A closed cycle for esterifying aromatic hydrocarbons with CO2 and alcohol

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.

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.

References

  1. 1.

    Artz, J. et al. Sustainable conversion of carbon dioxide: an integrated review of catalysis and life cycle assessment. Chem. Rev. 118, 434–504 (2018).

  2. 2.

    Liu, Q., Wu, L., Jackstell, R. & Beller, M. Using carbon dioxide as a building block in organic synthesis. Nat. Commun. 6, 5933 (2015).

  3. 3.

    Röhrscheid, F. Carboxylic acids, aromatic. Ullmann’s Encyclopedia of Industrial Chemistry (Wiley-VCH, 2000).

  4. 4.

    Ohara, T. et al. Acrylic acid and derivatives. Ullmann’s Encyclopedia of Industrial Chemistry (Wiley-VCH, 2011).

  5. 5.

    Kubitschke, J., Lange, H. & Strutz, H. Carboxylic acids, aliphatic. Ullmann’s Encyclopedia of Industrial Chemistry (Wiley-VCH, 2014).

  6. 6.

    CRC Handbook of Chemistry and Physics (CRC, 2017).

  7. 7.

    Guthrie, J. P., Pike, D. C. & Lee, Y.-C. Equilibrium constants and heats of formation of methyl esters and N,N-dimethyl amides of substituted benzoic acids. Can. J. Chem. 70, 1671–1683 (1992).

  8. 8.

    Steele, W. V., Chirico, R. D., Cowell, A. B., Knipmeyer, S. E. & Nguyen, A. Thermodynamic properties and ideal-gas enthalpies of formation for methyl benzoate, ethyl benzoate, (R)-(+)-limonene, tert-amyl methyl ether, trans-crotonaldehyde, and diethylene glycol. J. Chem. Eng. Data 47, 667–688 (2002).

  9. 9.

    Cai, X. & Xie, B. Direct carboxylative reactions for the transformation of carbon dioxide into carboxylic acids and derivatives. Synthesis 45, 3305–3324 (2013).

  10. 10.

    Wang, X., Wang, H. & Sun, Y. Synthesis of acrylic acid derivatives from CO2 and ethylene. Chem 3, 211–228 (2017).

  11. 11.

    Schlosser, M., Jung, H. C. & Takagishi, S. Selective mono- or dimetalation of arenes by means of superbasic reagents. Tetrahedron 46, 5633–5648 (1990).

  12. 12.

    Olah, G. A. et al. Efficient chemoselective carboxylation of aromatics to arylcarboxylic acids with a superelectrophilically activated carbon dioxide−Al2Cl6/Al system. J. Am. Chem. Soc. 124, 11379–11391 (2002).

  13. 13.

    Suga, T., Mizuno, H., Takaya, J. & Iwasawa, N. Direct carboxylation of simple arenes with CO2 through a rhodium-catalyzed C–H bond activation. Chem Commun 50, 14360–14363 (2014).

  14. 14.

    Wu, J.-F. et al. Mechanistic insight into the formation of acetic acid from the direct conversion of methane and carbon dioxide on zinc-modified H–ZSM-5 zeolite. J. Am. Chem. Soc. 135, 13567–13573 (2013).

  15. 15.

    Patil, U. et al. Low temperature activation of methane over a zinc-exchanged heteropolyacid as an entry to its selective oxidation to methanol and acetic acid. Chem. Commun. 50, 12348–12351 (2014).

  16. 16.

    Banerjee, A., Dick, G. R., Yoshino, T. & Kanan, M. W. Carbon dioxide utilization via carbonate-promoted C–H carboxylation. Nature 531, 215–219 (2016).

  17. 17.

    Dick, G. R., Frankhouser, A. D., Banerjee, A. & Kanan, M. W. A scalable carboxylation route to furan-2,5-dicarboxylic acid. Green Chem. 19, 2966–2972 (2017).

  18. 18.

    Banerjee, A. & Kanan, M. W. Carbonate-promoted hydrogenation of carbon dioxide to multicarbon carboxylates. ACS Cent. Sci. 4, 606–613 (2018).

  19. 19.

    Sattler, A. Hydrogen/deuterium (H/D) exchange catalysis in alkanes. ACS Catal. 8, 2296–2312 (2018).

  20. 20.

    Utiyama, M. Exchange reaction of methane with deuterium over solid base catalysts. J. Catal. 53, 237–242 (1978).

  21. 21.

    Joubert, J. et al. Heterolytic splitting of H2 and CH4 on γ-alumina as a structural probe for defect sites. J. Phys. Chem. B 110, 23944–23950 (2006).

