Probing properties of the interfacial perimeter sites in TiOx/Au/SiO2 with 2-propanol decomposition

Wu, Yi Y.; Kung, Harold H.

doi:10.1016/j.apcata.2017.06.027

Probing properties of the interfacial perimeter sites in TiO_x/Au/SiO₂ with 2-propanol decomposition

Journal Article · Fri Jun 23 00:00:00 EDT 2017 · Applied Catalysis. A, General

DOI:https://doi.org/10.1016/j.apcata.2017.06.027· OSTI ID:1870998

Wu, Yi Y. ^[1]; Kung, Harold H. ^[2]

Northwestern Univ., Evanston, IL (United States); Northwestern University
Northwestern Univ., Evanston, IL (United States)

The decomposition of 2-propanol was studied over SiO₂, SiO₂ with an overlayer of TiO₂ (Ti/SiO2), Au/SiO₂, and Au/SiO₂ with an overlayer of TiO₂ (Ti/[Au/SiO₂]) at 170–190 °C. There was no reaction on SiO₂. Propene was the only product on Ti/SiO₂, and its rate of formation increased proportionally with the Ti content. Acetone was the major product (selectivity 65–99%) on all Au-containing catalysts. Its rate of formation also increased with Ti loading. In addition, small amounts of propene were also formed on Ti/[Au/SiO₂] the rate of which increased with Ti loading. Characterization of the catalysts with N₂ adsorption, STEM, DR-UV-vis spectroscopy, XPS, XANES and EXAFS suggested that the Ti formed an amorphous TiO₂ overlayer on the catalyst. At high Ti loadings (4–5 wt.%), there were patches of thick porous TiO₂ layer, and some microdomains of crystalline TiO₂ could be detected. Au was present as 1–3 nm nanoparticles on all catalysts, before and after used in reaction. Only Lewis acid sites were detected based on results from pyridine adsorption, and their quantities increased with Ti loading. Based on the comparison of reaction rates, the dependence of the kinetics on 2-propanol partial pressure, the apparent activation energies, and the effect of co-feeding O₂ among different catalysts, it was concluded that propene was formed on the TiO₂ overlayer, acetone was formed primarily at the Au-TiO₂ interfacial perimeter sites, and α-C-H bond breaking preceding acetone formation was more facile on Au at the interfacial site than other surface Au atoms. Implication of these results to the selective acetone formation in the oxidation of propane in the presence of a O₂/H₂ mixture was discussed.

View Accepted Manuscript (DOE)

Research Organization:: Northwestern Univ., Evanston, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357; FG02-03ER15457

OSTI ID:: 1870998

Alternate ID(s):: OSTI ID: 1418046
OSTI ID: 1550208

Journal Information:: Applied Catalysis. A, General, Journal Name: Applied Catalysis. A, General Vol. 548; ISSN 0926-860X

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (45)

