Promotion of adsorptive and catalytic properties of zeolitic Brønsted acid sites by proximal extra-framework Si(OH)x groups

Zhao, Ruixue; Khare, Rachit; Zhang, Yang; Sanchez-Sanchez, Maricruz; Bermejo-Deval, Ricardo; Liu, Yue; Lercher, Johannes A.

doi:10.1038/s41929-022-00906-z

Title: Promotion of adsorptive and catalytic properties of zeolitic Brønsted acid sites by proximal extra-framework Si(OH)_x groups

Journal Article · 29 January 2023 · Nature Catalysis

DOI: https://doi.org/10.1038/s41929-022-00906-z · OSTI ID:2217528

^[1]; Khare, Rachit ^[1]; Zhang, Yang ^[1]; Sanchez-Sanchez, Maricruz ^[1]; Bermejo-Deval, Ricardo ^[1];

^[2];

^[3]

Technical Univ. of Munich (Germany)
Technical Univ. of Munich (Germany); East China Normal Univ. (ECNU), Shanghai (China)
Technical Univ. of Munich (Germany); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Institute for Integrated Catalysis

Steric confinement in zeolites influences the catalytic conversion of alkanes. For zeolitic Brønsted acid sites, proximate extra-framework species introduce additional confinement to the pore constraints, enhancing the catalytic activity of alkane cracking. Although extra-framework alumina has been the most studied, here we report the element-specific impact of silica species. Further, by grafting extra-framework silica species close to Brønsted acid sites in H-ZSM-5 zeolite, the binding of bases like pyridine and amines is strengthened via van der Waals interactions with their aryl or alkyl chains. Brønsted acid sites close to extra-framework silica achieve a higher reaction rate of protolytic cracking of n-pentane via enthalpic (unlike entropic, as with extra-framework alumina) stabilization of the transition state by 24–51 kJ mol⁻¹. The lower activation energy points to an earlier transition state than in the presence of extra-framework alumina, with a better stabilization of the carbonium ions in the transition state compared to the parent zeolite.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 2217528

Report Number(s):: PNNL-SA--183192

Journal Information:: Nature Catalysis, Journal Name: Nature Catalysis Journal Issue: 1 Vol. 6; ISSN 2520-1158

Publisher:: Springer NatureCopyright Statement

Country of Publication:: United States

Language:: English

References (68)

