Highly dispersed SiOx/Al2O3 catalysts illuminate the reactivity of isolated silanol sites

Mouat, Aidan R.; George, Cassandra; Kobayashi, Takeshi; Pruski, Marek; van Duyne, Richard P.; Marks, Tobin J.; Stair, Peter C.

doi:10.1002/anie.201505452

Title: Highly dispersed SiO_x/Al₂O₃ catalysts illuminate the reactivity of isolated silanol sites

Abstract

The reaction of γ-alumina with tetraethylorthosilicate (TEOS) vapor at low temperatures selectively yields monomeric SiO_x species on the alumina surface. These isolated (-AlO)₃Si(OH) sites are characterized by PXRD, XPS, DRIFTS of adsorbed NH₃, CO, and pyridine, and ²⁹Si and ²⁷Al DNP-enhanced solid-state NMR spectroscopy. The formation of isolated sites suggests that TEOS reacts preferentially at strong Lewis acid sites on the γ-Al₂O₃ surface, functionalizing the surface with “mild” Brønsted acid sites. As a result, for liquid-phase catalytic cyclohexanol dehydration, these SiO_x sites exhibit up to 3.5-fold higher specific activity than the parent alumina with identical selectivity.

Authors:

Mouat, Aidan R. ^[1]; George, Cassandra ^[1]; Kobayashi, Takeshi ^[2]; Pruski, Marek ^[2]; van Duyne, Richard P. ^[1]; Marks, Tobin J. ^[1]; Stair, Peter C. ^[1]

Northwestern Univ., Evanston, IL (United States)
Iowa State Univ., Ames, IA (United States)

Publication Date:: Wed Sep 23 00:00:00 EDT 2015

Research Org.:: Ames Laboratory (AMES), Ames, IA (United States)

Sponsoring Org.:: USDOE

OSTI Identifier:: 1227425

Report Number(s):: IS-J-8828
Journal ID: ISSN 1433-7851

Grant/Contract Number:: CHE1213235; CHE0923236; AC02-06CH11357; FG02-03ER15457; DMR1121262; EEC0118025/003; SC0001329; AC02-07CH11358

Resource Type:: Journal Article: Accepted Manuscript

Journal Name:: Angewandte Chemie (International Edition)

Additional Journal Information:: Journal Volume: 54; Journal Issue: 45; Journal ID: ISSN 1433-7851

Publisher:: Wiley

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Mouat, Aidan R., George, Cassandra, Kobayashi, Takeshi, Pruski, Marek, van Duyne, Richard P., Marks, Tobin J., and Stair, Peter C. Highly dispersed SiOx/Al2O3 catalysts illuminate the reactivity of isolated silanol sites.  United States: N. p., 2015. 
        Web.  doi:10.1002/anie.201505452.

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                    Mouat, Aidan R., George, Cassandra, Kobayashi, Takeshi, Pruski, Marek, van Duyne, Richard P., Marks, Tobin J., & Stair, Peter C. Highly dispersed SiOx/Al2O3 catalysts illuminate the reactivity of isolated silanol sites.  United States.  https://doi.org/10.1002/anie.201505452

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                    Mouat, Aidan R., George, Cassandra, Kobayashi, Takeshi, Pruski, Marek, van Duyne, Richard P., Marks, Tobin J., and Stair, Peter C. 2015.  
        "Highly dispersed SiOx/Al2O3 catalysts illuminate the reactivity of isolated silanol sites".  United States.  https://doi.org/10.1002/anie.201505452.  https://www.osti.gov/servlets/purl/1227425.

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@article{osti_1227425,

  title        = {Highly dispersed SiOx/Al2O3 catalysts illuminate the reactivity of isolated silanol sites},

  author       = {Mouat, Aidan R. and George, Cassandra and Kobayashi, Takeshi and Pruski, Marek and van Duyne, Richard P. and Marks, Tobin J. and Stair, Peter C.},

  abstractNote = {The reaction of γ-alumina with tetraethylorthosilicate (TEOS) vapor at low temperatures selectively yields monomeric SiOx species on the alumina surface. These isolated (-AlO)3Si(OH) sites are characterized by PXRD, XPS, DRIFTS of adsorbed NH3, CO, and pyridine, and 29Si and 27Al DNP-enhanced solid-state NMR spectroscopy. The formation of isolated sites suggests that TEOS reacts preferentially at strong Lewis acid sites on the γ-Al2O3 surface, functionalizing the surface with “mild” Brønsted acid sites. As a result, for liquid-phase catalytic cyclohexanol dehydration, these SiOx sites exhibit up to 3.5-fold higher specific activity than the parent alumina with identical selectivity.},

  doi          = {10.1002/anie.201505452},

  url          = {https://www.osti.gov/biblio/1227425},
  journal      = {Angewandte Chemie (International Edition)},

  issn         = {1433-7851},

  number       = 45,

  volume       = 54,

  place        = {United States},

  year         = {Wed Sep 23 00:00:00 EDT 2015},

  month        = {Wed Sep 23 00:00:00 EDT 2015}

}

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Works referenced in this record:

A quantum-chemical approach to the generation of solid acidity in composite metal oxides
journal, January 1984

Kawakami, Hiroshi; Yoshida, Satohiro; Yonezawa, Teijiro
Journal of the Chemical Society, Faraday Transactions 2, Vol. 80, Issue 3
https://doi.org/10.1039/f29848000205

A Fast XPS study of the surface chemistry of ethanol over Pt{111}
journal, January 2004

Lee, Adam F.; Gawthrope, David E.; Hart, Nicholas J.
Surface Science, Vol. 548, Issue 1-3
https://doi.org/10.1016/j.susc.2003.11.004

Acidic Crystalline Aluminosilicates. New Superactive, Superselective Cracking Catalysts
journal, September 1964

Plank, C. J.; Rosinski, E. J.; Hawthorne, W. P.
Industrial & Engineering Chemistry Product Research and Development, Vol. 3, Issue 3
https://doi.org/10.1021/i360011a001

Thin silica layer on alumina: evidence of the acidity in the monolayer
journal, August 1990

Niwa, Miki.; Katada, Naonobu.; Murakami, Yuichi.
The Journal of Physical Chemistry, Vol. 94, Issue 16
https://doi.org/10.1021/j100379a052

The Acidity of Zeolites: Concepts, Measurements and Relation to Catalysis: A Review on Experimental and Theoretical Methods for the Study of Zeolite Acidity
journal, October 2013

Derouane, E. G.; Védrine, J. C.; Pinto, R. Ramos
Catalysis Reviews, Vol. 55, Issue 4
https://doi.org/10.1080/01614940.2013.822266

Acidic catalysts for the dehydration of glycerol: Activity and deactivation
journal, August 2009

Suprun, Wladimir; Lutecki, Michal; Haber, Thomas
Journal of Molecular Catalysis A: Chemical, Vol. 309, Issue 1-2
https://doi.org/10.1016/j.molcata.2009.04.017

Solid Acids and Bases
book, January 1970

Tanabe, Kozo
Solid Acids and Bases: Their Catalytic Properties
https://doi.org/10.1016/B978-0-12-683250-1.50005-5

XPS analysis of oxides
journal, July 1988

Paparazzo, E.
Surface and Interface Analysis, Vol. 12, Issue 2
https://doi.org/10.1002/sia.740120210

SURFACE HYDROXYL GROUPS ON γ-ALUMINA ¹
journal, October 1960

Peri, J. B.; Hannan, R. B.
The Journal of Physical Chemistry, Vol. 64, Issue 10
https://doi.org/10.1021/j100839a044

Deactivation of a silica-alumina catalyst by coke deposition
journal, November 1993

Garcia-Ochoa, Felix; Santos, Aurora
Industrial & Engineering Chemistry Research, Vol. 32, Issue 11
https://doi.org/10.1021/ie00023a028

Modification of polymer-gel structures
journal, February 1984

Yoldas, Bulent E.
Journal of Non-Crystalline Solids, Vol. 63, Issue 1-2
https://doi.org/10.1016/0022-3093(84)90393-4

Synthesis of amorphous aluminosilicates by grafting: Tuning the building and final structure of the deposit by selecting the appropriate synthesis conditions
journal, February 2014

Caillot, Maxime; Chaumonnot, Alexandra; Digne, Mathieu
Microporous and Mesoporous Materials, Vol. 185
https://doi.org/10.1016/j.micromeso.2013.10.032

Surface chemistry of atomic layer deposition: A case study for the trimethylaluminum/water process
journal, June 2005

Puurunen, Riikka L.
Journal of Applied Physics, Vol. 97, Issue 12, Article No. 121301
https://doi.org/10.1063/1.1940727

Impact of solvent for individual steps of phenol hydrodeoxygenation with Pd/C and HZSM-5 as catalysts
journal, January 2014

He, Jiayue; Zhao, Chen; Lercher, Johannes A.
Journal of Catalysis, Vol. 309
https://doi.org/10.1016/j.jcat.2013.09.009

FT-IR Studies on Light Olefin Skeletal Isomerization Catalysis
journal, October 1998

