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，预计到2024年其收入将增长至2200亿美元。精细化学品的重要类别的实例是药物、农用化学品、调味剂和香料以及特殊材料（例如，聚合物）。随着人们对能源利用、环境影响和安全性的日益关注，迫切需要开发新型、温和、高效的精细化学品合成工艺，实现可持续发展。电化学催化已经有了一个显着的复兴，研究人员探索如何使用导电性作为试剂合成精细化学品。这些节能、电力驱动的工艺可以轻松与可再生能源集成，并避免使用危险和有毒化学品，这使它们成为化学合成的强大绿色工具。然而，目前，电催化方法通常使用所谓的均相催化体系，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。这些系统由于其在反应条件下有限的稳定性而经常遭受高催化剂负载。此外，由于与催化剂分离和再循环相关的挑战，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，非均相催化剂已被用于解决上述问题。虽然它们是稳定的和方便地可回收的，但它们的整体催化效率通常不如它们的均相对应物。近年来，一类新的多相催化剂，即单原子催化剂（SACs），正成为催化科学的一个新的前沿。在这种情况下，催化剂的活性金属中心作为孤立的单原子存在，其通过载体材料稳定。活性炭可以作为均相催化剂和多相催化剂之间的桥梁，具有综合两类催化剂的优点，如高活性、高选择性、高稳定性和可重复使用性。事实上，清洁能源转化反应的许多突破（例如，氧还原、氢析出、CO2还原）。这些材料在电化学应用中显示了巨大的潜力，但使用SAC的电催化精细化学合成仍然是未开发的。交叉偶联反应作为药物合成中最常用的一类反应，在2010年获得了诺贝尔化学奖。在这个项目中，我们将利用SAC的固有特性，通过创建全新的非均相电化学交叉偶联反应作为概念验证的例子，来彻底改变精细化学合成。通过与大连化学物理研究所黄延强教授的新合作，（DICP，SAC概念的诞生地），Karl Ryder教授（UoL）和MOF技术，将使用金属有机框架（MOF）作为前体合成新型镍基SAC，和这些SAC催化反应的机制将使用现代材料表征技术进行研究。尖端有机合成、电化学、材料科学和最先进的多相催化的交叉点。该领域的成功将带来经济和环境效益，并使制药等精细化学品的生产能够使用更可持续的工艺进行。对催化剂结构-性能关系和反应机理的理解将使新的SAC系统的设计成为可能，该系统可用于一系列化学反应，扩大其影响。