Gas-phase oxidation of 2-propanol over Au/TiO ₂ catalysts to probe metal-support interactions Holz, Marie C.; Kähler, Kevin; Tölle, Katharina physica status solidi (b), Vol. 250, Issue 6 https://doi.org/10.1002/pssb.201248504	journal	March 2013
Relationships between Microstructure and Surface Acidity of Ti-Si Mixed Oxide Catalysts Liu, Z. F.; Tabora, J.; Davis, R. J. Journal of Catalysis, Vol. 149, Issue 1 https://doi.org/10.1006/jcat.1994.1277	journal	September 1994
Aqueous phase epoxidation of 1-butene catalyzed by suspension of Au/TiO2 +TS-1 Jiang, Jian; Kung, Harold H.; Kung, Mayfair C. Gold Bulletin, Vol. 42, Issue 4 https://doi.org/10.1007/BF03214950	journal	December 2009
Nonstoichiometric Titanium Oxides via Pulsed Laser Ablation in Water Huang, Chang-Ning; Bow, Jong-Shing; Zheng, Yuyuan Nanoscale Research Letters, Vol. 5, Issue 6 https://doi.org/10.1007/s11671-010-9591-4	journal	April 2010
Thermal desorption of gases Redhead, P. A. Vacuum, Vol. 12, Issue 4 https://doi.org/10.1016/0042-207X(62)90978-8	journal	July 1962
Reactions of aliphatic alcohols on the {011}-facetted Ti02 (001) surface Kim, K. S.; Barteau, M. A. Journal of Molecular Catalysis, Vol. 63, Issue 1 https://doi.org/10.1016/0304-5102(90)85172-E	journal	November 1990
TiO2–SiO2 mixed oxide modified with H2SO4 Jung, Seong Moon; Grange, Paul Applied Catalysis A: General, Vol. 228, Issue 1-2 https://doi.org/10.1016/S0926-860X(01)00960-7	journal	March 2002
In situ FTIR spectra of pyridine adsorbed on SiO2–Al2O3, TiO2, ZrO2 and CeO2: general considerations for the identification of acid sites on surfaces of finely divided metal oxides Zaki, Mohamed I.; Hasan, Muhammad A.; Al-Sagheer, Fakhryia A. Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 190, Issue 3 https://doi.org/10.1016/S0927-7757(01)00690-2	journal	October 2001
Propan-2-ol transformation on simple metal oxides TiO2, ZrO2 and CeO2 Haffad, D.; Chambellan, A.; Lavalley, J. C. Journal of Molecular Catalysis A: Chemical, Vol. 168, Issue 1-2 https://doi.org/10.1016/S1381-1169(00)00516-1	journal	March 2001
The effect of water on the acidity of TiO2 and sulfated titania Kulkarni, Apoorva P.; Muggli, Darrin S. Applied Catalysis A: General, Vol. 302, Issue 2 https://doi.org/10.1016/j.apcata.2006.01.033	journal	April 2006
XPS characterization of Au/TiO2 catalysts: Binding energy assessment and irradiation effects Kruse, Norbert; Chenakin, Sergey Applied Catalysis A: General, Vol. 391, Issue 1-2 https://doi.org/10.1016/j.apcata.2010.05.039	journal	January 2011
Comprehensive IR study on acid/base properties of metal oxides Tamura, Masazumi; Shimizu, Ken-ichi; Satsuma, Atsushi Applied Catalysis A: General, Vol. 433-434 https://doi.org/10.1016/j.apcata.2012.05.008	journal	August 2012
Aerobic oxidation of alcohols over Au/TiO2: An insight on the promotion effect of water on the catalytic activity of Au/TiO2 Yang, Xiaomin; Wang, Xiuna; Liang, Changhai Catalysis Communications, Vol. 9, Issue 13 https://doi.org/10.1016/j.catcom.2008.05.021	journal	July 2008
Which sites are the active sites in TiO2–SiO2 mixed oxides? Notari, Bruno; Willey, Ronald J.; Panizza, Marta Catalysis Today, Vol. 116, Issue 2 https://doi.org/10.1016/j.cattod.2006.02.086	journal	August 2006
Gas-phase selective oxidation of toluene on TiO2–sepiolite supported vanadium oxidesInfluence of vanadium loading on conversion and product selectivities Bautista, F.; Campelo, J.; Luna, D. Catalysis Today, Vol. 128, Issue 3-4 https://doi.org/10.1016/j.cattod.2007.06.079	journal	October 2007
The effect of gold particle size on AuAu bond length and reactivity toward oxygen in supported catalysts Miller, J. T.; Kropf, A. J.; Zha, Y. Journal of Catalysis, Vol. 240, Issue 2 https://doi.org/10.1016/j.jcat.2006.04.004	journal	June 2006
Reaction kinetic analysis of the gas-phase epoxidation of propylene over Au/TS-1 Taylor, B.; Lauterbach, J.; Blau, G. Journal of Catalysis, Vol. 242, Issue 1 https://doi.org/10.1016/j.jcat.2006.06.007	journal	August 2006
Propene epoxidation over Au/Ti-SBA-15 catalysts Sacaliuc, E.; Beale, A.; Weckhuysen, B. Journal of Catalysis, Vol. 248, Issue 2 https://doi.org/10.1016/j.jcat.2007.03.014	journal	June 2007
Oxidation of propane to propylene oxide on gold catalysts Bravo-Suárez, Juan J.; Bando, Kyoko K.; Lu, Jiqing Journal of Catalysis, Vol. 255, Issue 1 https://doi.org/10.1016/j.jcat.2008.01.030	journal	April 2008
Mechanistic study of propane selective oxidation with H2 and O2 on Au/TS-1 Bravosuarez, J.; Bando, K.; Fujitani, T. Journal of Catalysis, Vol. 257, Issue 1 https://doi.org/10.1016/j.jcat.2008.04.004	journal	July 2008
Ti-bridged silsesquioxanes as precursors of silica-supported titanium oxide catalysts for the epoxidation of cyclooctene Sakugawa, Shuko; Wada, Kenji; Inoue, Masashi Journal of Catalysis, Vol. 275, Issue 2 https://doi.org/10.1016/j.jcat.2010.08.010	journal	October 2010
