Pinheiro Araújo Thaylan, Mondelli Cecilia, Agrachev Mikhail, Zou Tangsheng, Willi Patrik O, Engel Konstantin M, Grass Robert N, Stark Wendelin J, Safonova Olga V, Jeschke Gunnar, Mitchell Sharon, Pérez-Ramírez Javier
Institute of Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH Zurich, Vladimir-Prelog-Weg 1, 8093, Zurich, Switzerland.
Laboratory of Physical Chemistry, Department of Chemistry and Applied Biosciences, ETH Zurich, Vladimir-Prelog-Weg 2, 8093, Zurich, Switzerland.
Nat Commun. 2022 Sep 24;13(1):5610. doi: 10.1038/s41467-022-33391-w.
Palladium promotion and deposition on monoclinic zirconia are effective strategies to boost the performance of bulk InO in CO-to-methanol and could unlock superior reactivity if well integrated into a single catalytic system. However, harnessing synergic effects of the individual components is crucial and very challenging as it requires precise control over their assembly. Herein, we present ternary Pd-InO-ZrO catalysts prepared by flame spray pyrolysis (FSP) with remarkable methanol productivity and improved metal utilization, surpassing their binary counterparts. Unlike established impregnation and co-precipitation methods, FSP produces materials combining low-nuclearity palladium species associated with InO monolayers highly dispersed on the ZrO carrier, whose surface partially transforms from a tetragonal into a monoclinic-like structure upon reaction. A pioneering protocol developed to quantify oxygen vacancies using in situ electron paramagnetic resonance spectroscopy reveals their enhanced generation because of this unique catalyst architecture, thereby rationalizing its high and sustained methanol productivity.
钯促进和沉积在单斜氧化锆上是提高块状氧化铟在一氧化碳制甲醇反应中性能的有效策略，如果能很好地整合到单一催化体系中，可能会释放出卓越的反应活性。然而，利用各组分的协同效应至关重要且极具挑战性，因为这需要对它们的组装进行精确控制。在此，我们展示了通过火焰喷雾热解（FSP）制备的三元钯-氧化铟-氧化锆催化剂，其甲醇生产率显著且金属利用率提高，超过了二元催化剂。与成熟的浸渍法和共沉淀法不同，FSP制备的材料结合了与高度分散在氧化锆载体上的氧化铟单层相关的低核钯物种，其表面在反应时部分从四方结构转变为类似单斜的结构。一种利用原位电子顺磁共振光谱定量氧空位的开创性方法表明，由于这种独特的催化剂结构，氧空位的生成增加，从而解释了其高且持续的甲醇生产率。
