Abstract
A short history of the relationships among adsorption, chemisorption, and catalysis with solid catalysts is reviewed. A special focus is on the development of quality and descriptions accuracy using computers, both for the modeling of elementary physical phenomena and adsorption, as well as for the solution of more complex problems like quantum chemical approach to chemisorption, kinetics over solid catalysts, and reactor systems. Modern approaches to the characterization of solid catalysts from the adsorption-desorption data based mainly on n-layer adsorption and non-linear three parameter BET isotherm regarding the volume of micropores as one of the parameters are demonstrated. Instrumentation techniques like infrared spectroscopy or NMR techniques for the analysis of the strength of component chemisorption are mentioned. As for the kinetics, a vague capability of the Langmuir-Hinshelwood-Hougen-Watson models to describe a reaction system in more complicated cases, e.g. bimolecular surface reactions, is discussed. In this context, the simplest model with a minimum number of parameters is advised. To estimate the most realistic values, intrinsic reaction kinetic and mass transport phenomena are taken into account. Usefulness of quantum mechanistic models for better understanding of the catalytic phenomena and more efficient design of catalysts are outlined.
Similar content being viewed by others
References
Balakrishnan, K., Sachdev, A., & Schwank, J. (1990). Chemisorption and FTIR study of bimetallic Pt-Au/SiO2 catalysts. Journal of Catalysis, 121, 441–455. DOI: 10.1016/0021-9517(90)90252-f.
Báleš, V., Bobok, D., & Kossaczký, E., (1983). Adsorption equilibriu on activated carbon of phenol, p-cresol, and p-nitroaniline in aqueous solutions. Chemical Papers, 37, 289–296.
Barrett, E. P., Joyner, L. G., & Halenda, P. P. (1951). The determination of pore volume and area distributions in porous substances. I. Computations from nitrogen isotherms. Journal of the American Chemical Society, 73, 373–380. DOI: 10.1021/ja01145a126.
Bell, A. T., & Head-Gordon, M. (2011). Quantum mechanical modeling of catalytic processes. Annual Review of Chemical and Biomolecular Engineering, 2, 453–477. DOI: 10.1146/annurev-chembioeng-061010-114108.
Belskaya, O. B., Danilova, I. G., Kazakov, M. O., Mironenko, R. M., Lavrenov, A. V., & Likholobov, V. A. (2012). FTIR Spectroscopy of adsorbed probe molecules for analyzing the surface properties of supported Pt (Pd) catalysts. In T. Theophanides (Ed.), Infrared spectroscopy -Materials science, engineering and technology. Rijeka, Croatia: InTech. DOI: 10.5772/36275.
Berkman, S., Morrell, J. C., & Egloff, G. (1940). Catalysis and adsorption. In S. Berkman (Ed.), Catalysis, inorganic and organic (pp. 60–152). New York, NY, USA: Reinhold.
Berland, K., & Hyldgaard, P. (2013). An analysis of van der Waals density functional components: Binding and corrugation of benzene and C60 on boron nitride and graphene. Physical Review B, 87, 205421. DOI: 10.1103/PhysRevB.87.205421.
Berzelius, J. J. (1835). Sur un force jusqu’ici peu remarquée qui est probablement active dans la formation des composés organiques. Jahres-Bericht, 14, 237–245.
Besedová, E., & Bobok, D. (1995). Adsorption of acetone and cumene on activated carbon. I: Single-component adsorption equilibria of acetone and cumene on Supersorbon HS-4. Adsorption Science & Technology, 12, 39–50.
Besedová, E., Bobok, D., Bafrncová, S., & Steltenpohl, P. (2004). Modelling of gas phase adsorption on activated carbon I. Experiment and equilibrium model. Chemical Papers, 58, 391–396.
Biffis, A., Corain, B., Cvengrošová, Z., Hronec, M., Jeřábek, K., & Králik, M. (1996). Relationships between physico-chemical properties and catalytic activity of polymer-supported palladium catalysts II. Mathematical model. Applied Catalysis A: General, 142, 327–346. DOI: 10.1016/0926-860x(96)00063-4.
