Mechanisms of carbon monoxide hydrogenation yielding formaldehyde catalyzed by the representative strong mineral acid, H2SO4, and Lewis–Brønsted superacid, HF/AlF3

Literature Information

Publication Date 2017-06-26
DOI 10.1039/C7CP03362A
Impact Factor 3.676
Authors

Olimpia Rybacka, Marcin Czapla, Piotr Skurski


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Abstract

The mechanism of the CO + H2 → H2CO reaction catalyzed by acidic systems was investigated theoretically using the ab initio MP2 and CCSD(T) methods and the aug-cc-pVDZ basis set (the effects of the surrounding solvent molecules were approximated by employing the polarized continuum solvation model). Two representative acids were chosen to verify the usefulness of such catalysts in this process: sulfuric acid (as a strong mineral acid) and HAlF4 (as a superacid). Detailed mechanisms in both gas and liquid phases proceeding either along a concerted path or according to a stepwise route were investigated and discussed. The most important findings include the observation that both acids seem to catalyze the carbon monoxide hydrogenation in a qualitatively similar way but only the HAlF4 superacid is predicted to effectively reduce the activation barriers to render the whole process plausible.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 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.

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