On the structure and coordination of the oxygen-donating species in Ti↑MCM-41/TBHP oxidation catalysts: a density functional theory and EXAFS study

Literature Information

Publication Date 2002-03-04
DOI 10.1039/B104735N
Impact Factor 3.676
Authors

Nikolas Kaltsoyannis


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Abstract

We present a combined density functional theory and EXAFS investigation into the geometry and coordination of the oxygen-donating species in surface grafted, tert-butyl hydroperoxide (TBHP) exposed Ti↑MCM-41 oxidation catalysts. The formation of a number of different Ti(η2-peroxo) and Ti(η1-peroxo) type species, including radical and anionic complexes, has been examined, arising from the attack of peroxide (where both hydrogen peroxide and TBHP have been studied) on a tetrahedral TiIV site, together with and without one molecule of water. BP86/DZVP calculations show that the Ti(η1-OOtBu) complex is 33 kJ mol−1 lower in energy than the Ti(η2-OOtBu) complex which is contrary to previous estimates in the literature and we propose that 6-coordinate Ti(η1-OOR) complexes, where R is the peroxide substituent (i.e. R = H for H2O2 and R = tBu for TBHP), are the oxygen-donating species in peroxide/titanosilicate mixtures. X-ray absorption analysis is in good agreement with our DFT predictions that Ti–peroxo species in TBHP/Ti↑MCM-41 systems are 6-coordinate. Furthermore, our DFT cluster calculations and X-ray absorption analysis collectively reveal the presence of 6-coordinate ‘Ti(η2-OOtBu)(OHR)’ and ‘Ti(η1-OOtBu)(OHR)·H2O’ complexes in TBHP/Ti↑MCM-41 catalysts.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
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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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