A computational study of the competing reaction mechanisms of the photo-catalytic reduction of CO2 on anatase(101)

文献情報

出版日 2016-08-12

DOI 10.1039/C6CP02642G

インパクトファクター 3.676

著者

Chung Man Ip, Alessandro Troisi

原文を見る

要旨

We perform a computational study of three different reaction mechanisms for the photo-catalytic reduction of CO2 on the TiO2 anatase(101) surface known as (i) the carbene, (ii) the formaldehyde and (iii) the glyoxal pathways. We define a set of approximations that allows testing a number of mechanistic hypotheses and design experiments to validate them. We find that the energetically most favourable reaction mechanism among those proposed in the literature is the formaldehyde path, and the rate-limiting step is likely to be the formation of CH3 radicals from dissociation of CH3OH. We show that an intermediate that supports this mechanism is OCH2OH. We also find that formaldehyde would be an energetically favorable intermediate forming from CO and HCO, intermediates that are proposed in the early stage of the carbene and glyoxal pathways respectively. Some possible variants of mechanisms and methods to ease the formation of CH3 radicals are also discussed.

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.