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，主要是由于大量的二氧化碳形式的温室气体排放到大气中。在这方面，将二氧化碳催化升级为燃料和高价值化学品，例如乙醇，似乎是解决空气中二氧化碳超载的最有价值的解决办法之一。催化二氧化碳加氢制乙醇（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。在众多已开发的催化剂中，金、钯基纳米材料是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 < 400 h-1）和相对苛刻的反应条件（T大于或等于200℃，p> 3 MPa）阻碍了这些作品的工业化。在此，本研究的重点是通过在富氧的My/TiO2-x（即M=In3+, Fe3+）上逐原子构建原子精确的Au/Pd位点，以最大限度地提高原子利用效率和金属/邻近氧空位的位数，从而进一步提高温和条件下的乙醇产率。此外，还将结合多种operando光谱技术（如operando x射线吸收光谱和稳态同位素瞬态动力学分析），鉴定C-C耦合的中间体和机理，从而建立清晰的结构-性能关系，为未来CO2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宏伟目标，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.