Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

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

Journal Article · · Nature Catalysis
 [1];  [1];  [1];  [1];  [1];  [2];  [3]
  1. Technical Univ. of Munich (Germany)
  2. Technical Univ. of Munich (Germany); East China Normal Univ. (ECNU), Shanghai (China)
  3. Technical Univ. of Munich (Germany); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Institute for Integrated Catalysis
+ Show Author Affiliations
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.
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)

High-Temperature Produced Catalytic Sites Selective forn-Alkane Dehydrogenation in Acid Zeolites: The Case of HZSM-5 journal June 2011
System-Dependent Dispersion Coefficients for the DFT-D3 Treatment of Adsorption Processes on Ionic Surfaces journal October 2011
An improvement of the resolution of the identity approximation for the formation of the Coulomb matrix journal September 2003
The ORCA program system: The ORCA program system journal June 2011
Determination of Integrated Molar Extinction Coefficients for Infrared Absorption Bands of Pyridine Adsorbed on Solid Acid Catalysts journal June 1993
n-Butane Isomerization over Acidic Mordenite journal September 1995
An Explanation for the Enhanced Activity for Light Alkane Conversion in Mildly Steam Dealuminated Mordenite: The Dominant Role of Adsorption journal August 2001
Results obtained with the correlation energy density functionals of becke and Lee, Yang and Parr journal May 1989
Integral approximations for LCAO-SCF calculations journal October 1993
The effective site on acid catalysts revealed in n-butene isomerization journal October 1964
The nature of active sites on zeolites V. In situ spectroscopic observations of hydrogen Y zeolite during cumene cracking journal July 1968
The nature of active sites on zeolites VIII. Rare earth Y zeolite journal March 1969
Shape selective reactions with zeolite catalysts III. Selectivity in xylene isomerization, toluene-methanol alkylation, and toluene disproportionation over ZSM-5 zeolite catalysts journal August 1982
Infrared studies of hydrogen bonding interaction between kaolinite surfaces and intercalated potassium acetate, hydrazine, formamide, and urea journal February 1966
Study of different states of nonframework aluminum in hydrothermally dealuminated HZSM-5 zeolites using diffuse reflectance i.r. spectroscopy journal April 1990
Isomerization and hydrocracking of C9 through C16 n-alkanes on Pt/HZSM-5 zeolite journal October 1983
A new type of acidic hydroxyl groups in ZSM-5 zeolite and in mordenite according to diffuse reflectance i.r. spectroscopy journal May 1988
Amine adsorption in H-ZSM-5 journal January 1990
Catalysis by Zeolites – Science and Technology book January 1994
Surface acidity of MCM-41 by in situ IR studies of pyridine adsorption journal February 1999
Changes in catalytic activity of MFI-type zeolites caused by dealumination in a steam atmosphere journal August 1998
Monomolecular cracking of n-hexane on Y, MOR, and ZSM-5 zeolites journal April 1999
An FT-IR study of the internal and external surfaces of HZSM5 zeolite journal February 2000
Effects of Light Rare Earth on Acidity and Catalytic Performance of HZSM-5 Zeolite for Catalytic Cracking of Butane to Light Olefins journal June 2007
Concentration of surface hydroxyl groups on MCM-41 journal February 1999
The Haag–Dessau mechanism of protolytic cracking of alkanes journal April 2000
Brønsted/Lewis Acid Sites Synergy in H-MCM-22 Zeolite Studied by 1H and 27Al DQ-MAS NMR Spectroscopy journal January 2012
Catalytic cracking of hydrocarbons over modified ZSM-5 zeolites to produce light olefins: A review journal May 2011
Influence of rare earth elements on the acid and metal sites of Pt/HBEA catalyst for short chain n-alkane hydroisomerization journal September 2013
Efficient, approximate and parallel Hartree–Fock and hybrid DFT calculations. A ‘chain-of-spheres’ algorithm for the Hartree–Fock exchange journal February 2009
Observation of a compensation relation for monomolecular alkane cracking by zeolites: the dominant role of reactant sorption journal May 2004
On the mechanism of catalyzed isobutane/butene alkylation by zeolites journal May 2004
Catalytic activity of Brønsted acid sites in zeolites: Intrinsic activity, rate-limiting step, and influence of the local structure of the acid sites journal December 2006
Solvation and acid strength effects on catalysis by faujasite zeolites journal February 2012
Acid strength and solvation in catalysis by MFI zeolites and effects of the identity, concentration and location of framework heteroatoms journal April 2014