Catalytic cracking of hydrocarbons over modified ZSM-5 zeolites to produce light olefins: A review Rahimi, Nazi; Karimzadeh, Ramin Applied Catalysis A: General, Vol. 398, Issue 1-2 https://doi.org/10.1016/j.apcata.2011.03.009	journal	May 2011
Effects of Light Rare Earth on Acidity and Catalytic Performance of HZSM-5 Zeolite for Catalytic Cracking of Butane to Light Olefins Xiaoning, Wang; Zhen, Zhao; Chunming, Xu Journal of Rare Earths, Vol. 25, Issue 3 https://doi.org/10.1016/S1002-0721(07)60430-X	journal	June 2007
Accurate Coulomb-fitting basis sets for H to Rn Weigend, Florian Physical Chemistry Chemical Physics, Vol. 8, Issue 9 https://doi.org/10.1039/b515623h	journal	January 2006
An improvement of the resolution of the identity approximation for the formation of the Coulomb matrix Neese, Frank Journal of Computational Chemistry, Vol. 24, Issue 14 https://doi.org/10.1002/jcc.10318	journal	September 2003
Effects of Si/Al Ratio on the Distribution of Framework Al and on the Rates of Alkane Monomolecular Cracking and Dehydrogenation in H-MFI Janda, Amber; Bell, Alexis T. Journal of the American Chemical Society, Vol. 135, Issue 51 https://doi.org/10.1021/ja4081937	journal	December 2013
An FT-IR study of the internal and external surfaces of HZSM5 zeolite Trombetta, Marcella; Armaroli, Tiziana; Gutièrrez Alejandre, Aı̀da Applied Catalysis A: General, Vol. 192, Issue 1 https://doi.org/10.1016/S0926-860X(99)00338-5	journal	February 2000
Acid properties of dealuminated beta zeolites studied by IR spectroscopy Guisnet, Michel; Ayrault, Philippe; Coutanceau, Christophe Journal of the Chemical Society, Faraday Transactions, Vol. 93, Issue 8 https://doi.org/10.1039/a607609b	journal	January 1997
On the Role of the Pore Size and Tortuosity for Sorption of Alkanes in Molecular Sieves Eder, F.; Lercher, J. A. The Journal of Physical Chemistry B, Vol. 101, Issue 8 https://doi.org/10.1021/jp961816i	journal	February 1997
Concentration of surface hydroxyl groups on MCM-41 Jentys, A.; Kleestorfer, K.; Vinek, H. Microporous and Mesoporous Materials, Vol. 27, Issue 2-3 https://doi.org/10.1016/S1387-1811(98)00265-0	journal	February 1999
System-Dependent Dispersion Coefficients for the DFT-D3 Treatment of Adsorption Processes on Ionic Surfaces Ehrlich, Stephan; Moellmann, Jonas; Reckien, Werner ChemPhysChem, Vol. 12, Issue 17 https://doi.org/10.1002/cphc.201100521	journal	October 2011
Study of different states of nonframework aluminum in hydrothermally dealuminated HZSM-5 zeolites using diffuse reflectance i.r. spectroscopy Loeffler, E.; Lohse, U.; Peuker, C. Zeolites, Vol. 10, Issue 4 https://doi.org/10.1016/0144-2449(94)90138-4	journal	April 1990
Isomorphous substitution in zeolite frameworks. 1. Acidity of surface hydroxyls in [B]-, [Fe]-, [Ga]-, and [Al]-ZSM-5 Chu, Cynthia T. W.; Chang, Clarence D. The Journal of Physical Chemistry, Vol. 89, Issue 9 https://doi.org/10.1021/j100255a005	journal	April 1985
Integral approximations for LCAO-SCF calculations Vahtras, O.; Almlöf, J.; Feyereisen, M. W. Chemical Physics Letters, Vol. 213, Issue 5-6 https://doi.org/10.1016/0009-2614(93)89151-7	journal	October 1993
On the mechanism of catalyzed isobutane/butene alkylation by zeolites Feller, Andreas; Guzman, Alexander; Zuazo, Iker Journal of Catalysis, Vol. 224, Issue 1 https://doi.org/10.1016/j.jcat.2004.02.019	journal	May 2004
Solvation and acid strength effects on catalysis by faujasite zeolites Gounder, Rajamani; Jones, Andrew J.; Carr, Robert T. Journal of Catalysis, Vol. 286 https://doi.org/10.1016/j.jcat.2011.11.002	journal	February 2012
