Skip to main content

Thank you for visiting You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

A closed cycle for esterifying aromatic hydrocarbons with CO2 and alcohol


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.

This is a preview of subscription content, access via your institution

Access options

Rent or buy this article

Prices vary by article type



Prices may be subject to local taxes which are calculated during checkout

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.


  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).

    Article  CAS  Google Scholar 

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

    Article  Google Scholar 

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

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

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

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

  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).

    Article  CAS  Google Scholar 

  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).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  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).

    Article  CAS  Google Scholar 

  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).

    Article  CAS  Google Scholar 

  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).

    Article  CAS  Google Scholar 

  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).

    Article  CAS  Google Scholar 

  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).

    Article  CAS  Google Scholar 

  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).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  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).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

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

    Article  CAS  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

  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).

    Article  CAS  Google Scholar 

  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).

    Article  CAS  Google Scholar 

  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).

    Article  CAS  Google Scholar 

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

    Article  Google Scholar 

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

    Article  CAS  Google Scholar 

  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).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    CAS  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  CAS  Google Scholar 

  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).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  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).

    Article  CAS  Google Scholar 

Download references


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

Authors and Affiliations



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.

Corresponding author

Correspondence to Matthew W. Kanan.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

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

Rights and permissions

Reprints and Permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

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).

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI:

This article is cited by


Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing