Multifunctional Electrochemical Flow Platform for High-Throughput Synthesis & Optimisation of Catalysts

用于高通量合成的多功能电化学流平台

• 批准号: EP/R009406/1
• 负责人: Charlotte Willans
• 金额: $ 94.46万
• 依托单位: University of Leeds
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2018
• 资助国家: 英国
• 起止时间: 2018 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FR009406%2F1
• 关键词: Multifunctional; Electrochemical; Flow; Platform; Throughput

We will develop new technology that greatly accelerates the process of discovering, developing and implementing sustainable organometallic catalysts for industrially-relevant reactions.Many reactions in pharmaceutical, agrochemical and fine chemicals processes require metal catalysts which rely on platinum group metals (PGMs) such as palladium, platinum and rhodium. PGMs are expensive and are on the European Commission's 2014 list of 20 critical raw materials (http://eur-lex.europa.eu/legal-content/EN/TXT/?uri=CELEX:52014DC0297), which possess serious risk of dwindling supply. Furthermore, PGMs are toxic, hence must be removed from final products to levels that are often difficult/costly to achieve (<5ppm for active pharmaceutical ingredients). The currently increasing use of PGMs in the chemicals industry is therefore untenable in the medium to long-term. Base-metals such as copper and iron are much more attractive to use as catalysts due to being significantly more abundant and typically having lower toxicity (depending upon speciation). Despite this, the use of base-metals in catalysis is rare in industry; a lack of understanding of the active species and mechanistic profiles of base-metal catalysts, which are more challenging to study than PGMs, means that reactions are unpredictable and often irreproducible. In addition, high catalyst loadings and harsh reaction conditions (when compared to, for example, palladium-catalysed reactions) are usually required.Catalysts are generally discovered and developed using a linear process, whereby a catalyst is designed and synthesised, tested and optimised in a specific reaction, examined for substrate scope under optimised conditions, and redesigned to try and produce more active and selective (2nd generation) catalysts. In addition to being slow and labour intensive, this process risks overlooking potentially valuable catalysts. For example, due to time constraints, a 2nd generation catalyst may only be tested under conditions that are optimum for the 1st generation catalyst, when alternative and improved conditions could be more suitable.This proposal seeks to bring together a range of complementary expertise across chemistry and engineering to develop new technology that is capable of rapidly synthesising, screening and self-optimising base-metal catalysts. Both the catalyst synthesis and catalytic reaction stages will be performed in flow cells, which enables online analysis of the output at each stage, and allows modification of the conditions as the reactions are running. Algorithms will be used so that the reactions become self-optimising i.e. conditions are automatically varied in response to the analytical data, enabling several sets of conditions to be screened for a number of catalysts within a relatively short period of time.Our aim is for the technology to be adopted by both academic and industrial laboratories for the development of catalysts more broadly. We will make all information relating to reactor designs, variables, algorithms etc. open access, so that other researchers can replicate and apply the technology. Data relating to base-metal catalysed reactions will be added to a searchable database; this will provide a valuable resource to others studying these types of reactions, enabling a more knowledge-based and frontier-leading approach to catalyst development.

我们将开发新技术，大大加快工业相关反应的可持续有机金属催化剂的发现、开发和实施过程。制药、农业化学和精细化学品工艺中的许多反应都需要依赖铂族金属 (PGM) 的金属催化剂，例如钯、铂和铑。铂族金属价格昂贵，并且被列入欧盟委员会 2014 年 20 种关键原材料清单 (http://eur-lex.europa.eu/legal-content/EN/TXT/?uri=CELEX:52014DC0297)，存在供应减少的严重风险。此外，铂族金属具有毒性，因此必须将其从最终产品中去除到通常难以/成本高昂的水平（活性药物成分<5ppm）。因此，目前化学工业中越来越多地使用铂族金属，从中长期来看是站不住脚的。铜和铁等贱金属作为催化剂使用起来更有吸引力，因为其含量明显更高，并且通常具有较低的毒性（取决于形态）。尽管如此，贱金属在催化中的应用在工业中还是很少见的。由于缺乏对贱金属催化剂的活性物质和机理特征的了解，这比铂族金属的研究更具挑战性，这意味着反应是不可预测的，而且通常是不可重现的。此外，通常需要高催化剂负载量和苛刻的反应条件（例如与钯催化反应相比）。催化剂通常是使用线性过程发现和开发的，即在特定反应中设计和合成、测试和优化催化剂，在优化条件下检查底物范围，并重新设计以尝试生产更具活性和选择性的（第二代）催化剂。除了缓慢且劳动密集之外，该过程还存在忽视潜在有价值的催化剂的风险。例如，由于时间限制，第二代催化剂只能在最适合第一代催化剂的条件下进行测试，而替代和改进的条件可能更合适。该提案旨在汇集化学和工程领域的一系列互补专业知识，开发能够快速合成、筛选和自我优化贱金属催化剂的新技术。催化剂合成和催化反应阶段都将在流通池中进行，这使得能够在线分析每个阶段的输出，并允许在反应运行时修改条件。将使用算法使反应变得自我优化，即条件根据分析数据自动变化，从而能够在相对较短的时间内筛选多种催化剂的多组条件。我们的目标是让学术和工业实验室采用该技术，以更广泛地开发催化剂。我们将开放所有与反应堆设计、变量、算法等相关的信息，以便其他研究人员可以复制和应用该技术。与贱金属催化反应相关的数据将被添加到可搜索的数据库中；这将为其他研究这些类型反应的人提供宝贵的资源，从而实现更加基于知识和前沿的催化剂开发方法。

项目成果

Electrochemistry in continuous systems

• DOI: 10.1016/j.cogsc.2020.100355
• 发表时间: 2020-12
• 期刊: Green and Sustainable Chemistry
• 作者: Thomas P. Nicholls;C. Schotten;C. Willans

Development of a multistep, electrochemical flow platform for automated catalyst screening

开发用于自动催化剂筛选的多步电化学流平台

• DOI: 10.1039/d2cy00587e
• 发表时间: 2022
• 期刊: Catalysis Science & Technology
• 影响因子: 5
• 作者: Schotten C

On-Demand Electrochemical Synthesis of Tetrakisacetonitrile Copper(I) Triflate and Its Application in the Aerobic Oxidation of Alcohols.

• DOI: 10.1021/acs.inorgchem.1c00488
• 发表时间: 2021-04
• 期刊: Inorganic chemistry
• 影响因子: 4.6
• 作者: Thomas P. Nicholls;R. Bourne;B. Nguyen;N. Kapur;C. Willans

A Dichotomy in Cross-Coupling Site Selectivity in a Dihalogenated Heteroarene: Influence of Mononuclear Pd, Pd Clusters, and Pd Nanoparticles-the Case for Exploiting Pd Catalyst Speciation.

• DOI: 10.1021/jacs.1c05294
• 发表时间: 2021-06-30
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Scott NWJ;Ford MJ;Jeddi N;Eyles A;Simon L;Whitwood AC;Tanner T;Willans CE;Fairlamb IJS
• 通讯作者: Fairlamb IJS

A Versatile Electrochemical Batch Reactor for Synthetic Organic and Inorganic Transformations and Analytical Electrochemistry

用于合成有机和无机转化以及分析电化学的多功能电化学间歇反应器

• DOI: 10.1021/acs.oprd.0c00091
• 发表时间: 2020
• 期刊: Organic Process Research & Development
• 影响因子: 3.4
• 作者: Stephen H