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

这一建议是一项独特的实验和理论联合工作，旨在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)的衬底。SAC提供了一条通向新的反应性和在未来催化剂中更有效地使用贵金属的途径，这两项都是向可持续能源行业过渡所必需的。该提议的核心是基于石墨烯的网络，它将使用一种新的自下而上的方法来产生，利用拓扑设计来绕过大多数常规表面合成的问题。我们将利用拓扑上非交替的芳香族分子与金属表面的大规模增强相互作用。使用这种前驱体能够通过脱氢偶联一步制备类石墨烯层。这一层将包含高度集中的拓扑缺陷，虽然缺乏长程结晶度，但将为形成SAC的单个金属吸附原子提供均匀分布的锚点。最好的前体分子将通过理论预筛选来选择，而催化活性的理论模拟将指导选择合适的金属原子物种与合成的石墨烯基片结合。类石墨烯衬底和所生产的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显微技术，在结构确定和各种光谱数据方面提供亚分辨率。由此获得的光谱将借助基于密度泛函理论的计算进行解释，为此将开发改进的光谱模拟方法。所生产的SAC将接受原理验证实验，以显示其对CO低温氧化的催化活性。申请者将进行实验和理论工作，预计将通过规划和解释实验和理论数据的协同效应，在这两个领域都显示出好处。这项工作将为SAC生产一类新的基于石墨烯的衬底。通过这个过程，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，并有可能在基础水平上改变许多工业相关过程。在这个项目中，申请者将通过增加扫描隧道显微镜和先进的基于同步辐射的技术来扩展他的实验方法组合，同时获得执行基于DFT的尖端光谱模拟的经验。由此产生的独特而广泛的技能集将使他能够在未来在理论和实验之间打造一份独立的职业生涯，同时创建一个广泛和持久的合作者网络。

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.