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Deciphering key intermediates in the transformation of carbon dioxide into heterocyclic products

Nature Catalysis volume 2, pages 62–70 (2019)Cite this article

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Abstract

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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Fig. 1: Comparison between conventional C−O coupling of CO2 using an epoxide and an approach using the hydroxyl group of the substrate.
Fig. 2: Catalytic behaviour.
Fig. 3: Gibbs free energy (B97-D3, kcal mol−1) profiles.
Fig. 4: Solid-state ATR infrared spectroscopy.
Fig. 5: Special sequence of ATR infrared measurements in solution.
Fig. 6: Operando high-pressure infrared spectroscopic analysis of the reaction between AlTHFL, GLY and CO2.

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Data availability

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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Acknowledgements

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.

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Author notes

  1. These authors contributed equally: Rui Huang, Jeroen Rintjema.

Authors and Affiliations

  1. Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology, Tarragona, Spain

    Rui Huang, Jeroen Rintjema, Joan González-Fabra, Eddy Martín, Eduardo C. Escudero-Adán, Carles Bo, Atsushi Urakawa & Arjan W. Kleij

  2. Departament de Química Física i Inorgánica, Universitat Rovira, i Virgili, Marcel-li Domingo, Tarragona, Spain

    Carles Bo

  3. Catalan Institute of Research and Advanced Studies (ICREA) , Barcelona, Spain

    Arjan W. Kleij

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Contributions

A.W.K. and A.U. conceived of the project. R.H. and J.R. (equal contribution) carried out both the spectroscopic measurements and the catalytic experiments, as well as the manuscript preparation. J.G.F. and C.B. performed DFT calculations. E.M. and E.C.E-A. helped with X-ray analysis. All authors contributed to scientific discussion and revised the manuscript.

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Correspondence to Carles Bo, Atsushi Urakawa or Arjan W. Kleij.

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Supplementary information

Supplementary Information

Supplementary Methods, Supplementary Discussion, Supplementary Figures 1–9, Supplementary Tables 1–5, Supplementary References

AlGLYL

Crystallographic data for AlGLYL complex

Supplementary Video 1

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

Supplementary Video 2

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

Supplementary Video 3

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

Supplementary Video 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

Supplementary Video 5

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

Supplementary Video 6

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

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