Article: Highly efficient multi-site synergistic catalysis of a polyoxovanadate-based metal–organic framework for benzylic C–H bond oxidation
Journal of materials chemistry A. 2022 Aug. 10, v. 10, no. 31
2022
Abstract: The selective oxidation of C–H bonds of benzylic compounds to synthesize high-value-added ketones remains a challenge under mild conditions, and the ambiguity of its oxidation mechanism limits the further development of this field. In this work, we ... ...
| Abstract | The selective oxidation of C–H bonds of benzylic compounds to synthesize high-value-added ketones remains a challenge under mild conditions, and the ambiguity of its oxidation mechanism limits the further development of this field. In this work, we construct a polyoxometalate-based metal–organic framework (POMOF), [CuI2Cuᴵᴵ(bix)₂]{V₄O₁₂} (1, bix = 1,4-bis(imidazole-1-ylmethyl)benzene), successfully achieving the efficient oxidation catalysis of various benzylic compounds with outstanding conversion, selectivity and durability under mild conditions. Our experimental studies suggest that the highly catalytic activity of 1 derives from its attractive structure with multiple active sites, which consists of Vⱽ centers in a unique U-type {V₄O₁₂}⁴⁻ ({V₄}) cluster and Cuᴵ and Cuᴵᴵ centers bridged to the {V₄} cluster. Importantly, further theoretical calculations indicate that there exists synergistic catalysis between Cuᴵ/{V₄} sites and Cuᴵᴵ/{V₄} sites for 1 as catalyst in the oxidation of benzylic compounds, where the {V₄} cluster mainly provides deprotonation and oxidation sites, and the Cuᴵ site plays a role in the reduction of the oxidant, while the Cuᴵᴵ site plays a role in the adsorption of the oxidant. This is the first POMOF whose catalytic mechanism towards the oxidation of benzylic C–H bonds is deeply studied through the combination of experiments and theoretical calculations, providing a new perspective for the design of related catalysts. |
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| Keywords | adsorption ; catalysts ; catalytic activity ; coordination polymers ; deprotonation ; durability ; oxidants ; oxidation |
| Language | English |
| Dates of publication | 2022-0810 |
| Size | p. 16514-16523. |
| Publishing place | The Royal Society of Chemistry |
| Document type | Article |
| ZDB-ID | 2702232-8 |
| ISSN | 2050-7496 ; 2050-7488 |
| ISSN (online) | 2050-7496 |
| ISSN | 2050-7488 |
| DOI | 10.1039/d2ta03886b |
| Database | NAL-Catalogue (AGRICOLA) |
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