NSF-DFG Echem: Synergistic Experimental and Computational Approaches to Designing Electrocatalysts with Proton-Responsive Ligand Architecture

使用非石化小分子在化学键中存储和释放能量是有吸引力的，因为其可扩展性，稳定性和短期或长期部署的灵活性。诱导非贵金属在非生物条件下催化反应，同时复制酶的活性和效率仍然是基础化学科学竞技场的挑战。准确地对化学储能新催化剂的性能进行基准测试和预测需要实验学家和理论家共同努力，以便更广泛的化学界能够使用新的工具。该计划受益于统一的实验和理论方法，以应对具有全球影响的现代挑战。一些酶使用连接到催化剂框架的侧基，提高H2生产过程中的质子转移速率和效率。使用这些模板作为灵感，使合成易处理的分子电催化剂，合成将集中在协调胺官能化的配体的非贵金属，这是前所未有的电催化。将使用光谱和电分析方法详细研究初级/次级配位球对电催化H2生产的影响。表征和机理分析将与计算数据集紧密结合，以指导实验室工作。电催化剂的性能将通过测量氧化还原电位，周转频率，过电位和探测标度关系来评估。实验和计算分析将通过计算M-H/N-H/C-H氧化还原电位和酸度来调查电催化剂的自由能景观。这些参数将指导合成工作，并预测哪些催化剂改性可以最大限度地减少中间体之间的自由能差异。将使用最先进的量子化学方法，包括自动筛选构象，溶剂化效应的治疗，和半自动化的反应网络探索工具。计算方法的发展和成熟将大大受益于它们在这些机械挑战中的应用。更广泛的主题，如可持续性，推动科学向前发展，利用自然作为灵感，使可再生能源更接近社会现实。（半）自动化计算工作流程的发展将帮助化学家在标准台式计算机而不是超级计算机上应用类似的工作流程来解决他们的问题。

Storing and releasing energy in chemical bonds using non-petrochemical small molecules is attractive because of its scalability, stability, and flexibility for short-term or long-term deployment. Coaxing non-precious metals to catalyze reactions under abiotic conditions while replicating the activity and efficiency of enzymes remains a challenge in the arena of fundamental chemical science. Accurately benchmarking and predicting the properties of new catalysts for chemical energy storage requires experimentalists and theorists to work together so new tools become accessible to the broader chemistry community. This program benefits from a unified experimental and theoretical approach to tackle modern challenges with global impact.Some enzymes use a pendant base attached to the catalyst framework, enhancing proton transfer rates and efficiencies during H2 production. Using these templates as inspiration for making synthetically tractable molecular electrocatalysts, synthesis will focus on coordinating amine-functionalized cyclopentadienyl ligands to non-precious metals, which are unprecedented in electrocatalysis. The impact of primary/secondary coordination spheres on electrocatalytic H2 production will be investigated in detail using spectroscopic and electroanalytical methods. Characterization and mechanistic analysis will be tightly coupled with computational datasets to guide laboratory efforts.Electrocatalyst performance will be assessed by measuring redox potential, turnover frequency, overpotential, and probing scaling relationships. Experimental and computational analyses will survey the free energy landscapes of electrocatalysts by calculating M-H/N-H/C-H redox potentials and acidities. These parameters will guide synthetic efforts and predict which catalyst modifications could minimize free energy differences between intermediates. State-of-the-art quantum chemical methods will be used, including automatic screening for conformers, treatment of solvation effects, and semi-automated reaction-network exploration tools. The development and maturation of computational methods will benefit greatly from their application to these mechanistic challenges.Broader themes such as sustainability drive the science forward, using Nature as inspiration to bring renewable energy closer to reality for society. The development of (semi)automated computational workflows will aid chemists to apply similar workflows to their problems on standard desktop computers instead of supercomputers.