Clean catalysis for sustainable development

清洁催化促进可持续发展

• 批准号: EP/J018139/1
• 负责人: Paul Kamer
• 金额: $ 269.87万
• 依托单位: University of St Andrews
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2012
• 资助国家: 英国
• 起止时间: 2012 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FJ018139%2F1
• 关键词: Clean; catalysis; sustainable; development

A sustainable society requires the efficient use of energy and renewable matter. It consequently demands selective new methodologies for the preparation of advanced materials. In this context and as resources based on fossil reserves are rapidly depleting, there are two requirements: first, a change from traditional stoichiometric, high energy methods that produce huge amounts of chemical waste to mild and clean catalytic processes; second, a major step change in chemicals production with fossil fuels being replaced by renewable resources as chemical starter units.The long term aim and vision of catalysis research at EaStCHEM and of this Critical Mass proposal in particular is to develop all-catalytic routes to useful chemicals from renewable resources. We will provide a research environment that both improves and expands the wide range of catalytic processes used in the chemical and pharmaceutical industries. To do this we will exploit renewable and alternative feedstocks including CO2, lignocellulose and other feedstocks formed on multimillion tonnes scale as waste products from agriculture and wood processing.This proposed change in how we access our essential chemicals requires a new generation of catalysts. The challenge is even larger because the renewable substrates are not only difficult to activate (CO2, lignin) but are often available not as pure substrates but as components of a very diverse crude mixtures (e.g. methyl oleate in tall oil). Therefore, novel robust catalysts are required which are capable of combining high activity with superb selectivity and substrate compatibility. The required selectivity resulting in high atom economy, efficiency and environmental factor will only be feasible through the development of new scientific and technological tools. To achieve this challenging objective, existing catalysts must undergo major improvements and new catalysts must be designed for as yet uncatalyzed reactions. As we believe homogenous catalysts offer the unique combination of unprecedented activities and high selectivity, it is timely to combine EaStCHEM's strengths in homogeneous catalysis in this critical mass program to develop sustainable production methods by changing to all-catalytic conversions of renewable feedstocks. The switch to a society which relies on chemical production from all-renewable resources is a challenge of GRAND proportions, and a roadmap for this change must be broken down into smaller components with suitable experts addressing achievable goals. In this proposal we have assessed the strengths in catalysis across EaStCHEM and have designed projects at a variety of risk levels that will significantly impact on the overall change necessary in the challenging move "from oil to biomass". We will: 1. use CO2 as an ever abundant C1 building block in chemical processes that exploit newly developed state-of-the-art catalytic transformations for C-H activation/carboxylation, polymer formation, as well as electro- and chemical reduction processes. 2. We will develop optimal catalysts for ether cleavage in 'real life samples' of lignin for maximising the potential of lignocellulose as a source of fuels and fine chemicals. By combining our expertise in ligand design and computational methods we will develop efficient catalyst based on N-heterocyclic carbenes, wide bite angle phosphines and oxidative enzymes and chemocatalysts.3. We will develop novel catalytic methods to convert renewable and waste feedstocks to important products such as fuels, chemicals and polymers.As we anticipate that this combined effort will include the de-novo development of new catalyst we will also create a ligand and catalyst synthesis and discovery centre which will support the catalyst development process of all the workpackages for the full duration of the project and thereafter. By focusing our experience and skills in catalysis, we will contribute to a post-fossil fuels world.