Bobok, D., Kossaczký, E., & Ilavský, J. (1970a). Adsorption equilibria of n-heptane on the molecular sieve Calsit 5. Chemical Papers-Chemické Zvesti, 24, 3–12.
Bobok, D., Kossaczký, E., & Ilavský, J. (1970b). Sorption of n-alkanes on the molecular sieves. I. Description of the equipment. Chemical Papers-Chemické Zvesti, 24, 134–138.
Bobok, D., Kossaczký, E., & Šefčíková, M. (1975). Description of equilibrium data of the adsorption of n-heptane on molecular sieve 5 A by an actual form of the Freundlich isotherm. Chemical Papers-Chemické Zvesti, 29, 303–311.
Bobok, D., Kossaczký, E., & Báleš, V. (1979). Adiabatic adsorption of carbon dioxide in fixed bed of the molecular sieve Calsit 5. Chemical Papers-Chemické Zvesti, 33, 357–364.
Bobok, D., Havalda, I., Kossaczky, E., & Ondrejková, M., (1982). Calculation of nonlinearly placed parameters by the method of planned experiment. Chemical Papers-Chemické Zvesti, 36, 433–445.
Bobok, D., Ondrejková, M., & Kossaczký, E. (1989). Diffusion coefficients of n-heptane in a particle of molecular sieve NaY. Chemical Papers-Chemické Zvesti, 43, 345–361.
Bobok, D., & Besedová, E. (2001). The diffusion of chlorinated hydrocarbons in particles of activated carbon. Adsorption Science & Technology, 19, 813–820. DOI: 10.1260/02636170 11494600.
Bobok, D., Besedová, E., Sebeš, K., & Steltenpohl, P. (2004). Application of the adsorbate pore filling correction model to diffusion of ethanol vapours in activated carbon. Petroleum & Coal, 46(1), 41–46.
Bond, G. C. (1957). Platinum metals as hydrogenation catalysts. Platinum Metals Review, 1, 87–93.
Chang, D. J., Min, J. H., Moon, K. H., Park, Y. K., Jeon, J. K., & Ihm, S. K. (2004). Robust numerical simulation of pressure swing adsorption process with strong adsorbate CO2. Chemical Engineering Science, 59, 2715–2725. DOI:10.1016/j.ces.2004.01.067.
Che, M., & Vedrine, J. C. (2012). General introduction. In M. Che, & J. C. Vedrine (Eds.), Characterization of solid materials and heterogeneous catalysts — From structure to surface reactivity (pp. XXXI–XLIII). Weinheim, Germany: Wiley-VCH. DOI: 10.1002/9783527645329.
Chovancová, M., Herain, J., Khandl, V., Moncmanová, A., & Valtýni, J. (1986). Dynamics of adsorption of industrial vapour on carbon sorbent. Chemical Papers-Chemické Zvesti, 40, 19–30.
Dąbrowski, A. (2001). Adsorption — from theory to practice. Advances in Colloid and Interface Science, 93, 135–224. DOI: 10.1016/s0001-8686(00)00082-8.
Dada, A. O., Olalekan, A. P., Olatunya, A. M., & Dada, O. (2012). Langmuir, Freundlich, Temkin and Dubinin-Radushkevich isotherms studies of equilibrium sorption of Zn2+ unto phosphoric acid modified rice husk. IOSR Journal of Applied Chemistry, 3, 38–45. DOI: 10.9790/5736-0313845.
Ertl, G. (1990). Elementary steps in heterogeneous catalysis. Angewandte Chemie International Edition, 29, 1219–1227. DOI:10.1002/anie.199012191.
Ertl, G. (2008). Reactions at surfaces: From atoms to complexity (Nobel lecture). Angewandte Chemie International Edition, 47, 3524–3535. DOI:10.1002/anie.200800480.
Evans, M. G., & Polanyi, M. (1935). Some applications of the transition state method to the calculation of reaction velocities, especially in solution. Transactions of the Faraday Society, 31, 875–894. DOI: 10.1039/tf9353100875.
Eyring, H. (1935). The activated complex in chemical reactions. The Journal of Chemical Physics, 3, 107–115. DOI: 10.1063/1.1749604.
