Defect-engineered metal-organic frameworks for carbon dioxide capture

用于二氧化碳捕获的缺陷工程金属有机框架

• 批准号: EP/R01910X/1
• 负责人: Marco Taddei
• 金额: $ 12.37万
• 依托单位: Swansea University
• 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%2FR01910X%2F1
• 关键词: Defect; engineered; metal; organic; frameworks

Since the Industrial Revolution, mankind has started to heavily interfere with the natural carbon cycle by extracting and burning increasingly larger amounts of fossil fuels, which has led to release huge amounts of CO2 in the atmosphere at an unprecedented rate, causing climate change. In order to mitigate the effects of climate change, the recently established Paris Agreement sets the goal of limiting the rise in the average global temperature to 2 degrees by 2100. This will require keeping cumulative CO2 emissions from all anthropogenic sources since year 1860 to less than 840 gigatons of carbon. If global carbon emissions continue to grow as they have in the last decade, the 2 degrees carbon budget will be spent by year 2035. This dictates to look for alternative energy sources and sustainable processes to enable the transition to a low-carbon economy.CO2 capture, storage and utilisation (CCSU) is regarded as one of the key technologies to reduce CO2 emissions while fossil fuels are progressively phased out. Adoption of this technology on a large scale depends on its efficiency and economic viability, demanding the constant development of new materials able to combine excellent performances with long-term stability and affordability. The ideal sorbent for CO2 capture (CC) should have high mass uptake capacity, be selective towards CO2 over other gases, be able to be regenerated with a low energy penalty and be stable over various working cycles. CC from large point sources, such as coal- or gas-fired power plants and industrial facilities, is the most attractive option. These sources are responsible for about half of the global emissions and they generate concentrated CO2 streams that are easier to treat, if compared with direct air CO2 capture.This project aims at developing new solid sorbents for CC by exploiting defects in zirconium-based metal-organic frameworks (Zr-MOFs) to functionalise them with a wide range of amino groups. Zr-MOFs are a class of crystalline and highly porous materials constructed from the connection of hexanuclear zirconium oxide-hydroxide clusters and carboxylate linkers. They are attractive for their remarkable stability, especially in the presence of water, which makes them suitable for practical applications. The CO2 adsorption capacity of bare Zr-MOFs is moderate, if compared to that of other sorbents. Functionalisation of Zr-MOFs using organic linkers with pending amino groups or through grafting of ethanolamine to the metal clusters has been demonstrated to increase their affinity for CO2. However, these methods are rather limited in scope. Defects in Zr-MOFs are reactive sites and can be exploited to introduce functional groups that cannot be otherwise inserted in the porous structure. Functionalisation of defective Zr-MOFs with amino groups of different nature (aliphatic, aromatic, heterocyclic) will allow to investigate and evaluate the influence of a large set of parameters on their CC performances. The resulting defect-engineered MOFs will be a library of novel, stable and versatile solid sorbents with tuneable physical-chemical properties for application in CC.Tata Steel will be part of this project as an industrial partner. This will provide an excellent case study for the proposed research, because the steelworks in Port Talbot are the largest industrial CO2 emitter in the UK and Tata Steel is committed to address this issue. The materials developed during this project will be tested in conditions relevant to CC from blast furnace gas. This gas is mainly composed of N2 (45-50%), CO (20-25%), CO2 (20-25%) and H2 (0-5%) and is normally flared, due to its low calorific value. Removal of CO2 would allow to recycle the CO-rich stream in the blast furnace for reduction of iron ore and to convert the captured CO2 into useful chemicals.

