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.
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A data set of input files and computational results is available in the ioChem-BD repository57 and can be accessed via https://doi.org/10.19061/iochem-bd-1-58. The data that support the plots within this paper and other findings of this study are available from the corresponding author upon reasonable request. CCDC 1850585 contains the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures.
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The authors acknowledge financial support by ICIQ, ICREA, the CERCA Program/Generalitat de Catalunya and the Spanish Ministerio de Economıa y Competitividad (MINECO: CTQ2012-34153, CTQ2017-88920-P and CTQ2016-75499-R (AEI/FEDER-UE), and Severo Ochoa Excellence Accreditation 2014−2018, SEV-2013-0319). R.H. thanks the COFUND postdoctoral programme of the EU. The Research Support Area of ICIQ is also thanked for their experimental assistance.
The authors declare no competing interests.
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Supplementary Methods, Supplementary Discussion, Supplementary Figures 1–9, Supplementary Tables 1–5, Supplementary References
Crystallographic data for AlGLYL complex
The simulated IR vibrational model of the phenolic C–O stretching band of the ligand part in the aluminum catalyst (AlTHFL) corresponding to peak 1 in Fig. 4
The simulated IR vibrational model of the C‒N stretching band of the ligand part in the aluminum catalyst (AlTHFL) corresponding to peak 2 in Fig. 4
The simulated IR vibrational model of the C‒O‒C stretching band of the THF ligand in the aluminum catalyst (AlTHFL) corresponding to peak 3 in Fig. 4
The simulated IR vibrational model of the phenolic O‒Al stretching band in the aluminum catalyst (AlTHFL) corresponding to peak 4 in Fig. 4
The simulated IR vibrational model of the O‒Al stretching band of the THF ligand in the aluminum catalyst (AlTHFL) corresponding to peak 5 in Fig. 4
The simulated IR vibrational model of the typical aromatic C–H band of the ligand part in the aluminum catalyst (AlTHFL) corresponding to peak 6 in Fig. 4
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Huang, R., Rintjema, J., González-Fabra, J. et al. Deciphering key intermediates in the transformation of carbon dioxide into heterocyclic products. Nat Catal 2, 62–70 (2019). https://doi.org/10.1038/s41929-018-0189-z