Nano-Integration of Metal-Organic Frameworks and Catalysis for the Uptake and Utilisation of CO2

金属有机框架的纳米集成和二氧化碳吸收和利用的催化作用

• 批准号: EP/H046305/1
• 负责人: Frank Marken
• 金额: $ 151.3万
• 依托单位: University of Bath
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2010
• 资助国家: 英国
• 起止时间: 2010 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FH046305%2F1
• 关键词: Nano; Integration; Metal; Organic; Frameworks

Carbon dioxide levels have risen steadily with the combustion of fossil fuels and additional positive feedback effects due to natural CO2 sources. Recycling of CO2 driven by solar/renewable energy is an effective approach to address the problem. In a recent edition of Science (25th Sept 2009) entirely dedicated to this problem the opportunities and potential benefits arising form CO2 uptake from the open air (as opposed to capture during production) have been highlighted. The urgent need for capture and utilisation of CO2 is self-evident. Research in CO2 capture and in CO2 utilisation is currently based on a range of separate technologies and often ineffective e.g. for amine or alkaline sequestration. By combining ( nano-integrating ) capture and utilisation into a single continuous process the efficiency can be improved and at the same time the energy required to drive CO2 reduction is minimised. This project focuses on one-step CO2 capture and utilisation by linking catalysts directly with a novel CO2 absorber. Nano-scale-integration of CO2 uptake and utilisation processes will provide new highly efficient single-step processes to turn CO2 into useful products (polymers, carbohydrates, fuels). The main vision for this project is the idea of a catalyst nanostructure embedded into/immobilised onto a CO2 supplying membrane (Metal-Organic-Framework, MOF) substrate so that enhanced localised diffusion can deliver a high rate of CO2 into the active catalyst site.Metal Organic Frameworks (MOFs) have emerged as a front-runner for the uptake and storage of CO2 but have never been employed to support catalysts. Effective catalysts for the conversion of CO2 into useful chemical products have been discovered but usually require high concentration industrial CO2. In this project two areas of existing strength in the South-West, CO2 absorption and catalytic utilisation, are combined to provide new nano-structured functional catalyst membranes tailored to both capture and concentrate CO2 from the free atmosphere and convert it into useful products in a single continuous process. The developed technology based on functionalised and specifically tailored MOF-membranes will be entirely new. The catalytic processes will be driven by solar energy (photo- or bio-catalysis), renewable energy, or waste heat from carbon creating processes. Nanotechnology is integral to this project. Metal organic frameworks (MOFs) are promising materials for the specific absorption and storage of high concentrations of CO2. In a new approach the MOFs will be made into nanostructured membranes, which will concentrate CO2 from the atmosphere and feed it directly into a nanostructured catalyst layer. As the CO2 is reduced, fresh CO2 will be continuously drawn in with the catalyst located in the diffusion layer (with effective hemi-spherical diffusion of CO2 to the nano-catalyst). Three types of catalysis will be investigated for CO2 reduction: (i) direct gas phase reduction of CO2 to CO using a nanostructured catalyst and integrated MOF/catalyst materials for one step carbon capture and utilisation, (ii) CO2 will be electro-reduced on platinum or copper nanoparticles (or similar nano-structured catalysts) to form ethylene and higher hydrocarbons with nanostructured catalysts increasing the selectivity of process, (iii) bio-films of cyanobacteria will be used to fix CO2 from the MOF under illumination in a MFC setup. Nanostructuring of the conducting MOF surface with the biofilm attached is extremely important for good bacterial adhesion and function.Stages of effective modules (e.g. producing ethylene and producing CO) will be combined into reactors to deliver products of higher value (e.g. polymers, solvents, or fuels) in the second stage of the project. Parts and the overall process will be carefully assessed by life-cycle analysis and the desired end product will be a carbon negative process .

