Rational Modulation of Pt d Electrons to Significantly Enhance the Catalytic Dehydrogenation Performance of Liquid Organic Hydrogen Carriers

Understanding the intrinsic features of dehydrogenation reactions of liquid organic hydrogen carriers (LOHCs) is a formidable challenge due to the combined impact of electronic and geometric effects. Herein, we constructed a series of Pt/MO x catalysts (CeO 2 , MgO, ZrO 2 , TiO 2 , Al 2 O 3 , or SiO 2 ) with similar sizes of Pt (∼1.7 nm) to investigate the effects of Pt electron structures (tuned by electronic metal‒support interactions) on the catalytic dehydrogenation of LOHCs. The results revealed a volcano-shaped correlation between Pt d electrons on different supports and the turnover frequency of catalytic dehydrogenation. Importantly, the Pt/MgO catalyst exhibited the highest dehydrogenation activity. With decreasing d electron content, Pt/MgO increases the bonding orbital dominance of Pt‒C bonds and leads to stable adsorption of H6-monobenzyltoluene (MBT), which facilitates subsequent C‒H bond scission. This study offers insight for the strategic development of high-efficiency dehydrogenation catalysts via d electron density modulation of Pt sites.