Adsorption microcalorimetry as a tool in the characterization of amine-grafted mesoporous silicas for CO2 capture

  • 151 Accesses

  • 4 Citations


In this work, amine-grafted mesoporous silica were investigated using a adsorption microcalorimetry and supplementary techniques in order to study the influence of increasing the density of grafted amine on the CO2 binding mechanisms. A Tian–Calvet microcalorimeter coupled to a manometric setup was used to evaluate the energetic heterogeneity of adsorption sites and to calculate the thermokinetic parameter from the differential enthalpy curves. With such device, equilibrium adsorption isotherms of CO2 were simultaneously measured at 25 °C for all samples up to 1 bar. The adsorption microcalorimetric study suggests a change in active sites distribution as the density of grafted amines increases. The maximum thermokinetic parameter of 471 s for the pure silica support at 30.7 kJ mol−1 suggests that physisorption is the dominant binding mechanism. A different behavior occurs with the grafted samples: they have considerably higher enthalpy values corresponding to the formation of reacted species on the surface (chemisorbed CO2), which depend on grafted amine density and available free surface silanols. Kinetics of formation of chemisorption products, together with hindered CO2 diffusion, seriously impair the approach to equilibrium, which leads to a decrease in uptake upon isothermal pressure-swing cycles at low temperatures (25 °C). CO2 could be successfully desorbed at 120 °C from the sample with highest uptake (MSG60), which showed a constant uptake for three adsorption–desorption cycles using only vacuum at 50 °C.

This is a preview of subscription content, log in to check access.

Access options

Buy single article

Instant unlimited access to the full article PDF.

US$ 39.95

Price includes VAT for USA

Subscribe to journal

Immediate online access to all issues from 2019. Subscription will auto renew annually.

US$ 99

This is the net price. Taxes to be calculated in checkout.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11
Fig. 12


  1. Alkhabbaz, M.A., Bollini, P., Foo, G.S., Sievers, C., Jones, C.W.: Important Roles of enthalpic and entropic contributions to CO2 capture from simulated flue gas and ambient air using mesoporous silica grafted amines. J. Am. Chem. Soc. 136, 13170–13173 (2014)

  2. Auroux, A.: Calorimetry and thermal methods in catalysis. Springer Berlin Heidelberg, Berlin (2013)

  3. Aziz, B., Hedin, N., Bacsik, Z.: Quantification of chemisorption and physisorption of carbon dioxide on porous silica modified by propylamines: effect of amine density. Microporous Mesoporous Mater. 159, 42–49 (2012)

  4. Bacsik, Z., Ahlsten, N., Ziadi, A., Zhao, G., Garcia-Bennett, A.E., Martín-Matute, B., Hedin, N.: Mechanisms and kinetics for sorption of CO2 on bicontinuous mesoporous silica modified with n-propylamine. Langmuir 27, 11118–11128 (2011)

  5. Bollini, P., Brunelli, N.A., Didas, S.A., Jones, C.W.: Dynamics of CO2 adsorption on amine adsorbents. 2. Insights into adsorbent design. Ind. Eng. Chem. Res. 51, 15153–15162 (2012)

  6. Bourrelly, S., Llewellyn, P.L., Serre, C., Millange, F., Loiseau, T., Férey, G.: Different adsorption behaviors of methane and carbon dioxide in the isotypic nanoporous metal terephthalates MIL-53 and MIL-47. J. Am. Chem. Soc. 127, 13519–13521 (2005)

  7. Cardona-Martinez, N., Dumesic, J.A.: Applications of adsorption microcalorimetry to the study of heterogeneous catalysis. Adv. Catal. 38, 149–244 (1992)

  8. Choi, S., Drese, J.H., Jones, C.W.: Adsorbent materials for carbon dioxide capture from large anthropogenic point sources. ChemSusChem 2, 796–854 (2009)

  9. Condon, J.B.: Surface Area and Porosity Determinations by Physisorption: Measurements and Theory. Elsevier, Amsterdam (2006)

