Electrocatalytic Cross-Coupling Reactions with Heterogeneous Single Atom Catalysts

多相单原子催化剂的电催化交叉偶联反应

• 批准号: EP/Y002628/1
• 负责人: Qun Cao
• 金额: $ 19.56万
• 依托单位: University of Leicester
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2024
• 资助国家: 英国
• 起止时间: 2024 至 无数据
• 项目状态: 未结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FY002628%2F1
• 关键词: Electrocatalytic; Cross; Coupling; Reactions; Heterogeneous

Fine chemicals make up the largest portion of the global chemicals market with their revenues expected to grow to $220bn by 2024. Examples of important classes of fine chemicals, are pharmaceuticals, agrochemicals, flavours and fragrances and speciality materials (e.g., polymers). With the increasing attention on energy usage, environmental impact and safety, there is an urgent need to develop new, mild and efficient synthetic process for sustainable fine chemicals synthesis. There has been a remarkable renaissance of electrochemical catalysis, with researchers exploring how fine chemicals can be synthesised with using electrictricity as a reagent. These energy efficient, electricity-driven processes can be easily integrated with renewable energy sources and avoid the use of dangerous and toxic chemicals, which makes them a powerful green tool for chemical synthesis. However, at present, electrocatalytic methods typically utilise so called homogeneous catalytic systems, which requires transition metal catalysts, whereby all of the catalyst is fully dissolved in the reaction mixtures. These systems often suffer from high catalyst loadings due to their limited stability under the reaction conditions. Furthermore, the expensive homogeneous catalyst can only be used once due to the challenges associated with catalyst separation and recycling. With the rapid growth of nanoscience, heterogeneous catalysts have been exploited to tackle the aforementioned problems. Although they are stable and conveniently recyclable, their overall catalytic efficiencies are usually inferior to their homogeneous counterparts. In recent years, a new class of heterogeneous catalysts, namely single-atom catalysts (SACs), which are emerging as a new frontier in catalysis science. In this case, the active metal centre of the catalyst exists as isolated single atoms, which are stabilized by the support material., SACs can serve as a bridge between homogeneous and heterogeneous catalysts with the possibility of integrating the merits of both types of catalysts such as high activity, selectivity, stability and reusability. Indeed, many breakthroughs in clean energy conversion reactions (e.g., oxygen reduction, hydrogen evolution, CO2 reduction) using SACs has been reported recently. These have demonstrated their great potential in electrochemical applications, but electrocatalytic fine chemical synthesis using SACs remains unexplored. As the most frequently used class of reaction in pharmaceutical synthesis, the so called cross-coupling reactions were recognized in 2010 by the Nobel Prize in Chemistry. In this project, we will exploit the inherent properties of SACs to revolutionise fine chemical synthesis by creating completely new heterogeneous electrochemical cross-coupling reactions as proof-of-concept examples. Through newly forged collaborations with Prof. Yanqiang Huang from Dalian Institute of Chemical Physics (DICP, the birthplace of SACs concept), Prof. Karl Ryder (UoL) and MOF Technologies, novel nickel based SACs will be synthesized using metal organic frameworks (MOFs) as precursors, and the mechanisms of these SACs catalysed reactions will be studied using modern material characterization techniques This project is highly interdisciplinary and at the intersection of cutting-edge organic synthesis, electrochemistry, materials science and state-of-the-art heterogeneous catalysis. Success in the area will bring both economic and environmental benefits and enable the manufacture of fine chemicals, such as pharmaceuticals, to be prepared using more sustainable processes. The understanding of catalyst structure-performance relationships and reaction mechanisms will enable the design of new SACs systems, that can be exploited for a range of chemical reactions, broadening its impact.

精细化学品占全球化学品市场的最大份额，其收入预计到 2024 年将增长至 2200 亿美元。重要的精细化学品类别包括药品、农用化学品、香精香料以及特种材料（例如聚合物）。随着人们对能源使用、环境影响和安全性的日益关注，迫切需要开发新的、温和的、高效的合成工艺来实现可持续的精细化学品合成。随着研究人员探索如何使用电作为试剂合成精细化学品，电化学催化取得了显着的复兴。这些节能、电力驱动的工艺可以轻松地与可再生能源集成，并避免使用危险和有毒的化学品，这使它们成为化学合成的强大绿色工具。然而，目前，电催化方法通常利用所谓的均相催化系统，其需要过渡金属催化剂，由此所有催化剂完全溶解在反应混合物中。由于这些系统在反应条件下的稳定性有限，因此常常遭受高催化剂负载的困扰。此外，由于催化剂分离和回收方面的挑战，昂贵的均相催化剂只能使用一次。随着纳米科学的快速发展，多相催化剂已被用来解决上述问题。尽管它们稳定且可方便回收，但它们的总体催化效率通常不如同质同类产品。近年来，一类新型多相催化剂，即单原子催化剂（SAC），正在成为催化科学的新前沿。在这种情况下，催化剂的活性金属中心以孤立的单原子形式存在，并由载体材料稳定。SAC 可以作为均相和非均相催化剂之间的桥梁，并有可能整合两种类型催化剂的优点，例如具有高活性、选择性、稳定性和可重复使用性。事实上，最近报道了利用 SAC 在清洁能源转化反应（例如氧气还原、氢气析出、二氧化碳还原）方面取得的许多突破。这些已经证明了它们在电化学应用中的巨大潜力，但使用 SAC 的电催化精细化学合成仍未得到探索。作为药物合成中最常用的一类反应，所谓的交叉偶联反应于 2010 年获得诺贝尔化学奖。在这个项目中，我们将利用 SAC 的固有特性，通过创建全新的异质电化学交叉偶联反应作为概念验证示例，彻底改变精细化学合成。通过与大连化学物理研究所（DICP，SAC概念的发源地）黄彦强教授、Karl Ryder教授（伦敦大学）和MOF Technologies的新合作，将使用金属有机框架（MOF）合成新型镍基SAC作为前体，这些 SAC 催化反应的机制将使用现代材料表征技术进行研究。该项目是高度跨学科的，处于尖端有机合成、电化学、材料科学的交叉点和最先进的多相催化。该领域的成功将带来经济和环境效益，并使精细化学品（例如药品）的生产能够使用更可持续的工艺进行制备。对催化剂结构-性能关系和反应机制的理解将有助于设计新的 SAC 系统，该系统可用于一系列化学反应，扩大其影响。