Using topological design to develop defect-rich graphene-based substrates for single-atom catalysis

利用拓扑设计开发用于单原子催化的富含缺陷的石墨烯基基底

• 批准号: 453278757
• 负责人: Dr. Benedikt P. Klein
• 金额: --
• 依托单位: Diamond Light Source Limited
• 依托单位国家: 德国
• 项目类别: WBP Fellowship
• 财政年份: 2020
• 资助国家: 德国
• 起止时间: 2019-12-31 至 2023-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/453278757?language=en
• 关键词: Using; topological; design; develop; defect

This proposal presents a unique joint experimental and theoretical effort to design and test a novel defect-rich graphene-like carbon network as a substrate for single atom catalysis (SAC). SAC provides a pathway towards new reactivities and the more efficient use of precious metals in future catalysts, both necessary for the transition to a sustainable energy industry. The graphene-based network, central to the proposal, will be produced using a new bottom-up approach utilising topological design to circumvent most problems of regular on-surface synthesis. We will exploit the massively enhanced interaction of topologically non-alternant aromatic molecules towards metal surfaces. The use of such precursors enables the one-step preparation of a graphene-like layer by dehydrogenative coupling. This layer will contain a high concentration of topological defects, and, while lacking long range crystallinity, will provide uniform distribution of anchor sites for the single metal adatoms forming a SAC. The best precursor molecules will be chosen by theoretical pre-screening, while theoretical modelling of the catalytic activity will guide the choice of a suitable metal atom species to combine with the synthesised graphene-like substrate. The joint experimental and theoretical characterisation of both the graphene-like substrate and the produced SAC will involve advanced synchrotron spectroscopic and lab-based microscopic techniques, providing sub-Ångström resolution in structure determination and various spectroscopic data. The thereby obtained spectra will be interpreted with the help of DFT-based calculations, for which improved spectroscopy simulation methods will be developed. The produced SAC will be subjected to proof-of-principle experiments showing its catalytic activity for the low-temperature oxidation of CO.The applicant will perform experimental and theoretical work, which is expected to show benefits in both fields by way of synergetic effects in both planning and interpretation of experimental and theoretical data. The work will result in the production of a new class of graphene-based substrates for SAC. By this process, it will facilitate further research into a field critically important for the future of sustainable energy economics and with the potential of changing many industrially relevant processes on a fundamental level.During this project, the applicant will extend his portfolio of experimental methods by the addition of scanning tunnelling microscopy and advanced synchrotron based techniques, while simultaneously gaining experience in performing cutting-edge DFT-based spectroscopic simulations. The resulting uniquely broad skill set will enable him to forge an independent career at the interface between theory and experiment in the future, while at the same time creating a wide and long-lasting network of collaborators.

本文提出了一种独特的实验和理论结合的方法来设计和测试一种新型的富含缺陷的类石墨烯碳网络作为单原子催化（SAC）的底物。SAC为实现新的反应和在未来催化剂中更有效地利用贵金属提供了一条途径，这两者都是向可持续能源工业过渡所必需的。基于石墨烯的网络是该提案的核心，将采用一种新的自下而上的方法，利用拓扑设计来规避常规表面合成的大多数问题。我们将利用拓扑非交替芳香分子对金属表面的大规模增强相互作用。这种前体的使用使得通过脱氢偶联一步制备类石墨烯层成为可能。该层将包含高浓度的拓扑缺陷，并且，虽然缺乏长范围的结晶度，将为形成SAC的单个金属原子提供均匀分布的锚位点。最佳前体分子将通过理论预筛选来选择，而催化活性的理论建模将指导选择合适的金属原子种类来与合成的石墨烯样底物结合。类石墨烯衬底和生产的SAC的联合实验和理论表征将涉及先进的同步加速器光谱和基于实验室的微观技术，提供亚-Ångström分辨率的结构测定和各种光谱数据。由此获得的光谱将借助基于dft的计算进行解释，为此将开发改进的光谱模拟方法。所生产的SAC将进行原理验证实验，以证明其对co低温氧化的催化活性。申请人将进行实验和理论工作，期望通过在实验和理论数据的规划和解释方面的协同效应，在这两个领域显示效益。这项工作将为SAC生产一类新的石墨烯基衬底。通过这一过程，它将促进对一个对可持续能源经济学的未来至关重要的领域的进一步研究，并有可能在基本一级上改变许多工业相关过程。在此项目中，申请人将通过增加扫描隧道显微镜和先进的同步加速器技术来扩展他的实验方法组合，同时获得执行尖端dft的光谱模拟的经验。由此产生的独特的广泛技能将使他能够在未来的理论和实验之间建立一个独立的职业生涯，同时创建一个广泛而持久的合作者网络。