Farberow, C. A., Godinez-Garcia, A., Peng, G. W., Perez-Robles, J. F., Solorza-Feria, O., & Mavrikakis, M. (2013). Mechanistic studies of oxygen reduction by hydrogen on PdAg(110). ACS Catalysis, 3, 1622–1632. DOI: 10.1021/cs 4002699.
Foo, K. Y., & Hameed, B. H. (2010). Insights into the modeling of adsorption isotherm systems. Chemical Engineering Journal, 156, 2–10. DOI:10.1016/j.cej.2009.09.013.
Freundlich, H. (1932). Of the adsorption of gases. Section II. Kinetics and energetics of gas adsorption. Introductory paper to section II. Transactions of the Faraday Society, 28, 195–201. DOI: 10.1039/tf9322800195.
Frumkin, A. N. & Shlygin, A. I. (1935). Über die Platinelektrode. Acta Physico-Chimica URSS, 3, 791–818.
Grassi, M., Kaykioglu, G., Belgiorno, V., & Lofrano, G. (2012). Removal of emerging contaminants from water and wastewater by adsorption process. In G. Lofrano (Ed.), Emerging compounds removal from wastewater (pp. 15–37). Dordrecht, The Netherlands: Springer. DOI: 10.1007/978-94-007-3916-1_2.
Grunze, M., Bozso, F., Ertl, G., & Weiss, M. (1978). Interaction of ammonia with Fe(111) and Fe(100) surfaces. Applications of Surface Science, 1, 241–265. DOI: 10.1016/0378-5963(78)90017-x.
He, X. B., Lyu, J. H., Zhou, H., Zhuang, G. L., Zhong, X., Wang, J. G., & Li, X. N. (2014). Density functional theory study of p-chloroaniline adsorption on Pd surfaces and clusters. International Journal of Quantum Chemistry, 114, 895–899. DOI: 10.1002/qua.24681.
Hinedi, Z. R., Johnston, C. T., & Erickson, C. (1993). Chemisorption of benzene on Cu-montmorillonite as characterized by FTIR and 13C MAS NMR. Clays and Clay Minerals, 41, 87–94. DOI:10.1346/ccmn.1993.0410109.
Huang, P., & Carter, E. A. (2008). Advances in correlated electronic structure methods for solids, surfaces, and nanostructures. Annual Review of Physical Chemistry, 59, 261–290. DOI: 10.1146/annurev.physchem.59.032607.093528.
Harkins, W. D., & Jura, G. (1944). Surfaces of solids. XIII. A vapor adsorption method for the determination of the area of a solid without the assumption of a molecular area, and the areas occupied by nitrogen and other molecules on the surface of a solid. Journal of the American Chemical Society, 66, 1366–1373. DOI: 10.1021/ja01236a048.
Horniakova, J., Králik, M., Kaszonyi, A., & Mravec, D. (2001). A practical approach to the treatment of adsorption-desorption isotherms, acidity and catalytic behaviour of zeolite catalysts. Microporous and Mesoporous Materials, 46, 287–298. DOI:10.1016/s1387-1811(01)00309-2.
Hougen, O. A., & Watson, K. M. (1947). Chemical process principles. Part Three. Kinetics and catalysis. New York, NY, USA: Wiley.
Hu, M. M., Linder, D. P., Buongiorno Nardelli, M., & Striolo, A. (2013). Hydrogen adsorption on platinum-gold bimetallic nanoparticles: A density functional theory study. The Journal of Physical Chemistry C, 117, 15050–15060. DOI: 10.1021/jp3126285.
Hudec, P. (2012). Textúra tuhých materiálov. Charakterizácia adsorbentov a katalyzátorov fyzikálnou adsorpciou dusíka (Texture of solid materials. Characterisation of adsorbents and catalysts via physical nitrogen adsorption). Bratislava, Slovakia: STU. (in Slovak)
Ilavský, J., Kossaczký, E., & Bobok, D. (1970). Sorption of n-alkanes on the molecular sieves. II. A mathematical model for desorption. Chemical Papers-Chemické Zvesti, 24, 252–256.
Jagiello, J., & Thommes, M. (2004). Comparison of DFT characterization methods based on N2, Ar, CO2, and H2 adsorption applied to carbons with various pore size distributions. Carbon, 42, 1227–1232. DOI:10.1016/j.carbon.2004.01.022.
Jiang, Z., Li, L., Xu, J., & Fang, T. (2013). Density functional periodic study of the dehydrogenation of methane on Pd(111) surface. Applied Surface Science, 286, 115–120. DOI:10.1016/j.apsusc.2013.09.030.
Keil, F. J. (2013). Complexities in modeling of heterogeneous catalytic reactions. Computers & Mathematics with Applications, 65, 1674–1697. DOI:10.1016/j.camwa.2012.11.023.
Klappenberger, F. (2014). Two-dimensional functional molecular nanoarchitectures — Complementary investigations with scanning tunneling microscopy and X-ray spectroscopy. Progress in Surface Science, 89, 1–55. DOI: 10.1016/j.progsurf.2013.10.002.
Koper, M. T. M. (2009). Electrocatalysis: theory and experiment at the interface. Faraday Discussions, 140, 11–24. DOI: 10.1039/b812859f.
Kossaczký, E., & Bobok, D. (1974). Diffusion of n-pentane vapour in a crystal of molecular sieve 5A. Chemical Papers-Chemické Zvesti, 28, 166–172.
Kossaczký, E., Bobok, D., & Báleš, V. (1979). Adiabatic equilibrium desorption of carbon dioxide from molecular sieve fixed bed by the stream of inert gas. Chemical Papers-Chemické Zvesti, 33, 439–447.
Kossaczký, E., Kapusta, T., & Bobok, D. (1986). Some problems of simulation of nonisothermal adsorption. Chemical Papers-Chemické Zvesti, 40, 3–18.
Králik, M., Ilavský, J., Pašek, J., & Lehocký, P. (1990). Mathematical dynamic model of the continuous bubble column slurry reactor. Chemical Engineering and Processing: Process Intensification, 28, 127–132. DOI: 10.1016/0255-2701(90)80009-t.
Králik, M., Fišera, R., Zecca, M., D’Archivio, A. A., Galantini, L., Jeřábek, K., & Corain, B. (1998). Modelling of the deactivation of polymer-supported palladium catalysts in the hydrogenation of 4-nitrotoluene. Collection of Czechoslovak Chemical Communications, 63, 1074–1088. DOI:10.1135/cccc19981074.
Kralik, M., Vallusova, Z., Laluch, J., Mikulec, J., & Macho, V. (2008). Comparison of ruthenium catalysts supported on beta and mordenite in the hydrocycloalkylkation of benzene. Petroleum & Coal, 50(1), 44–51.
Kratky, V., Kralik, M., Mecarova, M., Stolcova, M., Zalibera, L., & Hronec, M. (2002). Effect of catalyst and substituents on the hydrogenation of chloronitrobenzenes. Applied Catalysis A: General, 235, 225–231. DOI: 10.1016/s0926-860x(02)00 274-0.
Lecloux, A. J. (1981). Texture of catalysts. In J. R. Anderson, & M. Boudart (Eds.), Catalysis: Science and technology (Vol. 2, pp. 171–230). Berlin, Germany: Springer.
LeVan, D. M., Carta, G., & Yon, C. M. (1997). Adsorption and ion exchange. In R. D. Perry, & D. W. Green (Eds.), Perry’s chemical engineers’ handbook (7th ed., Chapter 16). New York, NY, USA: McGraw-Hill.
Levenspiel, O. (1999). Chemical reaction engineering (3rd ed.). New York, NY, USA: Wiley.
Levenspiel, O. (2002). Modeling in chemical engineering. Chemical Engineering Science, 57, 4691–4696. DOI: 10.1016/s0009-2509(02)00280-4.
Llewellyn, P. L., Bloch, E., & Bourrelly, S. (2012). Surface area/porosity, adsorption, diffusion. In M. Che, & J. C. Védrine (Eds.), Characterization of solid materials and heterogeneous catalysts: From structure to surface reactivity (Vol. 1 & 2, Chapter 19, pp. 853–879). Wienheim, Germany: Wiley-VCH. DOI: 10.1002/9783527645329.ch19.