Trombetta, Marcella; Busca, Guido; Rossini, Stefano
Journal of Catalysis, Vol. 179, Issue 2
https://doi.org/10.1006/jcat.1998.2251

The surface of transitional aluminas: A critical review
journal, May 2014

Busca, Guido
Catalysis Today, Vol. 226
https://doi.org/10.1016/j.cattod.2013.08.003

Catalytically Active Sites for the Beckmann Rearrangement of Cyclohexanone Oxime to ε-Caprolactam
journal, August 1999

Heitmann, G. P.; Dahlhoff, G.; Hölderich, W. F.
Journal of Catalysis, Vol. 186, Issue 1
https://doi.org/10.1006/jcat.1999.2552

Quantification of Brønsted Acid Sites of Grafted Amorphous Silica-Alumina Compounds and their Turnover Frequency in m -Xylene Isomerization
journal, October 2013

Caillot, Maxime; Chaumonnot, Alexandra; Digne, Mathieu
ChemCatChem, Vol. 5, Issue 12
https://doi.org/10.1002/cctc.201300560

Grafted Poly(1→4-β-glucan) Strands on Silica: A Comparative Study of Surface Reactivity as a Function of Grafting Density
journal, December 2011

Gazit, Oz M.; Katz, Alexander
Langmuir, Vol. 28, Issue 1
https://doi.org/10.1021/la2036482

Understanding the Role of Defect Sites in Glucan Hydrolysis on Surfaces
journal, March 2013

Gazit, Oz M.; Katz, Alexander
Journal of the American Chemical Society, Vol. 135, Issue 11
https://doi.org/10.1021/ja311918z

Dynamic nuclear polarization at high magnetic fields
journal, February 2008

Maly, Thorsten; Debelouchina, Galia T.; Bajaj, Vikram S.
The Journal of Chemical Physics, Vol. 128, Issue 5
https://doi.org/10.1063/1.2833582

Surface Modification of Au/TiO ₂ Catalysts by SiO ₂ via Atomic Layer Deposition
journal, May 2008

Ma, Zhen; Brown, Suree; Howe, Jane Y.
The Journal of Physical Chemistry C, Vol. 112, Issue 25
https://doi.org/10.1021/jp801484h

The variety of Brønsted acid sites in amorphous aluminosilicates and zeolites
journal, July 2014

Caillot, Maxime; Chaumonnot, Alexandra; Digne, Mathieu
Journal of Catalysis, Vol. 316
https://doi.org/10.1016/j.jcat.2014.05.002

A Novel Method To Synthesize Amorphous Silica−Alumina Materials with Mesoporous Distribution without Using Templates and Pore-Regulating Agents
journal, January 2002

Yao, Nan; Xiong, Guoxing; He, Mingyuan
Chemistry of Materials, Vol. 14, Issue 1
https://doi.org/10.1021/cm010270w

Surface Enhanced NMR Spectroscopy by Dynamic Nuclear Polarization
journal, November 2010

Lesage, Anne; Lelli, Moreno; Gajan, David
Journal of the American Chemical Society, Vol. 132, Issue 44
https://doi.org/10.1021/ja104771z

Brønsted acid sites of zeolitic strength in amorphous silica-alumina
journal, January 2010

Poduval, Dilip G.; van Veen, J. A. Rob; Rigutto, Marcello S.
Chemical Communications, Vol. 46, Issue 20
https://doi.org/10.1039/c000019a

Catalytic Properties of Silica-Alumina Prepared by Chemical Vapor Deposition
journal, August 1987

Sato, Satoshi; Toita, Masato; Yu, Yu-Qing
Chemistry Letters, Vol. 16, Issue 8
https://doi.org/10.1246/cl.1987.1535

A methanol to olefins review: Diffusion, coke formation and deactivation on SAPO type catalysts
journal, December 2012

Chen, D.; Moljord, K.; Holmen, A.
Microporous and Mesoporous Materials, Vol. 164
https://doi.org/10.1016/j.micromeso.2012.06.046

ALD of SiO[sub 2] at Room Temperature Using TEOS and H[sub 2]O with NH[sub 3] as the Catalyst
journal, January 2004

Ferguson, J. D.; Smith, E. R.; Weimer, A. W.
Journal of The Electrochemical Society, Vol. 151, Issue 8
https://doi.org/10.1149/1.1768548

X-ray photoelectron spectroscopy of low-temperature anodic silicon oxides: LOW-TEMPERATURE ANODIC SILICON OXIDES
journal, June 1992

Galán, L.; Montero, I.; Rueda, F.
Surface and Interface Analysis, Vol. 19, Issue 1-12
https://doi.org/10.1002/sia.740190189