  10. da Silva, F.W.M., Maia, D.A.S., Oliveira, R.S., Moreno-Piraján, J.C., Sapag, K., Cavalcante, C.L., Zgrablich, G., Azevedo, D.C.S.: Adsorption microcalorimetry applied to the characterisation of adsorbents for CO2 capture. Can. J. Chem. Eng. 90, 1372–1380 (2012)

  11. Danon, A., Stair, P.C., Weitz, E.: FTIR study of CO2 adsorption on amine-grafted SBA-15: elucidation of adsorbed species. J. Phys. Chem. C 115, 11540–11549 (2011)

  12. Didas, S.A., Sakwa-Novak, M.A., Foo, G.S., Sievers, C., Jones, C.W.: Effect of amine surface coverage on the Co-adsorption of CO2 and water: spectral deconvolution of adsorbed species. J. Phys. Chem. Lett. 5, 4194–4200 (2014)

  13. Foo, G.S., Polo-Garzon, F., Fung, V., Jiang, D., Overbury, S.H., Wu, Z.: Acid–base reactivity of perovskite catalysts probed via conversion of 2-propanol over titanates and zirconates. ACS Catal. 7, 4423–4434 (2017)

  14. Fulvio, P.F., Pikus, S., Jaroniec, M.: Tailoring properties of SBA-15 materials by controlling conditions of hydrothermal synthesis. J. Mater. Chem. 15, 5049 (2005)

  15. Giraldo, L., Moreno-Piraján, J.C.: CO2 adsorption on activated carbon prepared from mangosteen peel: study by adsorption calorimetry. J. Therm. Anal. Calorim. 133, 337–354 (2018)

  16. Hahn, M.W., Jelic, J., Berger, E., Reuter, K., Jentys, A., Lercher, J.A.: Role of amine functionality for CO2 chemisorption on silica. J. Phys. Chem. B 120, 1988–1995 (2016)

  17. Hiyoshi, N., Yogo, K., Yashima, T.: Adsorption of carbon dioxide on modified mesoporous materials in the presence of water vapor. Stud. Surf. Sci. Catal. 154, 2995–3002 (2004)

  18. Kim, I., Svendsen, H.F.: Heat of absorption of carbon dioxide (CO2) in monoethanolamine (MEA) and 2-(aminoethyl)ethanolamine (AEEA) solutions. Ind. Eng. Chem. Res. 46, 5803–5809 (2007)

  19. Kim, S.N., Son, W.J., Choi, J.S., Ahn, W.S.: CO2 adsorption using amine-functionalized mesoporous silica prepared via anionic surfactant-mediated synthesis. Microporous Mesoporous Mater. 115, 497–503 (2008)

  20. Knöfel, C., Martin, C., Hornebecq, V., Llewellyn, P.L.: Study of carbon dioxide adsorption on mesoporous aminopropylsilane-functionalized silica and titania combining microcalorimetry and in situ infrared spectroscopy. J. Phys. Chem. C 113, 21726–21734 (2009)

  21. Lettow, J.S., Han, Y.J., Schmidt-Winkel, P., Yang, P., Zhao, D., Stucky, G.D., Ying, J.Y.: Hexagonal to mesocellular foam phase transition in polymer-templated mesoporous silica. Langmuir 16, 8291–8295 (2000)

  22. Lilić, A., Wei, T., Bennici, S., Devaux, J.F., Dubois, J.L., Auroux, A.: A comparative study of basic, amphoteric, and acidic catalysts in the oxidative coupling of methanol and ethanol for acrolein production. ChemSusChem 10, 3459–3472(2017)

  23. Llewellyn, P.: Characterization of microporous materials by adsorption microcalorimetry. Recent Adv. Gas Sep. Microporous Ceram. Membr. 6, 213–230 (2000)

  24. Maia, D.A.S., Alexandre de Oliveira, J.C., Nazzarro, M.S., Sapag, K.M., López, R.H., Lucena, S.M.P., Azevedo, D.C.S.: CO2 gas-adsorption calorimetry applied to the study of chemically activated carbons. Chem. Eng. Res. Des. 136, 753–760 (2018)

  25. Ojeda-López, R., Pérez-Hermosillo, I.J., Esparza-Schulz, J.M., Cervantes-Uribe, A., Domínguez-Ortiz, A.: SBA-15 materials: calcination temperature influence on textural properties and total silanol ratio. Adsorption 21, 659–669 (2015)