Lyu, J. H., Wang, J. G., Lu, C. S., Ma, L., Zhang, Q. F., He, X. B., & Li, X. N. (2014). Size-dependent halogenated nitrobenzene hydrogenation selectivity of Pd nanoparticles. The Journal of Physical Chemistry C, 118, 2594–2601. DOI: 10.1021/jp411442f.
McKelvy, M. L., Britt, T. R., Davis, B. L., Gillie, J. K., Graves, F. G., & Lentz, L. A. (1998). Infrared spectroscopy. Analytical Chemistry, 70, 119–178. DOI: 10.1021/a1980006k.
Melo, D. Q., Neto, V. O. S., Oliveira, J. T., Barros, A. L., Gomes, E. C. C., Raulino, G. S. C., Longuinotti, E., & Nascimento, R. F. (2013). Adsorption equilibria of Cu2+, Zn2+, and Cd2+ on EDTA-functionalized silica spheres. Journal of Chemical & Engineering Data, 58, 798–806. DOI: 10.1021/je3013364.
Morbidelli, M., Gavriilidis, A., & Varma, A. (2005). Catalyst design: Optimal distribution of catalyst in pellets, reactors, and membranes. Cambridge, UK: Cambridge University Press.
Murzin, D., & Salmi, T. (2005). Catalytic kinetics. Amsterdam, The Netherlands: Elsevier.
Ostwald, W. (1896). Lehrbuch der allgemeinen Chemie (Vol. 2, Part 1). Leipzig, Germany: Engelmann. (in German)
Pauling, L. (1949). A resonating-valence-bond theory of metals and intermetallic compounds. Proceedings of the Royal Society A, 196, 343–362. DOI:10.1098/rspa.1949.0032.
Peter, M., Flores Camacho, J. M., Adamovski, S., Ono, L. K., Dostert, K. H., O’Brien, C. P., Cuenya, B. R., Schauermann, S., & Freund, H. J. (2013). Trends in the binding strength of surface species on nanoparticles: how does the adsorption energy scale with the particle size?. Angewandte Chemie International Edition, 52, 5175–5179. DOI:10.1002/anie.201209476.
Rajniak, P., Brunovská, A., & Ilavský, J. (1982). Analysis of a one-component sorption in a single adsorbent particle by the orthogonal collocation method. II. Nonisothermal models. Chemical Papers-Chemické Zvesti, 36, 733–744.
Rajniak, P. (1985). Analysis of a one-component sorption in a single adsorbent particle by the orthogonal collocation method. IV. One-point collocation method and linear-driving-force approximation. Chemical Papers-Chemické Zvesti, 39, 447–457.
Rajniak, P., & Yang, R. T. (1993). A simple model and experiments for adsorption-desorption hysteresis: Water vapor on silica gel. AIChE Journal, 39, 774–786. DOI: 10.1002/aic.690390506.
Rajniak, P., & Yang, R. T. (1996). Unified network model for diffusion of condensable vapors in porous media. AIChE Journal, 42, 319–331. DOI:10.1002/aic.690420203.
Rajniak, P., Šoóš, M., & Yang, R. T. (1999). Unified network model for adsorption-desorption in systems with hysteresis. AIChE Journal, 45, 735–750. DOI: 10.1002/aic.690450409.
Risse, T., Carlsson, A., Bäumer, M., Klüner, T., & Freund, H. J. (2003). Using IR intensities as a probe for studying the surface chemical bond. Surface Science, 546, L829–L835. DOI:10.1016/j.susc.2003.09.044.
Rouquerol, J., Avnir, D., Fairbridge, C. W., Everett, D. H., Haynes, J. M., Pernicone, N., Ramsay, J. D. F., Sing, K. S. W., & Unger, K. K. (1994). Recommendations for the characterization of porous solids (Technical Report) Pure and Applied Chemistry, 66, 1739–1758. DOI:10.1351/pac199466081739.