IR Studies of NH ₃ , Pyridine, CO, and NO Adsorbed on Transition Metal Oxides Kung, Mayfair C.; Kung, Harold H. Catalysis Reviews, Vol. 27, Issue 3 https://doi.org/10.1080/01614948508064741	journal	August 1985
Fully optimized contracted Gaussian basis sets for atoms Li to Kr Schäfer, Ansgar; Horn, Hans; Ahlrichs, Reinhart The Journal of Chemical Physics, Vol. 97, Issue 4 https://doi.org/10.1063/1.463096	journal	August 1992
Changes in catalytic activity of MFI-type zeolites caused by dealumination in a steam atmosphere Masuda, Takao; Fujikata, Yoshihiro; Mukai, Shin R. Applied Catalysis A: General, Vol. 172, Issue 1 https://doi.org/10.1016/S0926-860X(98)00120-3	journal	August 1998
Determination of Integrated Molar Extinction Coefficients for Infrared Absorption Bands of Pyridine Adsorbed on Solid Acid Catalysts Emeis, C. A. Journal of Catalysis, Vol. 141, Issue 2 https://doi.org/10.1006/jcat.1993.1145	journal	June 1993
Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy Weigend, Florian; Ahlrichs, Reinhart Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305 https://doi.org/10.1039/b508541a	journal	January 2005
An Explanation for the Enhanced Activity for Light Alkane Conversion in Mildly Steam Dealuminated Mordenite: The Dominant Role of Adsorption van Bokhoven, J. A.; Tromp, M.; Koningsberger, D. C. Journal of Catalysis, Vol. 202, Issue 1 https://doi.org/10.1006/jcat.2001.3265	journal	August 2001
Results obtained with the correlation energy density functionals of becke and Lee, Yang and Parr Miehlich, Burkhard; Savin, Andreas; Stoll, Hermann Chemical Physics Letters, Vol. 157, Issue 3 https://doi.org/10.1016/0009-2614(89)87234-3	journal	May 1989
The nature of active sites on zeolites V. In situ spectroscopic observations of hydrogen Y zeolite during cumene cracking Ward, J. Journal of Catalysis, Vol. 11, Issue 3 https://doi.org/10.1016/0021-9517(68)90039-0	journal	July 1968
Adsorption of C2−C8 n -Alkanes in Zeolites De Moor, Bart A.; Reyniers, Marie-Françoise; Gobin, Oliver C. The Journal of Physical Chemistry C, Vol. 115, Issue 4 https://doi.org/10.1021/jp106536m	journal	September 2010
Effects of Zeolite Structural Confinement on Adsorption Thermodynamics and Reaction Kinetics for Monomolecular Cracking and Dehydrogenation of n -Butane Janda, Amber; Vlaisavljevich, Bess; Lin, Li-Chiang Journal of the American Chemical Society, Vol. 138, Issue 14 https://doi.org/10.1021/jacs.5b11355	journal	March 2016
Efficient, approximate and parallel Hartree–Fock and hybrid DFT calculations. A ‘chain-of-spheres’ algorithm for the Hartree–Fock exchange Neese, Frank; Wennmohs, Frank; Hansen, Andreas Chemical Physics, Vol. 356, Issue 1-3 https://doi.org/10.1016/j.chemphys.2008.10.036	journal	February 2009
Low-temperature Fourier-transform infrared investigation of the interaction of CO with nanosized ZSM5 and silicalite Zecchina, A.; Bordiga, S.; Spoto, G. J. Chem. Soc., Faraday Trans., Vol. 88, Issue 19 https://doi.org/10.1039/FT9928802959	journal	January 1992
Catalysis by Zeolites – Science and Technology Haag, W. O. Studies in Surface Science and Catalysis https://doi.org/10.1016/S0167-2991(08)63680-0	book	January 1994
Promotion of protolytic pentane conversion on H-MFI zeolite by proximity of extra-framework aluminum oxide and Brønsted acid sites Zhang, Yang; Zhao, Ruixue; Sanchez-Sanchez, Maricruz Journal of Catalysis, Vol. 370 https://doi.org/10.1016/j.jcat.2019.01.006	journal	February 2019