Fine control of the pore-opening size of the zeolite mordenite by chemical vapour deposition of silicon alkoxide
journal, January 1984

Niwa, Miki; Kato, Satoshi; Hattori, Tadashi
Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 80, Issue 11
https://doi.org/10.1039/f19848003135

Characterization of oxide surfaces and zeolites by carbon monoxide as an IR probe molecule
book, January 2002

Hadjiivanov, Konstantin I.; Vayssilov, Georgi N.
Advances in Catalysis
https://doi.org/10.1016/S0360-0564(02)47008-3

Infrared spectrum of ammonia adsorbed on silica-alumina
journal, February 1967

Basila, Michael R.; Kantner, Theodore R.
The Journal of Physical Chemistry, Vol. 71, Issue 3
https://doi.org/10.1021/j100862a001

Structure of SiO2 and Al2O3 Monolayer Catalysts: Investigation by Infrared-Spectroscopy and 29Si MAS NMR
journal, July 1994

Sheng, T. C.; Lang, S.; Morrow, B. A.
Journal of Catalysis, Vol. 148, Issue 1
https://doi.org/10.1006/jcat.1994.1215

Experimental and QM/MM investigation of the hydrated silica surface reactivity
journal, April 2005

Casarin, Maurizio; Falcomer, Daniele; Glisenti, Antonella
Chemical Physics Letters, Vol. 405, Issue 4-6
https://doi.org/10.1016/j.cplett.2005.02.076

A 29Si NMR investigation of the structure of amorphous silica—alumina supports
journal, January 1989

McMillan, M.; Brinen, J. S.; Carruthers, J. D.
Colloids and Surfaces, Vol. 38, Issue 1
https://doi.org/10.1016/0166-6622(89)80150-7

Viscous flow reactor with quartz crystal microbalance for thin film growth by atomic layer deposition
journal, August 2002

Elam, J. W.; Groner, M. D.; George, S. M.
Review of Scientific Instruments, Vol. 73, Issue 8, p. 2981-2987
https://doi.org/10.1063/1.1490410

Chemistry of Cracking Catalysts
journal, November 1949

Thomas, Charles L.
Industrial & Engineering Chemistry, Vol. 41, Issue 11
https://doi.org/10.1021/ie50479a042

Catalytic dehydration of ethanol over silica-alumina
journal, June 1969

Roca, F.
Journal of Catalysis, Vol. 14, Issue 2
https://doi.org/10.1016/0021-9517(69)90414-X

Mechanisms of xylene isomerization over acidic solid catalysts
journal, April 2000

Guisnet, M.; Gnep, N. S.; Morin, S.
Microporous and Mesoporous Materials, Vol. 35-36
https://doi.org/10.1016/S1387-1811(99)00207-3

Catalytic conversion of methane to more useful chemicals and fuels: a challenge for the 21st century
journal, December 2000

Lunsford, Jack H.
Catalysis Today, Vol. 63, Issue 2-4, p. 165-174
https://doi.org/10.1016/S0920-5861(00)00456-9

Synthesis of ketenes from carboxylic acids on functionalized silica monoliths at short contact times
journal, August 2000

Martinez, R.; Huff, M. C.; Barteau, M. A.
Applied Catalysis A: General, Vol. 200, Issue 1-2
https://doi.org/10.1016/S0926-860X(00)00649-9

Atomic layer deposition of SiO2 at room temperature using NH3-catalyzed sequential surface reactions
journal, February 2000

Klaus, J. W.; George, S. M.
Surface Science, Vol. 447, Issue 1-3
https://doi.org/10.1016/S0039-6028(99)01119-X

The nature of the relative bonding chemistry in zeolites: An XPS study
journal, November 1990

Barr, Tery L.
Zeolites, Vol. 10, Issue 8
https://doi.org/10.1016/0144-2449(90)90058-Y

Model silica-alumina acid catalysts for surface science and catalysis studies prepared by argon ion beam sputter deposition using HY-zeolite targets
journal, January 1991

B�sz�rm�nyi, Istvan; Nakayama, Taisei; McIntyre, Brian
Catalysis Letters, Vol. 10, Issue 5-6
https://doi.org/10.1007/BF00769169

Microstructure of silica monolayer solid acid catalysts determined by 29Si NMR spectroscopy
journal, May 1998

Katada, Naonobu; Niwa, Miki
Research on Chemical Intermediates, Vol. 24, Issue 5
https://doi.org/10.1163/156856798X00014

FT-IR characterization of silicated aluminas, active olefin skeletal isomerization catalysts
journal, January 1997

