Kots Pavel A, Xie Tianjun, Vance Brandon C, Quinn Caitlin M, de Mello Matheus Dorneles, Boscoboinik J Anibal, Wang Cong, Kumar Pawan, Stach Eric A, Marinkovic Nebojsa S, Ma Lu, Ehrlich Steven N, Vlachos Dionisios G
Center for Plastics Innovation, University of Delaware, 221 Academy St., Newark, DE, 19716, USA.
Department of Chemical and Biomolecular Engineering, University of Delaware, 150 Academy St., Newark, DE, 19716, USA.
Nat Commun. 2022 Sep 3;13(1):5186. doi: 10.1038/s41467-022-32934-5.
Ruthenium (Ru) is the one of the most promising catalysts for polyolefin hydrogenolysis. Its performance varies widely with the support, but the reasons remain unknown. Here, we introduce a simple synthetic strategy (using ammonia as a modulator) to tune metal-support interactions and apply it to Ru deposited on titania (TiO). We demonstrate that combining deuterium nuclear magnetic resonance spectroscopy with temperature variation and density functional theory can reveal the complex nature, binding strength, and H amount. H activation occurs heterolytically, leading to a hydride on Ru, an H on the nearest oxygen, and a partially positively charged Ru. This leads to partial reduction of TiO and high coverages of H for spillover, showcasing a threefold increase in hydrogenolysis rates. This result points to the key role of the surface hydrogen coverage in improving hydrogenolysis catalyst performance.
钌（Ru）是用于聚烯烃氢解最具前景的催化剂之一。其性能随载体的不同而有很大差异，但其原因仍不明晰。在此，我们引入一种简单的合成策略（以氨作为调节剂）来调控金属 - 载体相互作用，并将其应用于负载在二氧化钛（TiO₂）上的钌。我们证明，将变温氘核磁共振光谱与密度泛函理论相结合，能够揭示其复杂本质、结合强度以及氢含量。氢的活化以异裂方式发生，导致钌上形成一个氢化物、最近的氧原子上有一个氢，以及带部分正电荷的钌。这导致TiO₂的部分还原以及用于溢流的高氢覆盖率，使氢解速率提高了三倍。这一结果表明表面氢覆盖率在提高氢解催化剂性能方面的关键作用。
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