自工业革命以来，人类通过提取和燃烧越来越多的化石燃料，开始严重干扰自然碳循环，这导致以前所未有的速度向大气中释放大量二氧化碳，导致气候变化。为了减轻气候变化的影响，最近制定的《巴黎协定》设定了到2100年将全球平均气温上升幅度限制在2度以内的目标。这将需要将自1860年以来所有人为来源的二氧化碳累积排放量保持在840千兆吨以下。如果全球碳排放继续像过去十年那样增长，到2035年，2度碳预算将被消耗殆尽。这就要求寻找替代能源和可持续的工艺，以实现向低碳经济的过渡。二氧化碳捕获、储存和利用（CCSU）被认为是在化石燃料逐步淘汰的同时减少二氧化碳排放的关键技术之一。大规模采用该技术取决于其效率和经济可行性，需要不断开发新材料，这些新材料能够将联合收割机的优异性能与长期稳定性和可承受性相结合。用于CO2捕集（CC）的理想吸附剂应具有高质量吸收能力，相对于其他气体对CO2具有选择性，能够以低能量损失再生，并且在各种工作循环中稳定。来自大型点源的CC，如燃煤或燃气发电厂和工业设施，是最有吸引力的选择。这些来源约占全球排放量的一半，它们产生的浓缩CO2流与直接空气CO2捕集相比更容易处理。该项目旨在通过利用锆基金属有机框架（Zr-MOFs）中的缺陷，将其与广泛的氨基基团官能化，开发用于CC的新型固体吸附剂。Zr-MOFs是一类由六核氧化锆-氢氧化物簇和羧酸酯连接体连接而成的结晶和高度多孔的材料。它们因其显著的稳定性而具有吸引力，特别是在水的存在下，这使得它们适合于实际应用。与其他吸附剂相比，裸Zr-MOFs的CO2吸附能力适中。已经证明使用具有侧挂氨基的有机连接体或通过将乙醇胺接枝到金属簇上来官能化Zr-MOF可以增加它们对CO2的亲和力。然而，这些方法在范围上相当有限。Zr-M0 F中的缺陷是反应性位点，并且可以用于引入不能以其他方式插入多孔结构中的官能团。具有不同性质的氨基（脂肪族、芳香族、杂环）的缺陷Zr-MOF的官能化将允许研究和评估大量参数对其CC性能的影响。由此产生的缺陷工程MOF将是一个新的，稳定的和多功能的固体吸附剂库，具有可调的物理化学性能，适用于连铸。塔塔钢铁公司将作为工业合作伙伴参与该项目。这将为拟议的研究提供一个很好的案例研究，因为塔尔博特港的钢铁厂是英国最大的工业二氧化碳排放国，而塔塔钢铁公司致力于解决这一问题。该项目期间开发的材料将在与高炉煤气CC相关的条件下进行测试。该气体主要由N2（45-50%）、CO（20-25%）、CO2（20-25%）和H2（0-5%）组成，并且由于其低热值而通常被燃烧。去除CO2将允许在高炉中再循环富含CO的流以还原铁矿石，并将捕获的CO2转化为有用的化学品。

项目成果

"Shake 'n Bake" Route to Functionalized Zr-UiO-66 Metal-Organic Frameworks.

• DOI: 10.1021/acs.inorgchem.1c01839
• 发表时间: 2021-09-20
• 期刊: Inorganic chemistry
• 影响因子: 4.6
• 作者: D'Amato R;Bondi R;Moghdad I;Marmottini F;McPherson MJ;Naïli H;Taddei M;Costantino F
• 通讯作者: Costantino F

An Optimised Compaction Process for Zr-Fumarate (MOF-801)

• DOI: 10.3390/inorganics7090110
• 发表时间: 2019
• 期刊: Inorganics
• 影响因子: 2.9
• 作者: M. Taddei;M. McPherson;Abel Gougsa;J. Lam;J. Sewell;E. Andreoli

Band Gap Modulation in Zirconium-Based Metal-Organic Frameworks by Defect Engineering

• DOI: 10.1039/c9ta05216j
• 发表时间: 2019-05
• 期刊: Journal of Materials Chemistry A
• 影响因子: 11.9
• 作者: M. Taddei;Giulia E. M. Schukraft;Michael E. A. Warwick;D. Tiana;M. McPherson;Daniel R. Jones;C. Petit-C.-Pet