一个可持续发展的社会需要有效利用能源和可再生物质。因此，它需要有选择的新方法来制备先进的材料。在这种情况下，随着以化石储量为基础的资源迅速枯竭，有两个要求：第一，从传统的化学计量、高能量方法转变为温和和清洁的催化方法，因为这种方法会产生大量的化学废物;第二，化学品生产的重大变革，化石燃料被可再生资源取代作为化学品起始单元。催化研究的长期目标和愿景EaStCHEM和这个临界质量的建议，特别是开发全催化路线，以有用的化学品从可再生资源。我们将提供一个研究环境，既改善和扩大在化学和制药工业中使用的催化过程的范围。为此，我们将利用可再生和替代原料，包括二氧化碳、木质纤维素和其他数百万吨规模的原料，这些原料是农业和木材加工产生的废弃物。我们提议改变获取基本化学品的方式，这需要新一代催化剂。挑战甚至更大，因为可再生底物不仅难以活化（CO2、木质素），而且通常不是作为纯底物，而是作为非常多样化的粗混合物的组分（例如妥尔油中的油酸甲酯）。因此，需要能够将高活性与极好的选择性和底物相容性相结合的新型稳健催化剂。只有通过开发新的科学和技术工具，才能实现所需的选择性，从而提高原子经济性、效率和环境因素。为了实现这一具有挑战性的目标，必须对现有催化剂进行重大改进，并且必须为尚未催化的反应设计新的催化剂。由于我们相信均相催化剂提供了前所未有的活性和高选择性的独特组合，因此在这个临界质量计划中结合联合收割机EaStCHEM在均相催化方面的优势，通过改变可再生原料的全催化转化来开发可持续的生产方法是及时的。向依赖于所有可再生资源的化学品生产的社会转变是一个巨大的挑战，必须将这种变化的路线图分解为更小的组成部分，并由合适的专家解决可实现的目标。在本提案中，我们评估了EastCHEM在催化方面的优势，并设计了各种风险水平的项目，这些项目将对“从石油到生物质”这一具有挑战性的举措中所需的整体变化产生重大影响。我们将：1.利用CO2作为化学过程中丰富的C1结构单元，利用新开发的最先进的C-H活化/羧化催化转化、聚合物形成以及电化学和化学还原过程。2.我们将开发用于木质素“真实的样品”中醚裂解的最佳催化剂，以最大限度地发挥木质纤维素作为燃料和精细化学品来源的潜力。通过结合我们在配体设计和计算方法方面的专业知识，我们将开发基于N-杂环卡宾，宽咬合角膦和氧化酶的高效催化剂和化学催化剂。我们将开发新的催化方法，将可再生和废弃原料转化为重要产品，如燃料，化学品和聚合物。由于我们预计这种联合努力将包括新催化剂的重新开发，我们还将创建一个配体和催化剂合成和发现中心，该中心将在整个项目期间及之后支持所有工作包的催化剂开发过程。通过集中我们在催化方面的经验和技能，我们将为后化石燃料世界做出贡献。

项目成果

Applications of boroxide ligands in supporting small molecule activation by U(iii) and U(iv) complexes.

• DOI: 10.1039/c8dt05051a
• 发表时间: 2019-04
• 期刊: Dalton transactions
• 影响因子: 4
• 作者: P. Arnold;Laura Puig-Urrea;J. Wells;D. Yuan;Faye L. Cruickshank;Rowan D. Young

Chiral Wide-Bite-Angle Diphosphine Ligands: Synthesis, Coordination Chemistry, and Application in Pd-Catalyzed Allylic Alkylation

手性宽咬角二膦配体：合成、配位化学及其在 Pd 催化烯丙基烷基化中的应用

• DOI: 10.1021/om5008055
• 发表时间: 2015
• 期刊: Organometallics
• 影响因子: 2.8
• 作者: Czauderna C

Isothiourea-Catalyzed Enantioselective Addition of 4-Nitrophenyl Esters to Iminium Ions

• DOI: 10.1021/acscatal.7b02697
• 发表时间: 2018-02-01
• 期刊: ACS CATALYSIS
• 影响因子: 12.9
• 作者: Arokianathar, Jude N.;Frost, Aileen B.;Smith, Andrew D.
• 通讯作者: Smith, Andrew D.

Arylboronic Acid-Catalyzed Racemization of Secondary and Tertiary Alcohols.

• DOI: 10.1021/acs.joc.2c01602
• 发表时间: 2022-10-07
• 期刊: JOURNAL OF ORGANIC CHEMISTRY
• 影响因子: 3.6
• 作者: Boyce, Gregory R.;Musolino, Stefania F.;Yang, Jianing;Smith, Andrew D.;Taylor, James E.
• 通讯作者: Taylor, James E.

Catalytic depolymerisation of isolated lignins to fine chemicals using a Pt/alumina catalyst: part 1-impact of the lignin structure

• DOI: 10.1039/c4gc01678e
• 发表时间: 2015-01-01
• 期刊: GREEN CHEMISTRY
• 影响因子: 9.8
• 作者: Bouxin, Florent P.;McVeigh, Ashley;Jackson, S. David
• 通讯作者: Jackson, S. David