n-Butane Isomerization over Acidic Mordenite Asuquo, R. A.; Edermirth, G.; Lercher, J. A. Journal of Catalysis, Vol. 155, Issue 2 https://doi.org/10.1006/jcat.1995.1219	journal	September 1995
A new type of acidic hydroxyl groups in ZSM-5 zeolite and in mordenite according to diffuse reflectance i.r. spectroscopy Zholobenko, V. L.; Kustov, L. M.; Borovkov, V. Yu. Zeolites, Vol. 8, Issue 3 https://doi.org/10.1016/S0144-2449(88)80303-8	journal	May 1988
The Haag–Dessau mechanism of protolytic cracking of alkanes Kotrel, S.; Knözinger, H.; Gates, B. C. Microporous and Mesoporous Materials, Vol. 35-36 https://doi.org/10.1016/S1387-1811(99)00204-8	journal	April 2000
Challenges on molecular aspects of dealumination and desilication of zeolites Silaghi, Marius-Christian; Chizallet, Céline; Raybaud, Pascal Microporous and Mesoporous Materials, Vol. 191 https://doi.org/10.1016/j.micromeso.2014.02.040	journal	June 2014
Catalytic activity of Brønsted acid sites in zeolites: Intrinsic activity, rate-limiting step, and influence of the local structure of the acid sites Xu, B.; Sievers, C.; Hong, S. Journal of Catalysis, Vol. 244, Issue 2 https://doi.org/10.1016/j.jcat.2006.08.022	journal	December 2006
Brønsted/Lewis Acid Sites Synergy in H-MCM-22 Zeolite Studied by 1H and 27Al DQ-MAS NMR Spectroscopy Yu, Zhiwu; Wang, Qiang; Chen, Lei Chinese Journal of Catalysis, Vol. 33, Issue 1 https://doi.org/10.1016/S1872-2067(10)60287-2	journal	January 2012
Observation of a compensation relation for monomolecular alkane cracking by zeolites: the dominant role of reactant sorption van Bokhoven, Jeroen A.; Williams, Bryce A.; Ji, W. Journal of Catalysis, Vol. 224, Issue 1 https://doi.org/10.1016/j.jcat.2004.02.003	journal	May 2004
Dealumination mechanisms of zeolites and extra-framework aluminum confinement Silaghi, Marius-Christian; Chizallet, Céline; Sauer, Joachim Journal of Catalysis, Vol. 339 https://doi.org/10.1016/j.jcat.2016.04.021	journal	July 2016
Adsorption of water on ZSM 5 zeolites Jentys, Andreas; Warecka, Gerhard; Derewinski, Miroslav The Journal of Physical Chemistry, Vol. 93, Issue 12 https://doi.org/10.1021/j100349a032	journal	June 1989
The catalytic diversity of zeolites: confinement and solvation effects within voids of molecular dimensions Gounder, Rajamani; Iglesia, Enrique Chemical Communications, Vol. 49, Issue 34 https://doi.org/10.1039/c3cc40731d	journal	January 2013
Density functional calculations on first‐row transition metals Russo, Thomas V.; Martin, Richard L.; Hay, P. Jeffrey The Journal of Chemical Physics, Vol. 101, Issue 9 https://doi.org/10.1063/1.468265	journal	November 1994
Shape selective reactions with zeolite catalysts III. Selectivity in xylene isomerization, toluene-methanol alkylation, and toluene disproportionation over ZSM-5 zeolite catalysts Young, L. Journal of Catalysis, Vol. 76, Issue 2 https://doi.org/10.1016/0021-9517(82)90271-8	journal	August 1982
Infrared studies of hydrogen bonding interaction between kaolinite surfaces and intercalated potassium acetate, hydrazine, formamide, and urea Ledoux, Robert L.; White, Joel L. Journal of Colloid and Interface Science, Vol. 21, Issue 2 https://doi.org/10.1016/0095-8522(66)90029-8	journal	February 1966
Brønsted Acid Site and Pore Controlled Siting of Alkane Sorption in Acidic Molecular Sieves Eder, F.; Stockenhuber, M.; Lercher, J. A. The Journal of Physical Chemistry B, Vol. 101, Issue 27 https://doi.org/10.1021/jp9706487	journal	July 1997
