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A closed cycle for esterifying aromatic hydrocarbons with CO2 and alcohol

Nature Chemistry volume 11, pages 940–947 (2019)Cite this article

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Abstract

The ability to functionalize hydrocarbons with CO2 could create opportunities for high-volume CO2 utilization. However, current methods to form carbon–carbon bonds between hydrocarbons and CO2 require stoichiometric consumption of very resource-intensive reagents to overcome the low reactivity of these substrates. Here, we report a simple semi-continuous cycle that converts aromatic hydrocarbons, CO2 and alcohol into aromatic esters without consumption of stoichiometric reagents. Our strategy centres on the use of solid bases composed of an alkali carbonate (M2CO3, where M+ = K+ or Cs+) dispersed over a mesoporous support. Nanoscale confinement disrupts the crystallinity of M2CO3 and engenders strong base reactivity at intermediate temperatures. The overall cycle involves two distinct steps: (1) CO32–-promoted C–H carboxylation, in which the hydrocarbon substrate is deprotonated by the supported M2CO3 and reacts with CO2 to form a supported carboxylate (RCO2M); and (2) methylation, in which RCO2M reacts with methanol and CO2 to form an isolable methyl ester with concomitant regeneration of M2CO3.

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Fig. 1: A closed cycle for the esterification of benzene using CO2 and methanol.
Fig. 2: Characterization and proposed model of M2CO3/TiO2.
Fig. 3: Carboxylation, volatilization and cycling results for K and Cs2CO3/TiO2 (1×).
Fig. 4: Mechanistic studies.

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Data availability

The main data supporting the findings of this study are included in the paper and its Supplementary Information files. Additional raw data (NMR spectra, mass spectra and so on) are available from the corresponding author on reasonable request.

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Acknowledgements

We thank the Global Climate and Energy Project, TomKat Center for Sustainable Energy and Camille and Henry Dreyfus Foundation for support of this work. D.J.X. acknowledges the Arnold and Mabel Beckman Foundation for a postdoctoral fellowship. A.D.F. acknowledges support from a NASA Space Technology Research Fellowship. We thank L. Darago for assistance with collecting powder diffraction data, and the Karunadasa laboratory for use of their Micromeritics ASAP 2020. Part of this work was performed at the Stanford Nano Shared Facilities, supported by the National Science Foundation under award ECCS-1542152. GC–MS data were collected at the Vincent Coates Foundation Mass Spectrometry Laboratory at Stanford University Mass Spectrometry. Powder diffraction data were collected at Beamline 12.2.2 at the Advanced Light Source, and Beamline 11-BM at the Advanced Photon Source. The Advanced Light Source is supported by the Director, Office of Science, Office of Basic Energy Sciences of the US DOE under contract number DE-AC02-05CH11231. Use of the Advanced Photon Source at Argonne National Laboratory was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under contract number DE-AC02-06CH11357. Solid-state NMR was performed using EMSL (grid.436923.9)—a DOE Office of Science User Facility sponsored by the Office of Biological and Environmental Research.

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Authors and Affiliations

  1. Department of Chemistry, Stanford University, Stanford, CA, USA

    Dianne J. Xiao, Emma D. Chant, Amy D. Frankhouser, Allison Yau & Matthew W. Kanan

  2. Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, WA, USA

    Ying Chen & Nancy M. Washton

Authors
  1. Dianne J. Xiao
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Contributions

D.J.X. and M.W.K. conceived and designed the experiments. D.J.X. and E.D.C. performed all of the experiments except the solid-state NMR and transmission electron microscopy studies. A.D.F. and Y.C. performed the solid-state NMR studies. A.Y. performed the transmission electron microscopy studies. N.M.W., Y.C. and A.D.F. conceived and designed the solid-state NMR experiments. D.J.X. and M.W.K. wrote the initial draft of the paper, and all authors contributed to the final version.

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Correspondence to Matthew W. Kanan.

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Supplementary Information

Supplementary methods and analysis, Tables 1–14 and Figs. 1–26

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Xiao, D.J., Chant, E.D., Frankhouser, A.D. et al. A closed cycle for esterifying aromatic hydrocarbons with CO2 and alcohol. Nat. Chem. 11, 940–947 (2019). https://doi.org/10.1038/s41557-019-0313-y

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