TY - JOUR
T1 - Electronic modulation of metal-support interactions improves polypropylene hydrogenolysis over ruthenium catalysts
AU - Kots, Pavel A.
AU - Xie, Tianjun
AU - Vance, Brandon C.
AU - Quinn, Caitlin M.
AU - de Mello, Matheus Dorneles
AU - Boscoboinik, J. Anibal
AU - Wang, Cong
AU - Kumar, Pawan
AU - Stach, Eric A.
AU - Marinkovic, Nebojsa S.
AU - Ma, Lu
AU - Ehrlich, Steven N.
AU - Vlachos, Dionisios G.
N1 - Publisher Copyright:
© 2022, The Author(s).
PY - 2022/12
Y1 - 2022/12
N2 - 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 (TiO2). 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. H2 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 TiO2 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.
AB - 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 (TiO2). 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. H2 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 TiO2 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.
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U2 - 10.1038/s41467-022-32934-5
DO - 10.1038/s41467-022-32934-5
M3 - Article
C2 - 36057603
AN - SCOPUS:85137158238
SN - 2041-1723
VL - 13
JO - Nature communications
JF - Nature communications
IS - 1
M1 - 5186
ER -