Zhang Guangcheng, Liu Mengran, Fan Guoli, Zheng Lirong, Li Feng
State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China.
Beijing Institute of Aerospace Testing Technology, Beijing Key Laboratory of Research and Application for Aerospace Green Propellants, Beijing 100074, China.
ACS Appl Mater Interfaces. 2022 Jan 19;14(2):2768-2781. doi: 10.1021/acsami.1c20056. Epub 2022 Jan 7.
In a complex heterogeneous metal-catalyzed reaction process, unique cooperative effects between metal sites and surface-interface active sites, as well as favorable synergy between surface-interface active sites, can play crucial roles in improving their catalytic performances. In this work, a ZnO-modified Cu-based catalyst over defect-rich PrO nanosheets for high-efficiency CO hydrogenation to produce methanol was successfully constructed. It was demonstrated that an as-fabricated nanosheet-like Cu-based catalyst presented several structural advantages including the formation of highly dispersive Cu sites and the coexistence of abundant defective Pr-V-Pr structures (V: oxygen vacancy) and interfacial Cu-O-Pr sites. Combining structural characterization and catalytic reaction results with density functional theory calculations, it was clearly unveiled that the synergy between surface defective structures and Cu-PrO interfaces over the catalyst remarkably promoted the adsorption of CO and CO intermediate, thus boosting the CO hydrogenation simultaneously both the formate intermediate pathway and the intense reverse water-gas shift reaction-derived CO hydrogenation pathway, along with a high space-time yield of methanol of 0.395 g·g·h under mild reaction conditions (260 °C and 3.0 MPa). The study provides a new strategy to construct high-performance Cu-based catalysts for high-efficiency CO hydrogenation to produce methanol and a deep understanding of the promotional roles of synergy between surface-interface active sites in the CO hydrogenation.
在复杂的多相金属催化反应过程中，金属位点与表面-界面活性位点之间独特的协同效应，以及表面-界面活性位点之间良好的协同作用，在提高其催化性能方面可发挥关键作用。在这项工作中，成功构建了一种负载在富含缺陷的PrO纳米片上的ZnO修饰的铜基催化剂，用于高效CO加氢制甲醇。结果表明，所制备的纳米片状铜基催化剂具有几个结构优势，包括形成高度分散的Cu位点以及大量缺陷Pr-V-Pr结构（V：氧空位）和界面Cu-O-Pr位点的共存。结合结构表征、催化反应结果与密度泛函理论计算，清楚地揭示了催化剂表面缺陷结构与Cu-PrO界面之间的协同作用显著促进了CO和CO中间体的吸附，从而在温和反应条件（260℃和3.0MPa）下同时促进了CO加氢的甲酸中间体途径和强烈的逆水煤气变换反应衍生的CO加氢途径，甲醇的时空产率高达0.395 g·g⁻¹·h⁻¹。该研究为构建用于高效CO加氢制甲醇的高性能铜基催化剂提供了一种新策略，并深入理解了表面-界面活性位点之间的协同作用在CO加氢中的促进作用。