Surface acidity of MCM-41 by in situ IR studies of pyridine adsorption Chakraborty, Basab; Viswanathan, B. Catalysis Today, Vol. 49, Issue 1-3 https://doi.org/10.1016/S0920-5861(98)00431-3	journal	February 1999
The nature of active sites on zeolites VIII. Rare earth Y zeolite Ward, J. Journal of Catalysis, Vol. 13, Issue 3 https://doi.org/10.1016/0021-9517(69)90407-2	journal	March 1969
Influence of rare earth elements on the acid and metal sites of Pt/HBEA catalyst for short chain n-alkane hydroisomerization Martins, A.; Silva, J. M.; Ribeiro, M. F. Applied Catalysis A: General, Vol. 466 https://doi.org/10.1016/j.apcata.2013.06.043	journal	September 2013
The confinement effect in zeolites Sastre, G.; Corma, A. Journal of Molecular Catalysis A: Chemical, Vol. 305, Issue 1-2 https://doi.org/10.1016/j.molcata.2008.10.042	journal	June 2009
Brønsted/Lewis Acid Synergy in Dealuminated HY Zeolite: A Combined Solid-State NMR and Theoretical Calculation Study Li, Shenhui; Zheng, Anmin; Su, Yongchao Journal of the American Chemical Society, Vol. 129, Issue 36 https://doi.org/10.1021/ja072767y	journal	September 2007
High-Temperature Produced Catalytic Sites Selective forn-Alkane Dehydrogenation in Acid Zeolites: The Case of HZSM-5 Al-majnouni, Khalid A.; Yun, Jang Ho; Lobo, Raul F. ChemCatChem, Vol. 3, Issue 8 https://doi.org/10.1002/cctc.201100107	journal	June 2011
Proton Mobility, Intrinsic Acid Strength, and Acid Site Location in Zeolites Revealed by Varying Temperature Infrared Spectroscopy and Density Functional Theory Studies Losch, Pit; Joshi, Hrishikesh R.; Vozniuk, Olena Journal of the American Chemical Society, Vol. 140, Issue 50 https://doi.org/10.1021/jacs.8b11588	journal	November 2018
The Effect of Silanisation on the Catalytic and Sorption Properties of Zeolites O’Connor, C. T.; Möller, K. P.; Manstein, H. KONA Powder and Particle Journal, Vol. 25, Issue 0 https://doi.org/10.14356/kona.2007020	journal	January 2007
Probing the Spatial Proximities among Acid Sites in Dealuminated H-Y Zeolite by Solid-State NMR Spectroscopy Li, Shenhui; Huang, Shing-Jong; Shen, Wanling The Journal of Physical Chemistry C, Vol. 112, Issue 37 https://doi.org/10.1021/jp803494n	journal	July 2008
What Is Measured When Measuring Acidity in Zeolites with Probe Molecules? Boronat, Mercedes; Corma, Avelino ACS Catalysis, Vol. 9, Issue 2 https://doi.org/10.1021/acscatal.8b04317	journal	January 2019
Amine adsorption in H-ZSM-5 Parrillo, D. J.; Adamo, A. T.; Kokotailo, G. T. Applied Catalysis, Vol. 67, Issue 1 https://doi.org/10.1016/S0166-9834(00)84435-8	journal	January 1990
Solvent-determined mechanistic pathways in zeolite-H-BEA-catalysed phenol alkylation Liu, Yuanshuai; Baráth, Eszter; Shi, Hui Nature Catalysis, Vol. 1, Issue 2 https://doi.org/10.1038/s41929-017-0015-z	journal	January 2018
0.3 Å Makes the Difference: Dramatic Changes in Methanol-to-Olefin Activities between H-ZSM-12 and H-ZSM-22 Zeolites Wang, Qiong; Cui, Zhi-Min; Cao, Chang-Yan The Journal of Physical Chemistry C, Vol. 115, Issue 50 https://doi.org/10.1021/jp209182u	journal	November 2011
Fine control of the pore-opening size of zeolite ZSM-5 by chemical vapor deposition of silicon methoxide Niwa, Miki; Kato, Masaaki; Hattori, Tadashi The Journal of Physical Chemistry, Vol. 90, Issue 23 https://doi.org/10.1021/j100281a033	journal	November 1986
Chemical Mechanisms of Catalytic Cracking over Solid Acidic Catalysts: Alkanes and Alkenes Kissin, Yury V. Catalysis Reviews, Vol. 43, Issue 1-2 https://doi.org/10.1081/CR-100104387	journal	May 2001