Finocchio, Elisabetta; Busca, Guido; Rossini, Stefano
Catalysis Today, Vol. 33, Issue 1-3
https://doi.org/10.1016/S0920-5861(96)00106-X

Adsorption Assisted Desorption of NH ₃ on γ-Alumina Studied with Positron Emission Profiling
journal, April 2004

Sobczyk, D. P.; Hesen, J. J. G.; van Grondelle, J.
Catalysis Letters, Vol. 94, Issue 1/2
https://doi.org/10.1023/B:CATL.0000019328.16620.1d

2,6-Dimethylpyridine as a probe of the strength of Brønsted acid sites: study on zeolites. Application to alumina
journal, January 2005

Oliviero, Laetitia; Vimont, Alexandre; Lavalley, Jean-Claude
Phys. Chem. Chem. Phys., Vol. 7, Issue 8
https://doi.org/10.1039/B500689A

Works referencing / citing this record:

NMR Spectroscopic Characterization of Flame‐Made Amorphous Silica‐Alumina for Cyclohexanol and Glyceraldehyde Conversion
journal, October 2019

Wang, Zichun; Jiang, Yijiao; Stampfl, Catherine
ChemCatChem, Vol. 12, Issue 1
https://doi.org/10.1002/cctc.201901728

Shedding light on the atomic-scale structure of amorphous silica–alumina and its Brønsted acid sites
journal, January 2019

Perras, Frédéric A.; Wang, Zichun; Kobayashi, Takeshi
Physical Chemistry Chemical Physics, Vol. 21, Issue 35
https://doi.org/10.1039/c9cp04099d

Probing acid sites in solid catalysts with pyridine UV-Vis spectroscopy
journal, January 2018

Velthoen, Marjolein E. Z.; Nab, Sophie; Weckhuysen, Bert M.
Physical Chemistry Chemical Physics, Vol. 20, Issue 33
https://doi.org/10.1039/c8cp03991g

Strong electrostatic adsorption of Pt onto SiO ₂ partially overcoated Al ₂ O ₃ —Towards single atom catalysts
journal, December 2019

Bo, Zhenyu; McCullough, Lauren R.; Dull, Samuel
The Journal of Chemical Physics, Vol. 151, Issue 21
https://doi.org/10.1063/1.5128934

Acidity enhancement through synergy of penta- and tetra-coordinated aluminum species in amorphous silica networks
journal, January 2020

Wang, Zichun; Li, Tong; Jiang, Yijiao
Nature Communications, Vol. 11, Issue 1
https://doi.org/10.1038/s41467-019-13907-7

Atomic Layer Deposition (ALD) as a Way to Prepare New Mixed-Oxide Catalyst Supports: The Case of Alumina Addition to Silica-Supported Platinum for the Selective Hydrogenation of Cinnamaldehyde
journal, March 2019

Weng, Zhihuan; Zaera, Francisco
Topics in Catalysis, Vol. 62, Issue 12-16
https://doi.org/10.1007/s11244-019-01163-4

Shedding light on the atomic-scale structure of amorphous silica-alumina and its Brønsted acid sites
text, January 2019

Perras, Frédéric A.; Wang, Zichun; Kobayashi, Takeshi
ETH Zurich
https://doi.org/10.3929/ethz-b-000364135

Acidity enhancement through synergy of penta- and tetra-coordinated aluminum species in amorphous silica networks
text, January 2020

Wang, Zichun; Li, Tong; Jiang, Yijiao
ETH Zurich
https://doi.org/10.3929/ethz-b-000391784

Determining the Surface Structure of Silicated Alumina Catalysts via Isotopic Enrichment and Dynamic Nuclear Polarization Surface-Enhanced NMR Spectroscopy
journal, October 2017

Rankin, Andrew G. M.; Webb, Paul B.; Dawson, Daniel M.
The Journal of Physical Chemistry C, Vol. 121, Issue 41
https://doi.org/10.1021/acs.jpcc.7b08137

Three-Dimensional Structure Determination of Surface Sites
journal, January 2017

Berruyer, Pierrick; Lelli, Moreno; Conley, Matthew P.
Journal of the American Chemical Society, Vol. 139, Issue 2
https://doi.org/10.1021/jacs.6b10894

Acidity enhancement through synergy of penta- and tetra-coordinated aluminum species in amorphous silica networks
journal, January 2020

Wang, Zichun; Li, Tong; Jiang, Yijiao
Nature Communications, Vol. 11, Issue 1
https://doi.org/10.1038/s41467-019-13907-7

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Title: Highly dispersed SiOx/Al2O3 catalysts illuminate the reactivity of isolated silanol sites

