该中心是一个由科学家，工程师和行业领导者组成的网络，专注于解决复杂的大规模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获得支持，学习各种技能，本科研究生就许多年轻科学家感兴趣和关注的主题做出贡献。该奖项反映了NSF的法定使命，并通过使用基金会的智力价值和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

Utilizing Charge Effects and Minimizing Intramolecular Proton Rearrangement to Improve the Overpotential of a Thiosemicarbazonato Zinc HER Catalyst

• DOI: 10.1021/acs.inorgchem.9b01912
• 发表时间: 2019-10-07
• 期刊: INORGANIC CHEMISTRY
• 影响因子: 4.6
• 作者: Cronin, Steve P.;Al Mamun, Abdullah;Grapperhaus, Craig A.
• 通讯作者: Grapperhaus, Craig A.

Small molecule crystals with 1D water wires modulate electronic properties of surface water networks

• DOI: 10.1016/j.apmt.2020.100895
• 发表时间: 2021-03-01
• 期刊: APPLIED MATERIALS TODAY
• 影响因子: 8.3
• 作者: Saraei, Nina;Gupta, Alexander J.;Grapperhaus, Craig A.
• 通讯作者: Grapperhaus, Craig A.

Ligand and Linkage Isomers of Bis(ethylthiocarbamato) Copper Complexes with Cyclic C 6 H 8 Backbone Substituents: Synthesis, Characterization, and Antiproliferation Activity

具有环状 C 6 H 8 主链取代基的双（乙基硫代氨基甲酸酯）铜配合物的配体和连接异构体：合成、表征和抗增殖活性

• DOI: 10.1002/ejic.202300447
• 发表时间: 2023
• 期刊: European Journal of Inorganic Chemistry
• 影响因子: 2.3
• 作者: Bajaj, Kritika;Andres, Sarah A.;Hofsommer, Dillon T.;Chekwube Michael, Okolocha;Mashuta, Mark S.;Bates, Paula J.;Buchanan, Robert M.;Grapperhaus, Craig A.
• 通讯作者: Grapperhaus, Craig A.

Nitrogen-Doped Graphene Oxide Electrocatalysts for the Oxygen Reduction Reaction

• DOI: 10.1021/acsanm.8b02235
• 发表时间: 2019-03-01
• 期刊: ACS APPLIED NANO MATERIALS
• 影响因子: 5.9
• 作者: Dumont, Joseph H.;Martinez, Ulises;Gupta, Gautam
• 通讯作者: Gupta, Gautam

Effect of Stacking Interactions on the Translation of Structurally Related Bis(thiosemicarbazonato)nickel(II) HER Catalysts to Modified Electrode Surfaces

堆积相互作用对结构相关的双(氨基硫脲)镍(II) HER催化剂向修饰电极表面转化的影响

• DOI: 10.1021/acs.inorgchem.9b01209
• 发表时间: 2019
• 期刊: Inorganic Chemistry
• 影响因子: 4.6
• 作者: Gupta, Alexander J.;Vishnosky, Nicholas S.;Hietsoi, Oleksandr;Losovyj, Yaroslav;Strain, Jacob;Spurgeon, Joshua;Mashuta, Mark S.;Jain, Rahul;Buchanan, Robert M.;Gupta, Gautam
• 通讯作者: Gupta, Gautam