Abstract
Adsorption of various glycerol conformations at Brønsted sites in mordenite is studied by the density functional theory. It is shown that the adsorption energy depends on the initial conformation of the glycerol molecule and ranges from –44.0 kcal/mol (ββ conformation) to –64.7 kcal/mol (αγ conformation). In some cases, the glycerol molecule switches its conformation as a result of nanoconfinement. It is shown that the most energetically favorable adsorption of glycerol on mordenite proceeds via the primary OH group. High adsorption energy is due to the proton transfer from the zeolite Brønsted site to glycerol as a result of the hydrogen bond formation and also due to the formation of up to four additional hydrogen bonds with oxygen atoms of the zeolite framework. As a result, the backbone of the adsorbed molecule deforms, which fact should affect the course of chemical reactions involving glycerol.
REFERENCES
C. M. Lok, J. V. Doorn, and G. A. Almansa. Promoted ZSM-5 catalysts for the production of bio-aromatics, a review. Renewable Sustainable Energy Rev., 2019, 113, 109248. https://doi.org/10.1016/j.rser.2019.109248
S. He, K. Zuur, D. S. Santosa, A. Heeres, C. Liu, E. Pidko, and H. J. Heeres. Catalytic conversion of pure glycerol over an un-modified H-ZSM-5 zeolite to bio-based aromatics. Appl. Catal., B, 2021, 281, 119467. https://doi.org/10.1016/j.apcatb.2020.119467
L.-H. Chen, M.-H. Sun, Z. Wang, W. Yang, Z. Xie, and B.-L. Su. Hierarchically structured zeolites: From design to application. Chem. Rev., 2020, 120(20), 11194-11294. https://doi.org/10.1021/acs.chemrev.0c00016
Z. Wang, L. Wang, Y. Jiang, M. Hunger, and J. Huang. Cooperativity of Brønsted and Lewis acid sites on zeolite for glycerol dehydration. ACS Catal., 2014, 4(4), 1144-1147. https://doi.org/10.1021/cs401225k
V. S. Marakatti and A. B. Halgeri. Metal ion-exchanged zeolites as highly active solid acid catalysts for the green synthesis of glycerol carbonate from glycerol. RSC Adv., 2015, 5(19), 14286-14293. https://doi.org/10.1039/c4ra16052e
C. Baerlocher and L. B. McCusker. Database of Zeolite Structures. http://www.iza-structure.org/databases/ (accessed Nov 11, 2022).
I. Rodríguez-Iznaga, M. G. Shelyapina, and V. Petranovskii. Ion exchange in natural clinoptilolite: Aspects related to its structure and applications. Minerals, 2022, 12(12), 1628. https://doi.org/10.3390/min12121628
M. G. Shelyapina, E. A. Krylova, A. S. Mazur, A. A. Tsyganenko, Y. V. Shergin, E. A. Satikova, and V. Petranovskii. Active sites in H-mordenite catalysts probed by NMR and FTIR. Catalysts, 2023, 13(2), 344. https://doi.org/10.3390/catal13020344
A. Alberti. Location of Brønsted sites in mordenite. Zeolites, 1997, 19(5/6), 411-415. https://doi.org/10.1016/s0144-2449(97)00114-0
M. Brändle and J. Sauer. Acidity Differences between inorganic solids induced by their framework structure. A combined quantum mechanics/molecular mechanics ab initio study on zeolites. J. Am. Chem. Soc., 1998, 120(7), 1556-1570. https://doi.org/10.1021/ja9729037
J. Antúnez-García, D. H. Galván, V. Petranovskii, F. N. Murrieta-Rico, R. I. Yocupicio-Gaxiola, M. G. Shelyapina, and S. Fuentes-Moyado. Aluminum distribution in mordenite-zeolite framework: A new outlook based on density functional theory calculations. J. Solid State Chem., 2022, 306, 122725. https://doi.org/10.1016/j.jssc.2021.122725
G. Sastre, N. Katada, and M. Niwa. Computational study of Brønsted acidity of mordenite. Effect of the electric field on the infrared OH stretching frequencies. J. Phys. Chem. C, 2010, 114(36), 15424-15431. https://doi.org/10.1021/jp104316e
A. Bhan, A. D. Allian, G. J. Sunley, D. J. Law, and E. Iglesia. Specificity of sites within eight-membered ring zeolite channels for carbonylation of methyls to acetyls. J. Am. Chem. Soc., 2007, 129(16), 4919-4924. https://doi.org/10.1021/ja070094d
L. Díaz, A. Sierraalta, M. A. C. Nascimento, and R. Añez. Evaluation of Brønsted sites inside the H–MOR employing NH3: A theoretical study. J. Phys. Chem. C, 2013, 117(10), 5112-5117. https://doi.org/10.1021/jp3116287
