Ligand-centered copper, zinc, and metal-free hydrogen evolution catalysts

以配位体为中心的铜、锌和不含金属的析氢催化剂

• 批准号: 1665136
• 负责人: Craig Grapperhaus
• 金额: $ 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: 2017
• 资助国家: 美国
• 起止时间: 2017-07-01 至 2020-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1665136&HistoricalAwards=false
• 关键词: Ligand; centered; copper; zinc; metal

The Chemical Catalysis Program of the Chemistry Division supports the project by Professors Craig A. Grapperhaus and Pawel M. Kozlowski. Professors Grapperhaus and Kozlowski are faculty members of the Department of Chemistry at the University of Louisville. They are developing novel ligand-centered electrocatalysts for the evolution and oxidation of hydrogen. Hydrogen serves as a promising alternative carbon-free fuel and is an essential building block for industrial and agricultural processes. Currently, 95% of industrial hydrogen derives from unsustainable fossil-fuel cracking. The catalysts in this project employ a ligand-centered approach. Ligands are small molecules that bind a central metal into a complex. A major advantage of the ligand-centered approach is that the organic framework functions as the active site, allowing the development of catalysts that are metal-free or promoted by sustainable transition-metals (e.g. copper) or non-transition metals (e.g. zinc). The project facilitates the development of sustainable hydrogen evolution/oxidation systems, which have practical applications. It further strengthens connections between the researchers and the Conn Renewable Energy Center, a center that promotes partnerships among Kentucky's colleges and universities, private industries, and non-profit organizations dedicated to renewable energy solutions. Graduate students and undergraduate participants learn a diverse combination of skills including synthesis, characterization, electrochemistry, and computation. The project is well suited for undergraduate research students, who participate and make contributions on a topic of interest and concern to many young scientists-in-training.The catalysts in this project are at the forefront of an emerging ligand-centered approach that avoids traditional metal-hydrides, which have been well studied. In contrast, the ligand-centered approach remains underdeveloped, and fundamental questions regarding structure-activity relationships remain to be answered. Symmetric and asymmetric N2S2 bis-thiosemicarbazone catalysts are prepared under three metal loading conditions: 1) transition metal (copper); 2) non-transition metal (zinc); 3) metal-free. The functional groups on the ligands and metal-component are varied to evaluate ligand- and metal effects on catalytic activity. The requisite features required for ligand-centered hydrogen evolution/oxidation are being established through a systematic "trimming" of the bis-thiosemicarbazone framework involving the synthesis of new catalysts based on fragments of the larger ligand. Using insights developed during the project, a third-generation of ligand-centered catalysts are under design as "active site pockets" that position key components in the proper geometric positions to promote activity. The educational plan includes graduate and undergraduate training with an emphasis on minority and first-generation college students.

化学系的化学催化计划支持克雷格·A·格拉珀豪斯教授和帕维尔·M·科兹洛夫斯基教授的项目。格拉珀豪斯教授和科兹洛夫斯基教授是路易斯维尔大学化学系的教员。他们正在开发用于氢析出和氧化的新型配体中心电催化剂。氢气是一种很有前途的无碳替代燃料，是工农业生产过程中必不可少的组成部分。目前，95%的工业氢气来自不可持续的化石燃料裂解。该项目中的催化剂采用了以配体为中心的方法。配体是将中心金属结合成络合物的小分子。以配体为中心的方法的一个主要优点是有机骨架起到了活性中心的作用，允许开发不含金属或由可持续过渡金属(例如铜)或非过渡金属(例如锌)促进的催化剂。该项目促进了具有实际应用的可持续放氢/氧化系统的开发。它进一步加强了研究人员与康涅狄格州可再生能源中心之间的联系，康涅狄格州可再生能源中心是一个促进肯塔基州学院和大学、私营行业和致力于可再生能源解决方案的非营利组织之间的伙伴关系的中心。研究生和本科生学习各种技能的组合，包括合成、表征、电化学和计算。该项目非常适合本科生，他们参与并对许多正在接受培训的年轻科学家感兴趣和关注的主题做出了贡献。该项目中的催化剂处于一种新兴的以配体为中心的方法的前沿，该方法避免了传统的金属氢化物，这一方法已经得到了很好的研究。相反，以配体为中心的方法仍然不发达，关于结构-活性关系的基本问题仍有待回答。在三种金属负载条件下制备了对称和不对称N2S2双缩氨基硫脲催化剂：1)过渡金属(铜)；2)非过渡金属(锌)；3)无金属。配体和金属组分上的官能团是不同的，以评价配体和金属对催化活性的影响。以配体为中心的氢析出/氧化所需的必要特征正在通过对双缩氨基硫脲框架进行系统的“修剪”来确定，其中包括根据较大的配体片段合成新的催化剂。利用项目期间开发的见解，第三代以配体为中心的催化剂正在设计中，作为“活性中心口袋”，将关键组件放置在适当的几何位置以促进活性。该教育计划包括研究生和本科生培训，重点是少数民族和第一代大学生。

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.

Water wire clusters in isostructural Cu(II) and Ni(II) complexes: Synthesis, characterization, and thermal analyses

• DOI: 10.1016/j.ica.2019.04.012
• 发表时间: 2019-06
• 期刊: Inorganica Chimica Acta
• 影响因子: 2.8
• 作者: N. Saraei;O. Hietsoi;Brian C. Frye;Alexander J. Gupta;M. Mashuta;Gautam Gupta;R. M. Buchanan;C. Grapperhaus

Copper bis(thiosemicarbazone) Complexes with Pendent Polyamines: Effects of Proton Relays and Charged Moieties on Electrocatalytic HER

• DOI: 10.1002/ejic.202000774
• 发表时间: 2020-12-23
• 期刊: EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
• 影响因子: 2.3
• 作者: Calvary, Caleb A.;Hietsoi, Oleksandr;Grapperhaus, Craig A.
• 通讯作者: Grapperhaus, Craig A.

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