AtomCat4Fuel: Atomically construction of AuPd catalyst for efficient CO2 hydrogenation to ethanol

气候变化可以说是我们的星球在21世纪面临的最大挑战之一，主要是由于以二氧化碳形式向大气排放的大量温室气体。在这方面，将二氧化碳催化升级为燃料和高价值化学品，如乙醇，似乎是解决空气中二氧化碳超载的最有价值的解决方案之一。二氧化碳催化加氢制乙醇(CTE)不仅有助于减缓全球变暖，而且有助于缓解全球粮食短缺。在各种已开发的催化剂中，Au和Pd基纳米材料是CO2加氢制乙醇最有效的催化剂之一，值得进一步研究。然而，有限的乙醇活性(TOF&lt；400h-1)和相对苛刻的反应条件(T大于或等于200oC，P&gt；3 Mpa)阻碍了这些工作的工业化。在这里，这一建议集中于开发策略，通过逐个原子地在富氧空位的My/TiO2x(即M=In3+，Fe3+)上构建原子精确的Au/Pd位来最大化原子利用效率和金属/邻近氧空位的位置数量，以在温和的条件下进一步提高乙醇的产量。此外，各种操纵面光谱技术(例如，操纵面X射线吸收光谱和稳态同位素瞬时动力学分析)将被整合，以确定碳-碳耦合的中间体和机理，从而建立明确的结构-性能关系，并为未来二氧化碳催化剂的设计提供合理的指导，所有这些都将有助于实现欧盟委员会的雄心勃勃的目标，即到2050年将所有来源的二氧化碳排放量减少80%-95%。

Climate change is arguably one of the most top challenges our planet facing during the 21st century, mainly due to huge amounts of greenhouse gas emissions in CO2 form to the atmosphere. In this regard, the catalytic upgradation of CO2 into fuels and high-value chemicals, e.g., ethanol, appears to be one of the most valuable solutions to address the overloaded CO2 in air. Catalytic CO2 hydrogenation to ethanol (CTE) not only contributes to slow down the global warming but also contributes to alleviate the global food shortage. Among various developed catalysts, Au- and Pd-based nano-materials emerge as one of the most effective catalysts for CO2 hydrogenation to ethanol, which deserves more research efforts. While the limited ethanol activity (TOF < 400 h-1) and relatively harsh reaction conditions (T greater than or equal to 200 oC, P > 3 MPa) preclude these works from industrialization. Herein, this proposal focuses on developing the strategies to maximize the atom utilization efficiency and the sites number of metal/adjacent oxygen vacancy, through atom-by-atom constructing atomically precise Au/Pd sites on oxygen-vacancy-rich My/TiO2-x (i.e., M=In3+, Fe3+), to further improve ethanol productivity under mild conditions. Furthermore, various operando spectroscopy techniques (e.g., operando X-ray absorption spectroscopy and steady-state isotopic transient kinetic analysis) will be integrated to identify the intermediates and mechanism of C-C coupling, thus establishing a clear structure-performance relationship and providing a rational guidance for the design of future CO2 catalysts, all of which will contribute to the ambitious goal of European Commission for reducing CO2 emissions from all sources by 80%-95% by 2050.