(349m) Tuning the Interaction of Molecules with Lewis Acid Zeolite By Hot Carriers

Manipulating the interaction between Lewis acid catalysts and reactants/intermediates to tune catalyst activity has received considerable interests in the field of biomass conversion. Changing the metal dopant in the Lewis acid zeolites is normally applied; however, only few of elements can be introduced into zeolite to form a strong Lewis acid. In this study, we bring a new approach to tune the interaction between zeolite and molecules by integrating a plasmonic catalyst with zeolite. This hybrid catalyst can take advantage of local surface plasmon resonance to generate the highly energetic charge carries into the system and combine them with the exceptional properties of zeolites. Here, by performing the DFT calculations, we investigated the effect of the hot carriers on the interaction between zeolite and molecules. We find that while there is no remarkable change in the heat adsorption of ammonia on Zr-BEA or Si-BEA under the effect of the hot electron, the heat adsorption on Sn-BEA and Ti-BEA can be significantly reduced by 60% or 20%, respectively, due to the population of the hot electrons at the metal center. The mid-gap states and the strong electronegativity make this process more preferable for Sn-BEA. In contrast, the hot holes strengthen the interaction between zeolite and molecules, by at least 10% for ammonia adsorption. Interestingly, the hot holes can increase 3 times of the heat adsorption of ammonia on Si-BEA, from a weak interaction to an interaction as moderate as ammonia adsorbed on Ti-BEA. Our study thus provides the fundamental insights to unlock the potential of integrating plasmonic catalysts with zeolite and brings additional degrees of control to tune the interaction between catalysts and reactants, thereby enhancing the catalyst activity in heterogeneous catalysis.