Enzyme carbomimetics: Single site sustainable catalysts for alcohols amination

酶碳模拟物：用于醇胺化的单中心可持续催化剂

• 批准号: 2606065
• 金额: --
• 依托单位: Imperial College London
• 依托单位国家: 英国
• 项目类别: Studentship
• 财政年份: 2021
• 资助国家: 英国
• 起止时间: 2021 至 无数据
• 项目状态: 未结题
• 来源: https://gtr.ukri.org/projects?ref=studentship-2606065
• 关键词: Enzyme; carbomimetics; Single; site; sustainable

Amines are ubiquitous in chemistry, with a global market market at more than $15 billion in 2020, and growing by more than 4% every year. They are key intermediates in the chemical industry, with extensive applications as corrosion inhibitors, agrochemicals, pharmaceuticals, detergents, fabric softeners, lubricants, polymers, and food additives. Amines are made from NH3 alkylation on the industrial scale, by alcohol alkylation, nitroarene reduction, or halide substitution. These processes require harsh conditions (>50 bar, 100-250 C), external reductants and/or emit stoichiometric amounts of hydrogen halide waste. Heterogeneous catalysts are typically used, and suffer from low selectivity and activity due to the low reactivity of NH3 compared to higher amines. The aim of the project is to use high-throughput synthetic approaches to identify single-site metals supported on nitrogen-doped carbon (MN4@C) catalysts (carbozymes) for the selective alkylation of NH3 with alcohols. Alcohols only yield H2O as a byproduct, and are abundant in biomass precursors, thus constituting ideal starting materials for large scale applications towards a more sustainable industry in a circular economy.Single-site catalysts (SSC) will solve issues associated with heterogeneous catalysts (surface poisoning, low selectivity) while ensuring a 100% metal efficiency, with carbon and nitrogen as sustainable elements that are suitable to prevent SSC degradation into oxides or carbides. Catalyst discovery will be assisted by theoretical approaches (DFT and machine learning (ML)), to identify mechanistical pathways as well as to optimise and discover new unknown catalysts (i.e. dual sites). The project will also test the best performing catalysts for flow conditions for an easier impmentation into chemical industry.

胺在化学中无处不在，2020年全球市场规模超过150亿美元，每年增长4%以上。它们是化学工业中的关键中间体，广泛应用于缓蚀剂、农用化学品、制药、洗涤剂、织物柔软剂、润滑剂、聚合物和食品添加剂。胺在工业规模上通过醇烷基化、硝基芳烃还原或卤化物取代由NH3烷基化制备。这些方法需要苛刻的条件（>50巴，100-250 ℃）、外部还原剂和/或排放化学计量量的卤化氢废物。通常使用非均相催化剂，并且由于与高级胺相比NH3的低反应性，非均相催化剂具有低选择性和低活性。该项目的目的是使用高通量合成方法来识别负载在氮掺杂碳（MN4@C）催化剂（carbozymes）上的单中心金属，用于NH3与醇的选择性烷基化。醇类仅产生H2O作为副产物，并且富含生物质前体，因此构成了大规模应用的理想起始原料，以实现循环经济中更可持续的工业。单活性中心催化剂（SSC）将解决与多相催化剂相关的问题（表面中毒，低选择性），同时确保100%的金属效率，其中碳和氮作为可持续元素，其适合于防止SSC降解成氧化物或碳化物。催化剂的发现将通过理论方法（DFT和机器学习（ML））来辅助，以确定机制途径以及优化和发现新的未知催化剂（即双位点）。该项目还将测试流动条件下性能最佳的催化剂，以便更容易地应用于化学工业。