  26. Potter, M.E., Pang, S.H., Jones, C.W.: Adsorption microcalorimetry of CO2 in confined aminopolymers. Langmuir 33, 117–124 (2017)

  27. Rouquerol, F., Rouquerol, J., Sing, K.S.W., Llewellyn, P.L., Maurin, G.: Adsorption by Powders and Porous Solids: Principles, Methodology and Applications, 2nd Ed. Elsevier, Amsterdam (2014)

  28. Saha, A.: Structure-function, recyclability and calorimetry studies of CO2 adsorption on some amine modified type I & type II sorbents. Int. J. Greenh. Gas Control 78, 198–209 (2018)

  29. Sánchez-Zambrano, K.S., Duarte, L.L., Maia, D.A.S., Vilarrasa-García, E., Bastos-Neto, M., Rodríguez-Castellón, E., Azevedo, D.C.S.: CO2 capture with mesoporous silicas modified with amines by double functionalization: assessment of adsorption/desorption cycles. Materials 11, 887 (2018)

  30. Savino, R., Casadonte, F., Terracciano, R.: Mesopore protein digestion: a new forthcoming strategy in proteomics. Molecules 16, 5938–5962 (2011)

  31. Schmidt-Winkel, P., Lukens, W.W., Zhao, D., Yang, P., Chmelka, B.F., Stucky, G.D.: Mesocellular siliceous foams with uniformly sized cells and windows. J. Am. Chem. Soc. 121, 254–255 (1999)

  32. Sumida, K., Rogow, D.L., Mason, J.A., McDonald, T.M., Bloch, E.D., Herm, Z.R., Bae, T.-H., Long, J.R.: Carbon dioxide capture in metal-organic frameworks. Chem. Rev. 112, 724–781 (2012)

  33. Thommes, M., Kaneko, K., Neimark, A.V., Olivier, J.P., Rodriguez-Reinoso, F., Rouquerol, J., Sing, K.S.W.: Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report). Pure Appl. Chem. (2015).

  34. Vilarrasa-Garcia, E., Moya, E.M.O., Cecilia, J.A., Cavalcante, C.L. Jr., Jiménez-Jiménez, J., Azevedo, D.C.S., Rodríguez-Castellón, E.: CO2 adsorption on amine modified mesoporous silicas: Effect of the progressive disorder of the honeycomb arrangement. Microporous Mesoporous Mater. 209, 172–183 (2015)

  35. Vilarrasa-García, E., Cecilia, J.A., Santos, S.M.L., Cavalcante, C.L. Jr., Jiménez-Jiménez, J., Azevedo, D.C.S., Rodríguez-Castellón, E.: CO2 adsorption on APTES functionalized mesocellular foams obtained from mesoporous silica. Microporous Mesoporous Mater. 187, 125–134 (2014)

  36. Yoo, C.J., Lee, L.C., Jones, C.W.: Probing intramolecular versus intermolecular CO2 adsorption on amine-grafted SBA-15. Langmuir 31, 13350–13360 (2015)

  37. Zhao, D., Feng, J., Huo, Q., Melosh, N., Fredrickson, G.H., Chmelka, B.F., Stucky, G.D.: Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores. Science 279, 548–552 (1998)

Download references


The authors are thankful to Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq), together with Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES), for funding grants to Sanchez-Zambrano, Vilarrasa-Garcia and Maia. Analytical support (29Si RMN) provided by the Institute of Chemistry at UNICAMP (Brazil) is gratefully acknowledged.

Author information

Correspondence to D. C. S. Azevedo.

Additional information

Publisher’s Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Sánchez-Zambrano, K.S., Vilarrasa-García, E., Maia, D.A.S. et al. Adsorption microcalorimetry as a tool in the characterization of amine-grafted mesoporous silicas for CO2 capture. Adsorption 26, 165–175 (2020) doi:10.1007/s10450-019-00064-y

Download citation


  • APTES-grafted silica
  • CO2 adsorption
  • Microcalorimetry
  • Thermokinetic parameter