In-depth Understanding of Catalytic Activation of Carbon Dioxide for Value-added Products

在可预见的未来，化石燃料的使用和由此产生的二氧化碳（CO2）的排放是不可避免的，为了避免大气中CO2浓度的增加所带来的气候变化，除了从战略角度来看是被动的CO2捕集与封存（CCS）技术之外，将排放的CO2转化为有用的和增值的化学品或产品（CO2捕获和利用或简称CCU）具有内在的重要性，并且用于CO2转化的催化剂开发在这些技术进步中起着至关重要的作用。在成功研发CO2重整甲烷催化剂的基础上，本研究计划侧重于了解CO2催化转化中C-O键断裂和C-H键形成的机理，旨在扩展催化剂结构的基础知识，这对于开发新型高效CO2转化催化剂以实现所需的CO2利用率是必要的。 该方法包括使用原子层沉积（ALD）的方法来制备具有已知的和均匀的结构的模型催化剂，并使用先进的仪器表征，如在原位和/或操作光谱表征在加拿大光源（CLS）的催化机理研究。密度泛函理论（DFT）计算也将用于帮助确认理解。本项目的近期目标是建立催化剂结构与催化剂性能之间的关系，即CH 4反应体系中CO2重整中C-O键断裂和CO2加氢制甲醇中C-H键形成。长期目标是了解复杂的自然CO2转化过程（如光合作用）的催化剂结构，并模拟CO2利用的自然催化过程。在拟议的研究计划中，高素质人才（HQP）培训计划包括使用ALD技术制备催化剂和使用CLS同步加速器技术进行催化机理研究以及DFT计算领域的博士和硕士学生。

In the foreseeable future, the use of fossil fuels for energy is inevitable and so is the emission of carbon dioxide (CO2) from it. To avoid the predicted climate change from the increase of CO2 concentration in the atmosphere, in addition to the technologies of CO2 capture and storage (CCS), which are passive from a strategic point of view, conversion of the emitted CO2 into useful and value-added chemicals or products (CO2 capture and utilization or CCU in short) is inherently important, and catalyst development for CO2 conversion plays a vital role in these technology advances. Building on the successful research and development of a catalyst for CO2 reforming of methane (CH4), this proposed research program focuses on the understanding of the mechanisms of C-O bond breakage and C-H bond formation in catalytic conversion of CO2, aiming to extend fundamental knowledge of catalyst structures that is necessary to the development of new and powerful catalysts for CO2 conversion to achieve desired CO2 utilization. The methodology includes using the atomic layer deposition (ALD) method to prepare the model catalysts with known and uniform structures and using advanced instrumental characterization such as in situ and/or operando spectroscopic characterizations at the Canadian Light Source (CLS) for the catalytic mechanism studies. Density functional theory (DFT) calculations will also be used to help confirm the understanding. The short-term objectives of this program are to establish the relationship between the catalyst structures and catalytic performance on C-O bond breakage in CO2 reforming of CH4 reaction system and on C-H bond formation in CO2 hydrogenation for methanol. The long-term goal is to understand the catalyst structures of the complex, natural CO2 conversion processes such as photosynthesis and mimic the natural catalytic processes for CO2 utilization. The highly qualified personnel (HQP) training plan in the proposed research program includes PhD and MSc students in the fields of catalyst preparation using ALD technology and catalytic mechanism studies with CLS synchrotron technologies as well as the DFT calculations.