Monomolecular cracking of n-hexane on Y, MOR, and ZSM-5 zeolites Babitz, S. M.; Williams, B. A.; Miller, J. T. Applied Catalysis A: General, Vol. 179, Issue 1-2 https://doi.org/10.1016/S0926-860X(98)00301-9	journal	April 1999
Toward reliable density functional methods without adjustable parameters: The PBE0 model Adamo, Carlo; Barone, Vincenzo The Journal of Chemical Physics, Vol. 110, Issue 13 https://doi.org/10.1063/1.478522	journal	April 1999
The effective site on acid catalysts revealed in n-butene isomerization Ozaki, A. Journal of Catalysis, Vol. 3, Issue 5 https://doi.org/10.1016/0021-9517(64)90142-3	journal	October 1964
Impact of the local environment of Brønsted acid sites in ZSM-5 on the catalytic activity in n-pentane cracking Schallmoser, S.; Ikuno, T.; Wagenhofer, M. F. Journal of Catalysis, Vol. 316 https://doi.org/10.1016/j.jcat.2014.05.004	journal	July 2014
Origin of the size-dependence of the equilibrium van der Waals binding between nanostructures Tao, Jianmin; Perdew, John P.; Tang, Hong The Journal of Chemical Physics, Vol. 148, Issue 7 https://doi.org/10.1063/1.5018572	journal	February 2018
Acid strength and solvation in catalysis by MFI zeolites and effects of the identity, concentration and location of framework heteroatoms Jones, Andrew J.; Carr, Robert T.; Zones, Stacey I. Journal of Catalysis, Vol. 312 https://doi.org/10.1016/j.jcat.2014.01.007	journal	April 2014
The ORCA program system: The ORCA program system Neese, Frank Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 1 https://doi.org/10.1002/wcms.81	journal	June 2011
Hydrolysis of zeolite framework aluminum and its impact on acid catalyzed alkane reactions Xue, Nianhua; Vjunov, Aleksei; Schallmoser, Stefan Journal of Catalysis, Vol. 365 https://doi.org/10.1016/j.jcat.2018.07.015	journal	September 2018
A Periodic DFT Study of the Synergistic Mechanisms between Extraframework Aluminum Species and Bro̷nsted Acid Sites in HY Zeolites Zheng, Jian; Qin, Yucai; Li, Qiang Industrial & Engineering Chemistry Research, Vol. 59, Issue 7 https://doi.org/10.1021/acs.iecr.9b05277	journal	January 2020
Isomerization and hydrocracking of C9 through C16 n-alkanes on Pt/HZSM-5 zeolite Weitkamp, Jens; Jacobs, Peter A.; Martens, Johan A. Applied Catalysis, Vol. 8, Issue 1 https://doi.org/10.1016/0166-9834(83)80058-X	journal	October 1983

Similar Records

Promotion of protolytic pentane conversion on H-MFI zeolite by proximity of extra-framework aluminum oxide and Brønsted acid sites

Journal Article · 2019 · Journal of Catalysis · OSTI ID:1643789

Zhang, Yang; Zhao, Ruixue; Sanchez-Sanchez, Maricruz; +5 more

On the Nature of Extra-Framework Aluminum Species and Improved Catalytic Properties in Steamed Zeolites

Journal Article · 2022 · Molecules · OSTI ID:1893324

Khivantsev, Konstantin; Jaegers, Nicholas R.; Kovarik, Libor; +3 more

Linking low and high temperature NO oxidation mechanisms over Brønsted acidic chabazite to dynamic changes of the active site

Journal Article · 2020 · Journal of Catalysis · OSTI ID:1765166

Salavati-fard, Taha; Lobo, Raul F.; Grabow, Lars C.

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Title: Promotion of adsorptive and catalytic properties of zeolitic Brønsted acid sites by proximal extra-framework Si(OH)x groups

Citation Formats

References (68)

Similar Records

Related Subjects

Title: Promotion of adsorptive and catalytic properties of zeolitic Brønsted acid sites by proximal extra-framework Si(OH)_x groups