MOFs and ZIFs as dual functional adsorbents/catalysts (DFA/Cs) for sustainable chemical processes, environmental protection, and clean energy

二氧化碳（CO2）的排放导致全球变暖和气候变化，影响人类生活和环境。就目前的碳捕获技术而言，即使有政府的激励措施，工业和商业利益也微乎其微。为了降低大气中二氧化碳的浓度，已经实施了各种策略，如分离、储存和利用二氧化碳。碳循环的每个阶段（即捕获、再生和转化）都有自己的材料要求。最近对金属有机框架（MOFs）的研究表明，这些材料在应对二氧化碳挑战方面具有潜力和有效性。越来越多的人认为二氧化碳是一种资源和商业机会，而不是一种有处理成本的废物。越来越多的低成本和相对纯净的二氧化碳可以从不同的工业中获得，用于固碳和储存。因此，二氧化碳将成为转化为燃料和化学品的成本几乎为零（甚至为负）的原料。在此，我建议开发基于金属有机骨架（MOF）和沸石咪唑酸骨架（ZIF）的新型双功能吸附剂/催化剂（DFA/Cs），并将其用于将CO2分离/转化为增值化学品，包括但不限于聚碳酸酯和聚氨基甲酸酯聚合物。这些生物聚合物将获得碳信用额度。这两种聚合物主要以高毒性光气（COCl2）为关键原料生产。用二氧化碳代替光气将带来更安全、更环保的技术。该提案的主要目标是建立一个坚实的基础研究计划，以合理设计基于mof / zif的新型催化剂家族，为二氧化碳转化为聚碳酸酯聚合物等增值化学品提供高催化性能的可能性。具体成果包括：(A)合理设计了一类基于MOF/ zif的双功能吸附剂/催化剂（DFA/Cs）。(B) MOF/ZIF催化CO2转化为聚碳酸酯聚合物的性能。(C)利用管式膜反应器建立MOF/ZIF-DFA/Cs在CO2分离转化为聚碳酸酯聚合物中的基本结构/吸附/催化关系。

Emissions of carbon dioxide (CO2) lead to global warming and climate changes that affect human life and the environment. With the current carbon-capture technologies, there is very little industrial and commercial interest, even in the presence of government incentives. To mitigate the concentration of CO2 in the atmosphere, various strategies have been implemented such as separation, storage, and utilization of CO2. Each stage in the carbon cycle (i.e. capturing, regeneration and conversion) has its own materials requirements. Recent work on metal-organic frameworks (MOFs) demonstrated the potential and effectiveness of these materials in addressing the CO2 challenge. There is an increasing trend to consider carbon dioxide as a resource and a business opportunity rather than a waste product with a cost for disposal. Increasing amounts of low-cost and relatively pure CO2 are available from different industries for carbon sequestration and storage. Hence, CO2 will be a feed-stock of nearly zero (or even negative) cost for conversion to fuels and chemicals. Herein, I propose to develop novel dual functional adsorbents/catalysts (DFA/Cs) based on metal organic framework (MOF) and zeolitic imidazolate framework (ZIF), and use them in the separation/conversion of CO2 into value-added chemicals including but not limited to polycarbonate and poly carbamate polymers. These bio-polymers will be entitled to carbon credits. These two polymers are mainly manufactured using highly toxic phosgene (COCl2), as a key raw material. Replacing phosgene with CO2 will lead to a safer and more eco-friendly technology. The main objective of this proposal is to establish a solid fundamental research program leading to the rational design of a novel family of catalysts, based on MOFs/ZIFs, which offer the possibility of demonstrating high catalytic performance for carbon dioxide conversion to value-added chemicals such as polycarbonate polymers. The specific deliverables of this proposal include: (A) Rational design of a family of MOF/ZIF-based dual functional adsorbent/catalyst (DFA/Cs). (B) Catalytic performance of MOF/ZIF in the conversion of CO2 to polycarbonate polymers. (C) Establish fundamental structure/adsorption/catalytic relationships of MOF/ZIF-DFA/Cs  in separation and conversion of CO2 to polycarbonate polymers using a tubular membrane reactor.