Robertson, A. J. B. (1983). The development of ideas on heterogeneous catalysis. Platinum Metals Review, 27, 31–39.
Rothenberg, G. (2008). Catalysis: Concepts and green applications. Weinheim, Germany: Wiley-VCH. DOI:10.1002/9783527621866.
Ruthven, D. M. (1984). Principles of adsorption & adsorption processes. Hoboken, NJ, USA: Wiley.
Somorjai, G. A. (1994). Introduction to surface chemistry and catalysis. Hoboken, NJ, USA: Wiley.
Satterfield, C. N. (1980). Heterogeneous catalysis in practice. New York, NY, USA: McGraw-Hill.
Sautet, P. (2012). Quantum chemistry methods. In M. Che, & J. C. Védrine (Eds.), Characterization of solid materials and heterogeneous catalysts: From structure to surface reactivity (Vol. 1 & 2, Chapter 24, pp. 1119–1145). Wienheim, Germany: Wiley-VCH. DOI: 10.1002/9783527645329.24.
Shen, S. B., Pan, T. L., Liu, X. Q., Yuan, L., Wang, J. C., Zhang, Y. J., & Guo, Z. C. (2010). Adsorption of Rh(III) complexes from chloride solutions obtained by leaching chlorinated spent automotive catalysts on ion-exchange resin Diaion WA21J. Journal of Hazardous Materials, 179, 104–112. DOI:10.1016/j.jhazmat.2010.02.064.
Schneider, P. (1995). Adsorption isotherms of microporousmesoporous solids revisited. Applied Catalysis A: General, 129, 157–165. DOI: 10.1016/0926-860x(95)00110-7.
Scholtzová, E., Tunega, D., Madejová, J., Pálková, H., & Komadel, P. (2013). Theoretical and experimental study of montmorillonite intercalated with tetramethylammonium cation. Vibrational Spectroscopy, 66, 123–131. DOI:10.1016/j.vibspec.2013.02.006.
Schrödinger, E. (1926). An undulatory theory of the mechanics of atoms and molecules. Physical Review, 28, 1049–1070. DOI: 10.1103/PhysRev.28.1049.
Schwab, G. M. (1981). History of concepts in catalysis. In J. R. Anderson, & M. Boudart (Eds.), Catalysis: Science and technology (Vol. 2, pp. 1–11). Berlin, Germany: Springer.
Sing, K. S. W., Everett, D. H., Haul, R. A. W., Moscou, L., Pierotti, R. A., Rouquérol, J., & Siemieniewska, T. (1985). Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity. Pure and Applied Chemistry, 57, 603–619. DOI:10.1351/pac198557040603.
Šoóš, M., & Rajniak, P. (2001). Percolation model of adsorption-desorption equilibria with hysteresis. Chemical Papers, 55, 391–396.
Thomas, J. M., & Thomas, W. J. (1997). Principles and practice of heterogeneous catalysis. Weinheim, Germany: VCH.
Vannice, M. A. (2005). Kinetics of catalytic reactions. New York, NY, USA: Springer.
van Santen, R. A. (2010). Molecular catalytic kinetics concepts. In A. Cybulski, J. A. Moulijn, & A. Stankiewicz (Eds.), Novel concepts in catalysis and chemical eeactors: Improving the efficiency for the future (Chapter 1, pp. 1–30). Weinheim, Germany: Wiley-VCH. DOI: 10.1002/9783527630882.ch1.
Wisniak, J. (2010). The history of catalysis. From the beginning to Nobel Prizes. Educación Química, 21, 60–69.
Zaera, F. (2013). Shape-controlled nanostructures in heterogeneous catalysis. ChemSusChem, 6, 1797–1820. DOI:10.1002/cssc.201300398.
Author information
Authors and Affiliations
Corresponding author
Additional information
Dedicated to the memory of professor Elemír Kossaczký
Rights and permissions
About this article
Cite this article
Králik, M. Adsorption, chemisorption, and catalysis. Chem. Pap. 68, 1625–1638 (2014). https://doi.org/10.2478/s11696-014-0624-9
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.2478/s11696-014-0624-9