Abstract

Citation Formats

A quantum-chemical approach to the generation of solid acidity in composite metal oxides journal, January 1984

A Fast XPS study of the surface chemistry of ethanol over Pt{111} journal, January 2004

Acidic Crystalline Aluminosilicates. New Superactive, Superselective Cracking Catalysts journal, September 1964

Thin silica layer on alumina: evidence of the acidity in the monolayer journal, August 1990

The Acidity of Zeolites: Concepts, Measurements and Relation to Catalysis: A Review on Experimental and Theoretical Methods for the Study of Zeolite Acidity journal, October 2013

Acidic catalysts for the dehydration of glycerol: Activity and deactivation journal, August 2009

Solid Acids and Bases book, January 1970

XPS analysis of oxides journal, July 1988

SURFACE HYDROXYL GROUPS ON γ-ALUMINA 1 journal, October 1960

Deactivation of a silica-alumina catalyst by coke deposition journal, November 1993

Modification of polymer-gel structures journal, February 1984

Synthesis of amorphous aluminosilicates by grafting: Tuning the building and final structure of the deposit by selecting the appropriate synthesis conditions journal, February 2014

Surface chemistry of atomic layer deposition: A case study for the trimethylaluminum/water process journal, June 2005

Impact of solvent for individual steps of phenol hydrodeoxygenation with Pd/C and HZSM-5 as catalysts journal, January 2014

FT-IR Studies on Light Olefin Skeletal Isomerization Catalysis journal, October 1998

The surface of transitional aluminas: A critical review journal, May 2014

Catalytically Active Sites for the Beckmann Rearrangement of Cyclohexanone Oxime to ε-Caprolactam journal, August 1999

Quantification of Brønsted Acid Sites of Grafted Amorphous Silica-Alumina Compounds and their Turnover Frequency in m -Xylene Isomerization journal, October 2013

Grafted Poly(1→4-β-glucan) Strands on Silica: A Comparative Study of Surface Reactivity as a Function of Grafting Density journal, December 2011

Understanding the Role of Defect Sites in Glucan Hydrolysis on Surfaces journal, March 2013

Dynamic nuclear polarization at high magnetic fields journal, February 2008

Surface Modification of Au/TiO 2 Catalysts by SiO 2 via Atomic Layer Deposition journal, May 2008

The variety of Brønsted acid sites in amorphous aluminosilicates and zeolites journal, July 2014

A Novel Method To Synthesize Amorphous Silica−Alumina Materials with Mesoporous Distribution without Using Templates and Pore-Regulating Agents journal, January 2002

Surface Enhanced NMR Spectroscopy by Dynamic Nuclear Polarization journal, November 2010

Brønsted acid sites of zeolitic strength in amorphous silica-alumina journal, January 2010

Catalytic Properties of Silica-Alumina Prepared by Chemical Vapor Deposition journal, August 1987

A methanol to olefins review: Diffusion, coke formation and deactivation on SAPO type catalysts journal, December 2012

ALD of SiO[sub 2] at Room Temperature Using TEOS and H[sub 2]O with NH[sub 3] as the Catalyst journal, January 2004

X-ray photoelectron spectroscopy of low-temperature anodic silicon oxides: LOW-TEMPERATURE ANODIC SILICON OXIDES journal, June 1992

Fine control of the pore-opening size of the zeolite mordenite by chemical vapour deposition of silicon alkoxide journal, January 1984

Characterization of oxide surfaces and zeolites by carbon monoxide as an IR probe molecule book, January 2002

Infrared spectrum of ammonia adsorbed on silica-alumina journal, February 1967

Structure of SiO2 and Al2O3 Monolayer Catalysts: Investigation by Infrared-Spectroscopy and 29Si MAS NMR journal, July 1994

Experimental and QM/MM investigation of the hydrated silica surface reactivity journal, April 2005

A 29Si NMR investigation of the structure of amorphous silica—alumina supports journal, January 1989

Viscous flow reactor with quartz crystal microbalance for thin film growth by atomic layer deposition journal, August 2002

Chemistry of Cracking Catalysts journal, November 1949

Catalytic dehydration of ethanol over silica-alumina journal, June 1969

Mechanisms of xylene isomerization over acidic solid catalysts journal, April 2000

Catalytic conversion of methane to more useful chemicals and fuels: a challenge for the 21st century journal, December 2000

Synthesis of ketenes from carboxylic acids on functionalized silica monoliths at short contact times journal, August 2000

Atomic layer deposition of SiO2 at room temperature using NH3-catalyzed sequential surface reactions journal, February 2000

