Abstract
The adsorption of toluene on cerium oxide was investigated by using in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and density functional theory (DFT) calculations. It is shown that the toluene molecule undergoes dissociative adsorption with the loss of a hydrogen atom from the methyl group and the generation of both, a benzyl (C6H5–CH2−) and a surface hydroxyl species. Characteristic infrared signals are observed due to the formation of a methylene group at 2800 cm−1 (ν CH2) and 1300 cm−1 (δ CH2). All vibrational modes were identified combining DFT calculations of the optimized system and experimental evidences. An adsorbed stable benzyl structure was identified with a binding energy of about − 0.65 eV, which supports the experimental findings. Temperature programmed surface reaction followed by DRIFTS and mass spectrometry showed that benzyl species are oxidized by lattice oxygen to benzoate, formate and, finally, to CO and CO2. Understanding the reactivity of ceria surfaces is key to improve the performance of combustion catalysts for volatile organic compounds abatement.
Similar content being viewed by others
References
He C, Cheng J, Zhang X, Douthwaite M, Pattisson S, Hao Z (2019) Recent advances in the catalytic oxidation of volatile organic compounds: a review based on pollutant sorts and sources. Chem Rev 119:4471–4568. https://doi.org/10.1021/acs.chemrev.8b00408
Wang Q, Yeung KL, Bañares MA (2020) Ceria and its related materials for VOC catalytic combustion: a review. Catal Today 356:141–154. https://doi.org/10.1016/j.cattod.2019.05.016
Fornero EL, Bosco M, Aguirre A, Bonivardi A, Collins SE (2021) Highly disperse CeO2 nanoparticles on MgO hexagonal plates as oxidation catalyst. Appl Catal A 623:118282. https://doi.org/10.1016/j.apcata.2021.118282
Aguirre A, Fornero EL, Villarreal A, Collins SE (2021) Identification of key reaction intermediates during toluene combustion on a Pd/CeO2 catalyst using operando modulated DRIFT spectroscopy. Catal Today. https://doi.org/10.1016/j.cattod.2021.09.009
Schärringer P, Müller TE, Jentys A, Lercher JA (2009) Identification of reaction intermediates during hydrogenation of CD3CN on Raney-Co. J Catal 263:34–41. https://doi.org/10.1016/j.jcat.2009.01.009
Mi R, Li D, Hu Z, Yang RT (2021) Morphology effects of CeO2 nanomaterials on the catalytic combustion of toluene: a combined kinetics and diffuse reflectance infrared Fourier transform spectroscopy study. ACS Catal 11:7876–7889. https://doi.org/10.1021/acscatal.1c01981
López JM, Gilbank AL, García T, Solsona B, Agouram S, Torrente-Murciano L (2015) The prevalence of surface oxygen vacancies over the mobility of bulk oxygen in nanostructured ceria for the total toluene oxidation. Appl Catal B 174–175:403–412. https://doi.org/10.1016/j.apcatb.2015.03.017
Su Z, Yang W, Wang C, Xiong S, Cao X, Peng Y, Si W, Weng Y, Xue M, Li J (2020) Roles of oxygen vacancies in the bulk and surface of CeO2 for toluene catalytic combustion. Environ Sci Technol 54:12684–12692. https://doi.org/10.1021/acs.est.0c03981
Su Z, Si W, Liu H, Xiong S, Chu X, Yang W, Peng Y, Chen J, Cao X, Li J (2021) Boosting the catalytic performance of CeO2 in toluene combustion via the Ce–Ce homogeneous interface. Environ Sci Technol 55:12630–12639. https://doi.org/10.1021/acs.est.1c03999
Trovarelli A (2002) Catalysis by ceria and related materials. Imperial College Press, World Scientific Publishing Co., London
Widmann D, Krautsieder A, Walter P, Brückner A, Behm RJ (2016) How temperature affects the mechanism of CO oxidation on Au/TiO2: a combined EPR and TAP reactor study of the reactive removal of TiO2 surface lattice oxygen in Au/TiO2 by CO. ACS Catal 6:5005–5011. https://doi.org/10.1021/acscatal.6b01219