A. A. Gabrienko, I. G. Danilova, S. S. Arzumanov, L. V. Pirutko, D. Freude, and A. G. Stepanov. Direct measurement of zeolite Brønsted acidity by FTIR spectroscopy: Solid-state 1H MAS NMR approach for reliable determination of the integrated molar absorption coefficients. J. Phys. Chem. C, 2018, 122(44), 25386-25395. https://doi.org/10.1021/acs.jpcc.8b07429
A. Corma, G. Huber, L. Sauvanaud, and P. Oconnor. Biomass to chemicals: Catalytic conversion of glycerol/water mixtures into acrolein, reaction network. J. Catal., 2008, 257(1), 163-171. https://doi.org/10.1016/j.jcat.2008.04.016
E. A. Krylova, M. G. Shelyapina, A. Mazur, D. A. Baranov, A. A. Tsyganenko, and V. P. Petranovskii. Local structure of protonated mordenites with SiO2/Al2O3 ≈ 15 probed by multinuclear NMR. J. Struct. Chem., 2022, 63(6), 930-943. https://doi.org/10.1134/s0022476622060105
D. Michel, W. Böhlmann, J. Roland, and S. Mulla-Osman. Study of conformation and dynamics of molecules adsorbed in zeolites by 1H NMR. In: Molecules in Interaction with Surfaces and Interfaces / Eds. R. Haberlandt, D. Michel, A. Pöppl, and R. Stannarius: Lecture Notes in Physics, Vol. 634. Berlin/Heidelberg, Germany: Springer, 2004, 217-274. https://doi.org/10.1007/978-3-540-40024-0_6
M. G. Shelyapina, D. Y. Nefedov, A. O. Antonenko, H. Hmok, A. V. Egorov, M. I. Egorova, A. V. Ievlev, R. Yocupicio-Gaxiola, V. Petranovskii, J. Antúnez-García, and S. Fuentes. Dynamics of guest water molecules in pillared mordenite studied by 1H NMR relaxation. Appl. Magn. Reson., 2023, 54(10), 915-928. https://doi.org/10.1007/s00723-023-01589-w
M. G. Shelyapina, D. Y. Nefedov, A. O. Antonenko, G. A. Valkovskiy, R. I. Yocupicio-Gaxiola, and V. Petranovskii. Nanoconfined water in pillared zeolites probed by 1H nuclear magnetic resonance. Int. J. Mol. Sci., 2023, 24(21), 15898. https://doi.org/10.3390/ijms242115898
C. D′Agostino, P. Bräuer, J. Zheng, N. Robinson, A. P. E. York, L. Song, and X. Fan. Adsorbate/adsorbent interactions in microporous zeolites: mechanistic insights from NMR relaxation and DFT calculations. Mater. Today Chem., 2023, 29, 101443. https://doi.org/10.1016/j.mtchem.2023.101443
D. B. Rasmussen, J. M. Christensen, B. Temel, F. Studt, P. G. Moses, J. Rossmeisl, A. Riisager, and A. D. Jensen. Reaction mechanism of dimethyl ether carbonylation to methyl acetate over mordenite - a combined DFT/experimental study. Catal. Sci. Technol., 2017, 7(5), 1141-1152. https://doi.org/10.1039/c6cy01904h
K. Kongpatpanich, T. Nanok, B. Boekfa, M. Probst, and J. Limtrakul. Structures and reaction mechanisms of glycerol dehydration over H-ZSM-5 zeolite: A density functional theory study. Phys. Chem. Chem. Phys., 2011, 13(14), 6462. https://doi.org/10.1039/c0cp01720e
O. Bastiansen, H. Borgiel, and E. Saluste. Intra-molecular hydrogen bonds in ethylene glycol, glycerol, and ethylene chlorohydrin. Acta Chem. Scand., 1949, 3, 415-421. https://doi.org/10.3891/acta.chem.scand.03-0415
K.-H. Jeong, B.-J. Byun, and Y.-K. Kang. Conformational preferences of glycerol in the gas phase and in water. Bull. Korean Chem. Soc., 2012, 33(3), 917-924. https://doi.org/10.5012/bkcs.2012.33.3.917
G. Maccaferri, W. Caminati, and P. G. Favero. Free jet investigation of the rotational spectrum of glycerol. J. Chem. Soc. Faraday Trans., 1997, 93(23), 4115-4117. https://doi.org/10.1039/a705645a
J. J. Towey, A. K. Soper, and L. Dougan. The structure of glycerol in the liquid state: A neutron diffraction study. Phys. Chem. Chem. Phys., 2011, 13(20), 9397. https://doi.org/10.1039/c0cp02136a
H. Van Koningsveld. A conformational study on glycerol in a D2O solution by means of 220 Mc PMR data. Recl. Trav. Chim. Pays-Bas, 1970, 89(8), 801-812. https://doi.org/10.1002/recl.19700890806
A. V. Egorov, A. P. Lyubartsev, and A. Laaksonen. Molecular dynamics simulation study of glycerol–water liquid mixtures. J. Phys. Chem. B, 2011, 115(49), 14572-14581. https://doi.org/10.1021/jp208758r