  22. 22.

    Hattori, H. Heterogeneous basic catalysis. Chem. Rev. 95, 537–558 (1995).

  23. 23.

    Bruno, B., Hubert, S. & Werner, S. Process for the introduction of carboxyl groups into aromatic hydrocarbons. US patent US2948750A (1960).

  24. 24.

    Lee, S. C. et al. CO2 absorption and regeneration of alkali metal-based solid sorbents. Catal. Today 111, 385–390 (2006).

  25. 25.

    Lukić, I., Krstić, J., Jovanović, D. & Skala, D. Alumina/silica supported K2CO3 as a catalyst for biodiesel synthesis from sunflower oil. Bioresour. Technol. 100, 4690–4696 (2009).

  26. 26.

    Yamaguchi, T., Zhu, J.-H., Wang, Y., Komatsu, M. & Ookawa, M. Supported K-salts as a new solid base catalyst. Chem. Lett. 26, 989–990 (1997).

  27. 27.

    Chen, D. et al. Synthesis of monodisperse mesoporous titania beads with controllable diameter, high surface areas, and variable pore diameters (14−23 nm). J. Am. Chem. Soc. 132, 4438–4444 (2010).

  28. 28.

    Deng, X., Chen, K. & Tüysüz, H. Protocol for the nanocasting method: preparation of ordered mesoporous metal oxides. Chem. Mater. 29, 40–52 (2017).

  29. 29.

    Ono, Y. & Hattori, H. in Solid Base Catalysis 11–68 (Springer, 2011).

  30. 30.

    Busca, G. & Lorenzelli, V. Infrared spectroscopic identification of species arising from reactive adsorption of carbon oxides on metal oxide surfaces. Mater. Chem. 7, 89–126 (1982).

  31. 31.

    Kantschewa, M., Albano, E. V., Ertl, G. & Knözinger, H. Infrared and X-ray photoelectron spectroscopy study of K2CO3/γ-Al2O3. Appl. Catal. 8, 71–84 (1983).

  32. 32.

    Nebel, H., Neumann, M., Mayer, C. & Epple, M. On the structure of amorphous calcium carbonate—a detailed study by solid-state NMR spectroscopy. Inorg. Chem. 47, 7874–7879 (2008).

  33. 33.

    Albéric, M. et al. The crystallization of amorphous calcium carbonate is kinetically governed by ion impurities and water. Adv. Sci. 5, 1701000 (2018).

  34. 34.

    Walter, E. D. et al. Operando MAS NMR reaction studies at high temperatures and pressures. J. Phys. Chem. C 122, 8209–8215 (2018).

  35. 35.

    Mehta, H. S. et al. A novel high-temperature MAS probe with optimized temperature gradient across sample rotor for in-situ monitoring of high-temperature high-pressure chemical reactions. Solid State Nucl. Magn. Reson. 102, 31–35 (2019).

  36. 36.

    Bloembergen, N., Purcell, E. M. & Pound, R. V. Relaxation effects in nuclear magnetic resonance absorption. Phys. Rev. 73, 679–712 (1948).

  37. 37.

    Tanabe, K. & Yamaguchi, T. Basicity and acidity of solid surfaces. J. Res. Inst. Catal. Hokkaido Univ. 11, 179–184 (1964).

  38. 38.

    Van Deun, R. et al. Alkali-metal salts of aromatic carboxylic acids: liquid crystals without flexible chains. Eur. J. Inorg. Chem. 2005, 563–571 (2005).

  39. 39.

    Dabestani, R., Britt, P. F. & Buchanan, A. C. Pyrolysis of aromatic carboxylic acid salts: does decarboxylation play a role in cross-linking reactions? Energy Fuels 19, 365–373 (2005).

  40. 40.

    Shieh, W.-C., Dell, S. & Repič, O. Nucleophilic catalysis with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) for the esterification of carboxylic acids with dimethyl carbonate. J. Org. Chem. 67, 2188–2191 (2002).

  41. 41.

    Jun, S. et al. Synthesis of new, nanoporous carbon with hexagonally ordered mesostructure. J. Am. Chem. Soc. 122, 10712–10713 (2000).

  42. 42.

    Santos, B. A. V., Silva, V. M. T. M., Loureiro, J. M. & Rodrigues, A. E. Review for the direct synthesis of dimethyl carbonate. ChemBioEng Rev. 1, 214–229 (2014).

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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.

Author information

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.

Correspondence to Matthew W. Kanan.

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Supplementary information

Supplementary Information

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

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