Computational QM/MM investigation of the adsorption of MTH active species in H-Y and H-ZSM-5‡

文献情報

出版日 2018-12-21

DOI 10.1039/C8CP06736H

インパクトファクター 3.676

著者

S. A. F. Nastase, A. J. Logsdail

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要旨

The transformation of methanol-to-hydrocarbons (MTH) has significant potential as a route to synthesise low-cost fuels; however, the initial stages of the zeolite catalysed MTH process are not well understood. Here, we use hybrid quantum- and molecular-mechanical (QM/MM) embedded-cluster simulations to develop our understanding of the interaction between methanol and the zeolite catalysts H-ZSM-5, and for comparison, the larger pore H-Y. Energies and structures, calculated using hybrid-level density functional theory (hybrid-DFT) and higher-level correlated methods, are compared with previous experimental and computational results. We show that hydrogen-bonds between methanol adsorbates, formed through polarizable O–H bonds, substantially influence the adsorption energetics, structural parameters and vibrational frequencies. Our observations are extended by considering polar solvent molecules in the environment, with the presence of both water or methanol around the adsorption site leading to barrier-less transfer of the zeolite proton to an adsorbed methanol, which will significantly influence the reactivity of the adsorbed methanol.

掲載誌

Physical Chemistry Chemical Physics

CiteScore: 5.5

自己引用率: 10.3%

年間論文数: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.