Y. Nishida, R. Aono, H. Dohi, W. Ding, and H. Uzawa. 1H-NMR Karplus analysis of molecular conformations of glycerol under different solvent conditions: A consistent rotational isomerism in the backbone governed by glycerol/water interactions. Int. J. Mol. Sci., 2023, 24(3), 2766. https://doi.org/10.3390/ijms24032766
A. Charkhesht, D. Lou, B. Sindle, C. Wen, S. Cheng, and N. Q. Vinh. Insights into hydration dynamics and cooperative interactions in glycerol–water mixtures by terahertz dielectric spectroscopy. J. Phys. Chem. B, 2019, 123(41), 8791-8799. https://doi.org/10.1021/acs.jpcb.9b07021
M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, G. A. Petersson, H. Nakatsuji, X. Li, M. Caricato, A. V. Marenich, J. Bloino, B. G. Janesko, R. Gomperts, B. Mennucci, H. P. Hratchian, J. V. Ortiz, A. F. Izmaylov, J. L. Sonnenberg, D. Williams-Young, F. Ding, F. Lipparini, F. Egidi, J. Goings, B. Peng, A. Petrone, T. Henderson, D. Ranasinghe, V. G. Zakrzewski, J. Gao, N. Rega, G. Zheng, W. Liang, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, K. Throssell, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. J. Bearpark, J. J. Heyd, E. N. Brothers, K. N. Kudin, V. N. Staroverov, T. A. Keith, R. Kobayashi, J. Normand, K. Raghavachari, A. P. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, J. M. Millam, M. Klene, C. Adamo, R. Cammi, J. W. Ochterski, R. L. Martin, K. Morokuma, O. Farkas, J. B. Foresman, and D. J. Fox. Gaussian16, Revision A.03. Wallingford, CT, USA: Gaussian, Inc., 2016.
J. G. Brandenburg, S. Grimme. J. G. Brandenburg, and S. Grimme. Dispersion corrected Hartree–Fock and density functional theory for organic crystal structure prediction. In: Prediction and Calculation of Crystal Structures / Eds. S. Atahan-Evrenk and A. Aspuru-Guzik: Topics in Current Chemistry, Vol. 345. Cham, Switzerland: Springer, 2013, 1-23. https://doi.org/10.1007/128_2013_488
R. Krishnan, J.S. Binkley, R. Seeger, and J. A. Pople. Self-consistent molecular orbital methods. XX. A basis set for correlated wave functions. J. Chem. Phys., 1980, 72(1), 650-654. https://doi.org/10.1063/1.438955
A. D. McLean and G. S. Chandler. Contracted Gaussian basis sets for molecular calculations. I. Second row atoms, Z = 11-18. J. Chem. Phys., 1980, 72(10), 5639-5648. https://doi.org/10.1063/1.438980
I. V. Drebushchak and S. G. Kozlova. Hydrogen bond in the H3O(Ph3PO)3+ complex. Features of the electron density distribution. J. Struct. Chem., 2010, 51(1), 166-169. https://doi.org/10.1007/s10947-010-0023-1
A. T. Smith, P. N. Plessow, and F. Studt. Density functional theory calculations of diffusion barriers of organic molecules through the 8-ring of H-SSZ-13. Chem. Phys., 2021, 541, 111033. https://doi.org/10.1016/j.chemphys.2020.111033
A. V. Vorontsov, P. G. Smirniotis, and U. Kumar. A DFT Study on single Brønsted acid sites in zeolite beta and their interaction with probe molecules. Catalysts, 2023, 13(5), 833. https://doi.org/10.3390/catal13050833
S. Basu, A. K. Sen, and M. Mukherjee. Synthesis and performance evaluation of silica-supported copper chromite catalyst for glycerol dehydration to acetol. J. Chem. Sci., 2019, 131(8), 82. https://doi.org/10.1007/s12039-019-1662-1
Funding
This work was funded by the Russian Science Foundation (project No. 23-23-00448).
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
The authors of this work declare that they have no conflicts of interest.
Additional information
Russian Text © The Author(s), 2024, published in Zhurnal Strukturnoi Khimii, 2024, Vol. 65, No. 3, 124080.https://doi.org/10.26902/JSC_id124080
Publisher’s Note. Pleiades Publishing remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
About this article
Cite this article
Shelyapina, M.G., Maksimova, E.P. & Egorov, A.V. Adsorption of Glycerol at Brønsted Sites in Mordenite: a Density Functional Theory Study. J Struct Chem 65, 574–584 (2024). https://doi.org/10.1134/S0022476624030120
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1134/S0022476624030120