Deciphering key intermediates in the transformation of carbon dioxide into heterocyclic products
| Autor: | Eduardo C. Escudero-Adán, Atsushi Urakawa, Arjan W. Kleij, Carles Bo, Eddy Martin, Joan González-Fabra, Jeroen Rintjema, Rui Huang |
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| Rok vydání: | 2018 |
| Předmět: |
chemistry.chemical_classification
010405 organic chemistry Hydrogen bond Process Chemistry and Technology Intermolecular force Infrared spectroscopy Substrate (chemistry) Bioengineering 010402 general chemistry 01 natural sciences Biochemistry Combinatorial chemistry Catalysis Cycloaddition 0104 chemical sciences chemistry.chemical_compound chemistry Carbonate Alkyl |
| Zdroj: | RECERCAT (Dipòsit de la Recerca de Catalunya) Recercat. Dipósit de la Recerca de Catalunya instname |
| Popis: | The identification of catalytic intermediates in the conversion of carbon dioxide is vital for improved catalyst design and optimization of structure–reactivity relationships, but remains elusive. Here, we report that intermolecular hydrogen bonding interactions between an epoxy alcohol, water and the catalyst structure are crucial towards the formation of a cyclic carbonate from carbon dioxide. A combination of multiple in situ and ex situ techniques including substrate labelling, kinetic studies, computational analysis, operando infrared spectroscopy and X-ray diffraction was applied to identify and support the structural connectivities of several previously unknown intermediates. An epoxy alcohol–water cluster formed by hydrogen bonding was identified as the initial intermediate able to trap CO2 and an elusive alkyl carbonate anion was also detected. The synergistic spectroscopic and computational analysis shown here offers a unique insight under operando conditions, as well as a useful analytical blueprint for key suggested intermediates in other mechanistically related CO2 conversion processes. One of the major routes for the use of CO2 in chemical production is the formation of carbonates via cycloaddition of CO2 to epoxides. This work uses a range of experimental and computational techniques to map out the elusive key intermediates in this process. |
| Databáze: | OpenAIRE |
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