随着化石燃料的燃烧和天然CO2源产生的额外正反馈效应，二氧化碳水平稳步上升。太阳能/可再生能源驱动的CO2回收利用是解决这一问题的有效途径。在最近一期的《科学》（2009年9月25日）中，完全致力于这个问题，强调了从露天吸收二氧化碳（而不是在生产过程中捕获）所带来的机会和潜在利益。对二氧化碳的捕获和利用的迫切需要是不言而喻的。二氧化碳捕获和二氧化碳利用的研究目前基于一系列单独的技术，并且通常无效，例如胺或碱螯合。通过将（纳米集成）捕获和利用结合到一个连续的过程中，可以提高效率，同时将减少二氧化碳所需的能量降至最低。该项目的重点是通过将催化剂直接与新型CO2吸收剂连接来实现一步CO2捕获和利用。二氧化碳吸收和利用过程的纳米级集成将提供新的高效单步过程，将二氧化碳转化为有用的产品（聚合物，碳水化合物，燃料）。该项目的主要设想是将催化剂纳米结构嵌入/固定在CO2供应膜（金属有机框架，MOF）基底上，以便增强局部扩散可以将高速率的CO2输送到活性催化剂位点。金属有机框架（MOF）已成为吸收和储存CO2的领跑者，但从未用于支撑催化剂。已经发现了用于将CO2转化为有用的化学产品的有效催化剂，但通常需要高浓度的工业CO2。在该项目中，西南部现有的两个优势领域，CO2吸收和催化利用，结合起来，提供新的纳米结构功能催化剂膜，用于从自由大气中捕获和浓缩CO2，并在一个连续的过程中将其转化为有用的产品。基于功能化和专门定制的MOF膜开发的技术将是全新的。催化过程将由太阳能（光催化或生物催化）、可再生能源或碳生成过程的废热驱动。纳米技术是这个项目的组成部分。金属有机骨架（MOFs）是一种很有前途的高浓度CO2吸收和储存材料。在一种新的方法中，MOFs将被制成纳米结构的膜，它将从大气中浓缩CO2，并将其直接送入纳米结构的催化剂层。随着CO2被还原，新鲜CO2将被位于扩散层中的催化剂连续吸入（CO2有效地半球形扩散到纳米催化剂）。将研究三种类型的催化剂用于CO2还原：（i）使用纳米结构催化剂和集成的MOF/催化剂材料将CO2直接气相还原为CO，用于一步碳捕获和利用，（ii）CO2将在铂或铜纳米颗粒上电还原（或类似的纳米结构催化剂）形成乙烯和高级烃，其中纳米结构催化剂提高了工艺的选择性，（iii）蓝细菌的生物膜将用于在MFC装置中在照明下固定来自MOF的CO2。具有附着生物膜的导电MOF表面的纳米结构化对于良好的细菌粘附和功能极其重要。有效模块的阶段（例如生产乙烯和生产CO）将被组合成反应器，以在项目的第二阶段提供更高价值的产品（例如聚合物，溶剂或燃料）。将通过生命周期分析仔细评估部件和整个过程，所需的最终产品将是碳负过程。

项目成果

Nano-TiO2-flavin adenine dinucleotide film redox processes in contact to humidified gas | salt electrolyte

纳米TiO2-黄素腺嘌呤二核苷酸薄膜与加湿气体接触的氧化还原过程

• DOI: 10.1016/j.bioelechem.2012.01.010
• 发表时间: 2012
• 期刊: Bioelectrochemistry
• 影响因子: 5
• 作者: Halls J

Methanol Oxidation at Diamond-Supported Pt Nanoparticles: Effect of the Diamond Surface Termination

金刚石负载的 Pt 纳米粒子的甲醇氧化：金刚石表面终止的影响

• DOI: 10.1021/jp4039804
• 发表时间: 2013
• 期刊: The Journal of Physical Chemistry C
• 作者: Celorrio V

Electrochemical performance of Pd and Au-Pd core-shell nanoparticles on surface tailored carbon black as catalyst support

• DOI: 10.1016/j.ijhydene.2011.12.014
• 发表时间: 2012-04-01
• 期刊: INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
• 影响因子: 7.2
• 作者: Celorrio, V.;Montes de Oca, M. G.;Lazaro, M. J.
• 通讯作者: Lazaro, M. J.

Proton uptake vs. redox driven release from metal-organic-frameworks: Alizarin red S reactivity in UMCM-1

• DOI: 10.1016/j.jelechem.2012.11.016
• 发表时间: 2013-01-15
• 期刊: JOURNAL OF ELECTROANALYTICAL CHEMISTRY
• 影响因子: 4.5
• 作者: Halls, Jonathan E.;Ahn, Sunyhik D.;Marken, Frank
• 通讯作者: Marken, Frank

Redox Reactivity of Methylene Blue Bound in Pores of UMCM-1 Metal-Organic Frameworks

UMCM-1 金属有机框架孔中亚甲基蓝的氧化还原反应性

• DOI: 10.1080/15421406.2012.632738
• 发表时间: 2012
• 期刊: Molecular Crystals and Liquid Crystals
• 影响因子: 0.7
• 作者: Halls J