Enhanced Dehydrogenative H₂ Release from <i>N</i>-Containing Amphicyclic LOHC Boosted by Pd-Supported Nanosheet MFI Zeolites Having Strong Acidity and Large Mesoporosity

The amount and rate of H2 discharge from 2-[(n-methylcyclohexyl)methyl]piperidine (H12-MBP), an amphicyclic liquid organic hydrogen carrier (LOHC) having two cycle moieties (cyclohexane and piperidine) with different reactivities, are determined by dehydrogenation of a cyclohexane ring with less reactivity. To realize high H2 yields with rapid kinetics, the cyclohexane ring in the partially dehydrogenated 2-[n-methylcyclohexyl]methyl)pyridine (H6-MBP) that is generated as the intermediate species should be fully dehydrogenated to 2-(n-methylbenzyl)pyridine (H0-MBP). This is approached using Pd-supported nanosheet zeolites having mesoporous structures bearing high concentrations of strongly acidic sites on external surfaces, which can not only enhance the diffusion of bulky H12-MBP but also strongly bind the basic piperidine ring in H12-MBP and H6-MBP. The H2 yields and rate constants are correlated with the acidity, mesoporosity, and adsorption behaviors of the LOHCs. As these factors are strengthened, H2 yield and rate constants increased dramatically within the ranges of 16.0–64.7% and 0.0001–0.0013 min–1, respectively. The results prove that mesoporous zeolites can be used for constructing supported Pd catalysts achieving high H2 yields with rapid kinetics from N-containing amphicyclic LOHCs.