Aguirre A, Collins SE (2013) Selective detection of reaction intermediates using concentration-modulation excitation DRIFT spectroscopy. Catal Today 205:34–40. https://doi.org/10.1016/j.cattod.2012.08.020
Kresse G, Hafner J (1993) Ab initio molecular dynamics for liquid metals. Phys Rev B 47:558–561. https://doi.org/10.1103/PhysRevB.47.558
Kresse G, Furthmüller J (1996) Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys Rev B 54:11169–11186. https://doi.org/10.1103/PhysRevB.54.11169
Kresse G, Hafner J (1994) Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium. Phys Rev B 49:14251–14269. https://doi.org/10.1103/PhysRevB.49.14251
Blöchl PE (1994) Projector augmented-wave method. Phys Rev B 50:17953–17979. https://doi.org/10.1103/PhysRevB.50.17953
Kresse G, Hafner J (1994) Norm-conserving and ultrasoft pseudopotentials for first-row and transition elements. J Phys Condens Matter 6:8245–8257. https://doi.org/10.1088/0953-8984/6/40/015
Kresse G, Joubert D (1999) From ultrasoft pseudopotentials to the projector augmented-wave method. Phys Rev B 59:1758–1775. https://doi.org/10.1103/PhysRevB.59.1758
Dudarev SL, Botton GA, Savrasov SY, Humphreys CJ, Sutton AP (1998) Electron-energy-loss spectra and the structural stability of nickel oxide: an LSDA+U study. Phys Rev B 57:1505–1509. https://doi.org/10.1103/PhysRevB.57.1505
Perdew JP, Burke K, Ernzerhof M (1997) Generalized gradient approximation made simple [Phys. Rev. Lett. 77, 3865 (1996)]. Phys Rev Lett 78:1396–1396. https://doi.org/10.1103/PhysRevLett.78.1396
Bhasker-Ranganath S, Rahman MS, Zhao C, Calaza F, Wu Z, Xu Y (2021) Elucidating the mechanism of ambient-temperature aldol condensation of acetaldehyde on ceria. ACS Catal 11:8621–8634. https://doi.org/10.1021/acscatal.1c01216
Monkhorst HJ, Pack JD (1976) Special points for Brillouin-zone integrations. Phys Rev B 13:5188–5192. https://doi.org/10.1103/PhysRevB.13.5188
Grimme S, Antony J, Ehrlich S, Krieg H (2010) A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J Chem Phys 132:154104. https://doi.org/10.1063/1.3382344
Grimme S (2006) Semiempirical GGA-type density functional constructed with a long-range dispersion correction. J Comput Chem 27:1787–1799. https://doi.org/10.1002/jcc.20495
Kwon YJ, Son DH, Ahn SJ, Kim MS, Kim K (1994) Vibrational spectroscopic investigation of benzoic acid adsorbed on silver. J Phys Chem 98:8481–8487. https://doi.org/10.1021/j100085a030
Davydov A (2003) Molecular spectroscopy of oxide catalyst surfaces. John Wiley & Sons, Ltd. https://doi.org/10.1002/0470867981
Chang CC, Kokes RJ (1975) Base catalyzed adsorption of toluene by zinc oxide. J Catal 38:491–493. https://doi.org/10.1016/0021-9517(75)90114-1
Davydov AA (1988) Nature of oxide surface sites and their role in formation of toluene complexes. Mater Chem Phys 19:97–112. https://doi.org/10.1016/0254-0584(88)90003-X
Badri A, Binet C, Lavalley J-C (1996) An FTIR study of surface ceria hydroxy groups during a redox process with H2. J Chem Soc Faraday Trans 92:4669. https://doi.org/10.1039/ft9969204669
Binet C, Daturi M, Lavalley J-C (1999) IR study of polycrystalline ceria properties in oxidised and reduced states. Catal Today 50:207–225. https://doi.org/10.1016/S0920-5861(98)00504-5
Lustemberg PG, Bosco MV, Bonivardi A, Busnengo HF, Ganduglia-Pirovano MV (2015) Insights into the nature of formate species in the decomposition and reaction of methanol over cerium oxide surfaces: a combined infrared spectroscopy and density functional theory study. J Phys Chem C 119:21452–21464. https://doi.org/10.1021/acs.jpcc.5b05070
Fernández-Torre D, Kośmider K, Carrasco J, Ganduglia-Pirovano MV, Pérez R (2012) Insight into the adsorption of water on the clean CeO2 (111) surface with van der Waals and hybrid density functionals. J Phys Chem C 116:13584–13593. https://doi.org/10.1021/jp212605g