The nature of the relative bonding chemistry in zeolites: An XPS study journal, November 1990

Model silica-alumina acid catalysts for surface science and catalysis studies prepared by argon ion beam sputter deposition using HY-zeolite targets journal, January 1991

Microstructure of silica monolayer solid acid catalysts determined by 29Si NMR spectroscopy journal, May 1998

FT-IR characterization of silicated aluminas, active olefin skeletal isomerization catalysts journal, January 1997

Adsorption Assisted Desorption of NH 3 on γ-Alumina Studied with Positron Emission Profiling journal, April 2004

2,6-Dimethylpyridine as a probe of the strength of Brønsted acid sites: study on zeolites. Application to alumina journal, January 2005

NMR Spectroscopic Characterization of Flame‐Made Amorphous Silica‐Alumina for Cyclohexanol and Glyceraldehyde Conversion journal, October 2019

Shedding light on the atomic-scale structure of amorphous silica–alumina and its Brønsted acid sites journal, January 2019

Probing acid sites in solid catalysts with pyridine UV-Vis spectroscopy journal, January 2018

Strong electrostatic adsorption of Pt onto SiO 2 partially overcoated Al 2 O 3 —Towards single atom catalysts journal, December 2019

Acidity enhancement through synergy of penta- and tetra-coordinated aluminum species in amorphous silica networks journal, January 2020

Atomic Layer Deposition (ALD) as a Way to Prepare New Mixed-Oxide Catalyst Supports: The Case of Alumina Addition to Silica-Supported Platinum for the Selective Hydrogenation of Cinnamaldehyde journal, March 2019

Shedding light on the atomic-scale structure of amorphous silica-alumina and its Brønsted acid sites text, January 2019

Acidity enhancement through synergy of penta- and tetra-coordinated aluminum species in amorphous silica networks text, January 2020

Determining the Surface Structure of Silicated Alumina Catalysts via Isotopic Enrichment and Dynamic Nuclear Polarization Surface-Enhanced NMR Spectroscopy journal, October 2017

Three-Dimensional Structure Determination of Surface Sites journal, January 2017

Acidity enhancement through synergy of penta- and tetra-coordinated aluminum species in amorphous silica networks journal, January 2020

Title: Highly dispersed SiO_x/Al₂O₃ catalysts illuminate the reactivity of isolated silanol sites

A quantum-chemical approach to the generation of solid acidity in composite metal oxides
journal, January 1984

A Fast XPS study of the surface chemistry of ethanol over Pt{111}
journal, January 2004

Acidic Crystalline Aluminosilicates. New Superactive, Superselective Cracking Catalysts
journal, September 1964

Thin silica layer on alumina: evidence of the acidity in the monolayer
journal, August 1990

The Acidity of Zeolites: Concepts, Measurements and Relation to Catalysis: A Review on Experimental and Theoretical Methods for the Study of Zeolite Acidity
journal, October 2013

Acidic catalysts for the dehydration of glycerol: Activity and deactivation
journal, August 2009

Solid Acids and Bases
book, January 1970

XPS analysis of oxides
journal, July 1988

SURFACE HYDROXYL GROUPS ON γ-ALUMINA ¹
journal, October 1960

Deactivation of a silica-alumina catalyst by coke deposition
journal, November 1993

Modification of polymer-gel structures
journal, February 1984

Synthesis of amorphous aluminosilicates by grafting: Tuning the building and final structure of the deposit by selecting the appropriate synthesis conditions
journal, February 2014

Surface chemistry of atomic layer deposition: A case study for the trimethylaluminum/water process
journal, June 2005

Impact of solvent for individual steps of phenol hydrodeoxygenation with Pd/C and HZSM-5 as catalysts
journal, January 2014

FT-IR Studies on Light Olefin Skeletal Isomerization Catalysis
journal, October 1998

The surface of transitional aluminas: A critical review
journal, May 2014

Catalytically Active Sites for the Beckmann Rearrangement of Cyclohexanone Oxime to ε-Caprolactam
journal, August 1999

Quantification of Brønsted Acid Sites of Grafted Amorphous Silica-Alumina Compounds and their Turnover Frequency in m -Xylene Isomerization
journal, October 2013

Grafted Poly(1→4-β-glucan) Strands on Silica: A Comparative Study of Surface Reactivity as a Function of Grafting Density
journal, December 2011

Understanding the Role of Defect Sites in Glucan Hydrolysis on Surfaces
journal, March 2013

Dynamic nuclear polarization at high magnetic fields
journal, February 2008

Surface Modification of Au/TiO ₂ Catalysts by SiO ₂ via Atomic Layer Deposition
journal, May 2008