Impact of the local environment of Brønsted acid sites in ZSM-5 on the catalytic activity in n-pentane cracking journal July 2014
Dealumination mechanisms of zeolites and extra-framework aluminum confinement journal July 2016
Hydrolysis of zeolite framework aluminum and its impact on acid catalyzed alkane reactions journal September 2018
Promotion of protolytic pentane conversion on H-MFI zeolite by proximity of extra-framework aluminum oxide and Brønsted acid sites journal February 2019
Challenges on molecular aspects of dealumination and desilication of zeolites journal June 2014
The confinement effect in zeolites journal June 2009
A Periodic DFT Study of the Synergistic Mechanisms between Extraframework Aluminum Species and Bro̷nsted Acid Sites in HY Zeolites journal January 2020
What Is Measured When Measuring Acidity in Zeolites with Probe Molecules? journal January 2019
Isomorphous substitution in zeolite frameworks. 1. Acidity of surface hydroxyls in [B]-, [Fe]-, [Ga]-, and [Al]-ZSM-5 journal April 1985
Fine control of the pore-opening size of zeolite ZSM-5 by chemical vapor deposition of silicon methoxide journal November 1986
Adsorption of water on ZSM 5 zeolites journal June 1989
Brønsted/Lewis Acid Synergy in Dealuminated HY Zeolite:  A Combined Solid-State NMR and Theoretical Calculation Study journal September 2007
Effects of Si/Al Ratio on the Distribution of Framework Al and on the Rates of Alkane Monomolecular Cracking and Dehydrogenation in H-MFI journal December 2013
Effects of Zeolite Structural Confinement on Adsorption Thermodynamics and Reaction Kinetics for Monomolecular Cracking and Dehydrogenation of n -Butane journal March 2016
Proton Mobility, Intrinsic Acid Strength, and Acid Site Location in Zeolites Revealed by Varying Temperature Infrared Spectroscopy and Density Functional Theory Studies journal November 2018
Adsorption of C2−C8 n -Alkanes in Zeolites journal September 2010
0.3 Å Makes the Difference: Dramatic Changes in Methanol-to-Olefin Activities between H-ZSM-12 and H-ZSM-22 Zeolites journal November 2011
Probing the Spatial Proximities among Acid Sites in Dealuminated H-Y Zeolite by Solid-State NMR Spectroscopy journal July 2008
On the Role of the Pore Size and Tortuosity for Sorption of Alkanes in Molecular Sieves journal February 1997
Brønsted Acid Site and Pore Controlled Siting of Alkane Sorption in Acidic Molecular Sieves journal July 1997
Solvent-determined mechanistic pathways in zeolite-H-BEA-catalysed phenol alkylation journal January 2018
Low-temperature Fourier-transform infrared investigation of the interaction of CO with nanosized ZSM5 and silicalite journal January 1992
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
Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy journal January 2005
Accurate Coulomb-fitting basis sets for H to Rn journal January 2006
The catalytic diversity of zeolites: confinement and solvation effects within voids of molecular dimensions journal January 2013
Fully optimized contracted Gaussian basis sets for atoms Li to Kr journal August 1992
Density functional calculations on first‐row transition metals journal November 1994
Toward reliable density functional methods without adjustable parameters: The PBE0 model journal April 1999
Origin of the size-dependence of the equilibrium van der Waals binding between nanostructures journal February 2018
IR Studies of NH 3 , Pyridine, CO, and NO Adsorbed on Transition Metal Oxides journal August 1985
Chemical Mechanisms of Catalytic Cracking over Solid Acidic Catalysts: Alkanes and Alkenes journal May 2001
The Effect of Silanisation on the Catalytic and Sorption Properties of Zeolites journal January 2007

Figures / Tables (8)

Fig. 1(p. 2)figure Fig. 1
Fig. 2(p. 3)figure Fig. 2
Fig. 3(p. 4)figure Fig. 3
Fig. 4(p. 5)figure Fig. 4
Table 1(p. 5)table Table 1
Fig. 5(p. 6)figure Fig. 5
Table 2(p. 6)table Table 2
Fig. 6(p. 7)figure Fig. 6

Similar Records

Promotion of protolytic pentane conversion on H-MFI zeolite by proximity of extra-framework aluminum oxide and Brønsted acid sites
Journal Article · Thu Jan 31 23:00:00 EST 2019 · Journal of Catalysis · OSTI ID:1643789
On the Nature of Extra-Framework Aluminum Species and Improved Catalytic Properties in Steamed Zeolites
Journal Article · Tue Apr 05 20:00:00 EDT 2022 · Molecules · OSTI ID:1893324
Linking low and high temperature NO oxidation mechanisms over Brønsted acidic chabazite to dynamic changes of the active site
Journal Article · Fri May 29 20:00:00 EDT 2020 · Journal of Catalysis · OSTI ID:1765166

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY