Hybrid Diamond-Metal Structures from Diamondoids: Synthesis and Catalytic Applications

本研究项目旨在探索在过渡金属催化作用下，热力学上极其稳定、高度规则的纳米级碳笼（金刚石）的反应性和特性。我们概述了将纯sp3碳和过渡金属结合成独特有序结构的杂化材料的制备。由于金属-碳部分的密切联系，这种新型杂化物有望显示出迄今为止尚未报道的物理和催化性能。这种“自下而上”合成类金刚石结构的方法在纳米尺度上获得了大块金刚石的一些非常理想的特性（结构完整性、光学透明度、负电子亲和力等）。理想情况下，这种方法也可以通过创新的气相沉积技术和受过渡金属反应性（C-H活化和过渡金属促进C-C键形成）启发的化学方法，转化为纯度可控的类金刚石薄膜的生长。我们提出了一种合成、物理和计算相结合的方法，它将有机合成和材料科学的基本理解和应用结合在一起。在制备具有令人兴奋的物理性质的新型杂化材料方面有望取得进展，这些材料具有高催化剂活性和直接可分离性。所提出的工作被认为是前沿和探索性研究，因为从定义良好和适当功能化的纳米金刚石开始组装坚固的金属化纳米结构的主要目标以前从未解决过。此外，它还在“具有新特性和设计组件的对象生产”小节中解决了ANR调用描述符“用于未来产品的Axis 5-纳米材料和纳米技术”。我们提出的跨学科方法在纳米科学、过渡金属催化和混合材料方面开辟了令人兴奋的前景。这项ANR-DFG计划为法国和德国的研究人员提供了进一步科学合作的机会，从而希望能够形成一支优秀的欧洲团队。这个两国合作的创新项目明显地从正在进行的国家项目中脱颖而出，其特点是两国团队之间的理想互补和工作的充分整合。

This research project aims at exploring the reactivity and exploiting the properties of thermodynamically extremely stable, and highly regular, nm-sized carbon cages named diamondoids (nanodiamonds) in connection with transition metal catalysis. We outline the preparation of hybrid materials that combine pure sp3 carbon and transition metals into uniquely ordered structures. Such novel hybrids are expected to display hitherto unreported physical and catalytic properties due to the intimate connection of the metal-carbon moieties. The 'bottom-up' synthesis of diamond-like structures captures some of the highly desirable properties (structural integrity, optical transparency, negative electron affinity etc.) of bulk diamond at the nanoscale. Ideally, this approach could also be turned into growth of diamond-like films of controlled purity by innovative vapor phase deposition techniques and chemical methods inspired by transition metal reactivity (C-H activation and transition metal promoted C-C bond formation). We propose a combined synthetic, physical, and computational approach, which brings together both fundamental understanding as well as applications in organic synthesis and material sciences. Advances are expected in the preparation of novel hybrid materials with exciting physical properties enabling high catalyst activity and straightforward separability. The work proposed is considered frontier and explorative research since the main objective of assembling robust metallized nanostructures starting from well defined and appropriately functionalized nanodiamonds has never been tackled before. In addition, it also addresses the ANR call descriptors 'Axis 5-nanomaterials and nanotechnologies for products of the future' in the subsection concerning 'Objects production with novel properties and designed assemblies.' The transdisciplinary methodology we propose opens exciting perspectives in nanosciences, transition metal catalysis, and hybrid materials. This ANR-DFG program gives French and German researchers the opportunity to further their scientific collaborations, and thereby hopes to give rise to a European team of excellence. This bi-national innovative project clearly stands out from on-going national projects and is characterized by ideal complementarity between the teams of each country and full integration of the work.