Department of Chemistry, Duke University, Durham, North Carolina 27708, United States.
Department of Chemical and Biomolecular Engineering, North Carolina State University, Raleigh, North Carolina 27695, United States.
ACS Appl Mater Interfaces. 2023 Jul 5;15(26):31384-31392. doi: 10.1021/acsami.3c02829. Epub 2023 Jun 21.
High entropy oxide (HEO) has shown to be a new type of catalyst support with tunable composition-function properties for many chemical reactions. However, the preparation of a metal nanoparticle catalyst supported on a metal oxide support is time-consuming and takes multiple complicated steps. Herein, we used a one-step glycine-nitrate-based combustion method to synthesize highly dispersed rhodium nanoparticles on a high surface area HEO. This catalyst showed high selectivity to produce CO in CO hydrogenation with 80% higher activity compared to rhodium nanoparticle-based catalysts. We also studied the effect of different metal elements in HEO and demonstrated that high CO selectivity was achieved if one of the metals in the metal oxide support favored CO production. We identified that copper and zinc were responsible for the observed high CO selectivity due to their low *CO binding strength. During hydrogenation, a strong metal-support interaction was created through charge transfer and formed an encapsulated structure between rhodium nanoparticles and the HEO support to lower the *CO binding strength, which enabled high CO selectivity in the reaction. By combining different metal oxides into HEO as a catalyst support, high activity and high selectivity can be achieved at the same time in the CO hydrogenation reaction.
高熵氧化物 (HEO) 已被证明是一种新型的催化剂载体,具有可调组成-功能特性,可用于许多化学反应。然而,在金属氧化物载体上负载金属纳米粒子催化剂的制备过程既耗时又复杂,需要经过多个步骤。在此,我们使用一步甘氨酸-硝酸盐燃烧法,在高比表面积的 HEO 上合成了高度分散的铑纳米粒子。该催化剂在 CO 加氢反应中表现出很高的 CO 选择性,活性比基于铑纳米粒子的催化剂高 80%。我们还研究了 HEO 中不同金属元素的影响,结果表明,如果金属氧化物载体中的一种金属有利于 CO 的生成,则可以获得很高的 CO 选择性。我们发现铜和锌由于其CO 结合强度低而导致观察到的高 CO 选择性。在加氢过程中,通过电荷转移在 Rh 纳米粒子和 HEO 载体之间形成强的金属-载体相互作用,从而降低CO 的结合强度,这使得反应中具有很高的 CO 选择性。通过将不同的金属氧化物结合到 HEO 中作为催化剂载体,可以在 CO 加氢反应中同时实现高活性和高选择性。