Vecchietti J, Collins S, Delgado JJ, Małecka M, Rio E, Chen X, Bernal S, Bonivardi A (2011) Gold catalysts supported on cerium-gallium mixed oxide for the carbon monoxide oxidation and water gas shift reaction. Top Catal 54:201–209. https://doi.org/10.1007/s11244-011-9653-6
Bellamy LJ (1975) The infra-red spectra of complex molecules. Springer, Dordrecht
Miyata H, Mukai T, Ono T, Ohno T, Hatayama F (1988) Fourier-transform infrared investigation of intermediates in the oxidation of toluene on V2O5/TiO2. J Chem Soc Faraday Trans 1 84:2465–2475. https://doi.org/10.1039/F19888402465
Busca G, Lorenzelli V (1982) Infrared spectroscopic identification of species arising from reactive adsorption of carbon oxides on metal oxide surfaces. Mater Chem 7:89–126. https://doi.org/10.1016/0390-6035(82)90059-1
Kondo J, Ding N, Maruya K, Domen K, Yokoyama T, Fujita N, Maki T (1993) Infrared study of hydrogenation of benzoic acid to benzaldehyde on ZrO2 catalysts. Bull Chem Soc Jpn 66:3085–3090. https://doi.org/10.1246/bcsj.66.3085
Lu A, Sun H, Zhang N, Che L, Shan S, Luo J, Zheng J, Yang L, Peng D-L, Zhong C-J, Chen B (2019) Surface partial-charge-tuned enhancement of catalytic activity of platinum nanocatalysts for toluene oxidation. ACS Catal 9:7431–7442. https://doi.org/10.1021/acscatal.9b01776
Mo S, Zhang Q, Li J, Sun Y, Ren Q, Zou S, Zhang Q, Lu J, Fu M, Mo D, Wu J, Huang H, Ye D (2020) Highly efficient mesoporous MnO2 catalysts for the total toluene oxidation: oxygen-vacancy defect engineering and involved intermediates using in situ DRIFTS. Appl Catal B 264:118464. https://doi.org/10.1016/j.apcatb.2019.118464
Yang W, Su Z, Xu Z, Yang W, Peng Y, Li J (2020) Comparative study of α-, β-, γ- and δ-MnO2 on toluene oxidation: oxygen vacancies and reaction intermediates. Appl Catal B. https://doi.org/10.1016/j.apcatb.2019.118150
Giordano F, Trovarelli A, de Leitenburg C, Giona M (2000) A model for the temperature-programmed reduction of low and high surface area ceria. J Catal 193:273–282. https://doi.org/10.1006/jcat.2000.2900
Wang Y, Deng W, Wang Y, Guo L, Ishihara T (2018) A comparative study of the catalytic oxidation of chlorobenzene and toluene over Ce–Mn oxides. Mol Catal 459:61–70. https://doi.org/10.1016/j.mcat.2018.08.022
Sun H, Liu Z, Chen S, Quan X (2015) The role of lattice oxygen on the activity and selectivity of the OMS-2 catalyst for the total oxidation of toluene. Chem Eng J 270:58–65. https://doi.org/10.1016/j.cej.2015.02.017
Mirji SA, Halligudi SB, Sawant DP, Patil KR, Gaikwad AB, Pradhan SD (2006) Adsorption of toluene on Si(1 0 0)/SiO2 substrate and mesoporous SBA-15. Colloids Surf A 272:220–226. https://doi.org/10.1016/j.colsurfa.2005.07.019
Besselmann S, Löffler E, Muhler M (2000) On the role of monomeric vanadyl species in toluene adsorption and oxidation on V2O5/TiO2 catalysts: a Raman and in situ DRIFTS study. J Mol Catal A 162:401–411. https://doi.org/10.1016/s1381-1169(00)00307-1
Gordymova TA, Budneva AA, Davydov AA (1982) IR spectra of toluene adsorbed on γ-Al2/O3. React Kinet Catal 20:113–117
Acknowledgements
This research was funded by Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET) [Grant No. PIP-2014-11220130100086CO] and Agencia Nacional de Promoción de la Investigación, el Desarrollo Tecnológico y la Innovación (ANPCyT) [Grant Nos. PICT-2018-01332 and PICT-2017-1342].
Author information
Authors and Affiliations
Corresponding author
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary Information
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Heredia, L., Colombo, E., Quaino, P. et al. Toluene Adsorption on CeO2 (111) Studied by FTIR and DFT. Top Catal 65, 934–943 (2022). https://doi.org/10.1007/s11244-022-01625-2
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11244-022-01625-2