The variety of Brønsted acid sites in amorphous aluminosilicates and zeolites
journal, July 2014

A Novel Method To Synthesize Amorphous Silica−Alumina Materials with Mesoporous Distribution without Using Templates and Pore-Regulating Agents
journal, January 2002

Surface Enhanced NMR Spectroscopy by Dynamic Nuclear Polarization
journal, November 2010

Brønsted acid sites of zeolitic strength in amorphous silica-alumina
journal, January 2010

Catalytic Properties of Silica-Alumina Prepared by Chemical Vapor Deposition
journal, August 1987

A methanol to olefins review: Diffusion, coke formation and deactivation on SAPO type catalysts
journal, December 2012

ALD of SiO[sub 2] at Room Temperature Using TEOS and H[sub 2]O with NH[sub 3] as the Catalyst
journal, January 2004

X-ray photoelectron spectroscopy of low-temperature anodic silicon oxides: LOW-TEMPERATURE ANODIC SILICON OXIDES
journal, June 1992

Fine control of the pore-opening size of the zeolite mordenite by chemical vapour deposition of silicon alkoxide
journal, January 1984

Characterization of oxide surfaces and zeolites by carbon monoxide as an IR probe molecule
book, January 2002

Infrared spectrum of ammonia adsorbed on silica-alumina
journal, February 1967

Structure of SiO2 and Al2O3 Monolayer Catalysts: Investigation by Infrared-Spectroscopy and 29Si MAS NMR
journal, July 1994

Experimental and QM/MM investigation of the hydrated silica surface reactivity
journal, April 2005

A 29Si NMR investigation of the structure of amorphous silica—alumina supports
journal, January 1989

Viscous flow reactor with quartz crystal microbalance for thin film growth by atomic layer deposition
journal, August 2002

Chemistry of Cracking Catalysts
journal, November 1949

Catalytic dehydration of ethanol over silica-alumina
journal, June 1969

Mechanisms of xylene isomerization over acidic solid catalysts
journal, April 2000

Catalytic conversion of methane to more useful chemicals and fuels: a challenge for the 21st century
journal, December 2000

Synthesis of ketenes from carboxylic acids on functionalized silica monoliths at short contact times
journal, August 2000

Atomic layer deposition of SiO2 at room temperature using NH3-catalyzed sequential surface reactions
journal, February 2000

The nature of the relative bonding chemistry in zeolites: An XPS study
journal, November 1990

Model silica-alumina acid catalysts for surface science and catalysis studies prepared by argon ion beam sputter deposition using HY-zeolite targets
journal, January 1991

Microstructure of silica monolayer solid acid catalysts determined by 29Si NMR spectroscopy
journal, May 1998

FT-IR characterization of silicated aluminas, active olefin skeletal isomerization catalysts
journal, January 1997

Adsorption Assisted Desorption of NH ₃ on γ-Alumina Studied with Positron Emission Profiling
journal, April 2004

2,6-Dimethylpyridine as a probe of the strength of Brønsted acid sites: study on zeolites. Application to alumina
journal, January 2005

NMR Spectroscopic Characterization of Flame‐Made Amorphous Silica‐Alumina for Cyclohexanol and Glyceraldehyde Conversion
journal, October 2019

Shedding light on the atomic-scale structure of amorphous silica–alumina and its Brønsted acid sites
journal, January 2019

Probing acid sites in solid catalysts with pyridine UV-Vis spectroscopy
journal, January 2018

Strong electrostatic adsorption of Pt onto SiO ₂ partially overcoated Al ₂ O ₃ —Towards single atom catalysts
journal, December 2019

Acidity enhancement through synergy of penta- and tetra-coordinated aluminum species in amorphous silica networks
journal, January 2020

Atomic Layer Deposition (ALD) as a Way to Prepare New Mixed-Oxide Catalyst Supports: The Case of Alumina Addition to Silica-Supported Platinum for the Selective Hydrogenation of Cinnamaldehyde
journal, March 2019

Shedding light on the atomic-scale structure of amorphous silica-alumina and its Brønsted acid sites
text, January 2019

Acidity enhancement through synergy of penta- and tetra-coordinated aluminum species in amorphous silica networks
text, January 2020

Determining the Surface Structure of Silicated Alumina Catalysts via Isotopic Enrichment and Dynamic Nuclear Polarization Surface-Enhanced NMR Spectroscopy
journal, October 2017

Three-Dimensional Structure Determination of Surface Sites
journal, January 2017

Acidity enhancement through synergy of penta- and tetra-coordinated aluminum species in amorphous silica networks
journal, January 2020