Epoxidation catalysts derived from introduction of titanium centers onto the surface of mesoporous aluminophosphate: Comparisons with analogous catalysts based on mesoporous silica Raboin, Lorraine; Yano, Junko; Tilley, T. Don Journal of Catalysis, Vol. 285, Issue 1 https://doi.org/10.1016/j.jcat.2011.09.023	journal	January 2012
2-Propanol reactivity on in situ prepared Au(1 1 1)-supported TiO 2 nanocrystals Potapenko, Denis V.; Li, Zhisheng; Lou, Yang Journal of Catalysis, Vol. 297 https://doi.org/10.1016/j.jcat.2012.10.020	journal	January 2013
Quantifying accessible sites and reactivity on titania–silica (photo)catalysts: Refining TOF calculations Eaton, Todd R.; Campos, Michael P.; Gray, Kimberly A. Journal of Catalysis, Vol. 309 https://doi.org/10.1016/j.jcat.2013.09.015	journal	January 2014
Morphology and surface properties of fumed silicas Gun'ko, V. M.; Mironyuk, I. F.; Zarko, V. I. Journal of Colloid and Interface Science, Vol. 289, Issue 2 https://doi.org/10.1016/j.jcis.2005.05.051	journal	September 2005
Adsorption and dehydrogenation of 2-propanol on the surface of γ-Al2O3-supported gold Martinez-Ramirez, Z.; Gonzalez-Calderon, J. A.; Almendarez-Camarillo, A. Surface Science, Vol. 606, Issue 15-16 https://doi.org/10.1016/j.susc.2012.03.016	journal	August 2012
Quantification of crystalline and amorphous content in porous samples from electron energy loss spectroscopy Bertoni, G.; Beyers, E.; Verbeeck, J. Ultramicroscopy, Vol. 106, Issue 7 https://doi.org/10.1016/j.ultramic.2006.03.006	journal	May 2006
Controlled Postgrafting of Titanium Chelates for Improved Synthesis of Ti-SBA-15 Epoxidation Catalysts Bérubé, François; Nohair, Bendaoud; Kleitz, Freddy Chemistry of Materials, Vol. 22, Issue 6 https://doi.org/10.1021/cm9030667	journal	March 2010
The Reaction of Gold(III) with Some Bidentate Coördinating Groups ¹ Block, B. P.; Bailar, John C. Journal of the American Chemical Society, Vol. 73, Issue 10 https://doi.org/10.1021/ja01154a071	journal	October 1951
Vapor Pressure data for Isopropyl Alcohol and Tertiary Butyl Alcohol Parks, George S.; Barton, Bernard Journal of the American Chemical Society, Vol. 50, Issue 1 https://doi.org/10.1021/ja01388a004	journal	January 1928
Structural Assessment and Catalytic Consequences of the Oxygen Coordination Environment in Grafted Ti−Calixarenes Notestein, Justin M.; Andrini, Leandro R.; Kalchenko, Vitaly I. Journal of the American Chemical Society, Vol. 129, Issue 5 https://doi.org/10.1021/ja065830c	journal	February 2007
Role of Defects in the Adsorption of Aliphatic Alcohols on the TiO ₂ (110) Surface Farfan-Arribas, Enrique; Madix, Robert J. The Journal of Physical Chemistry B, Vol. 106, Issue 41 https://doi.org/10.1021/jp020729p	journal	October 2002
New Preparation Method of Gold Nanoparticles on SiO ₂ Zanella, Rodolfo; Sandoval, Alberto; Santiago, Patricia The Journal of Physical Chemistry B, Vol. 110, Issue 17 https://doi.org/10.1021/jp060601y	journal	May 2006
Silica-Supported Au Nanoparticles Decorated by TiO ₂ : Formation, Morphology, and CO Oxidation Activity Horváth, Anita; Beck, Andrea; Sárkány, Antal The Journal of Physical Chemistry B, Vol. 110, Issue 31 https://doi.org/10.1021/jp060977b	journal	August 2006
Influence of Re-adsorption and Surface Heterogeneity on the Microkinetic Analysis of Temperature-Programmed Desorption Experiments Xia, Xinyu; Strunk, Jennifer; Litvinov, Sergey The Journal of Physical Chemistry C, Vol. 111, Issue 16 https://doi.org/10.1021/jp0677748	journal	April 2007
Surface Chemistry of 2-Propanol on TiO ₂ (110): Low- and High-Temperature Dehydration, Isotope Effects, and Influence of Local Surface Structure Bondarchuk, Oleksandr; Kim, Yu Kwon; White, J. M. The Journal of Physical Chemistry C, Vol. 111, Issue 29 https://doi.org/10.1021/jp072298m	journal	July 2007
Concentration of hydroxyl groups on the surface of amorphous silicas Zhuravlev, L. T. Langmuir, Vol. 3, Issue 3 https://doi.org/10.1021/la00075a004	journal	May 1987
Adsorption and decomposition of aliphatic alcohols on titania Kim, K. S.; Barteau, M. A.; Farneth, W. E. Langmuir, Vol. 4, Issue 3 https://doi.org/10.1021/la00081a007	journal	May 1988
Selective oxidation with dioxygen by gold nanoparticle catalysts derived from 55-atom clusters Turner, Mark; Golovko, Vladimir B.; Vaughan, Owain P. H. Nature, Vol. 454, Issue 7207 https://doi.org/10.1038/nature07194	journal	August 2008
Propane reacts with O2 and H2 on gold supported TS-1 to form oxygenates with high selectivity Bravo-Suárez, J. J.; Bando, K. K.; Akita, T. Chemical Communications, Issue 28 https://doi.org/10.1039/b800620b	journal	January 2008
Metal nanoparticle catalysts decorated with metal oxide clusters Mashayekhi, Neema A.; Wu, Yi Y.; Kung, Mayfair C. Chemical Communications, Vol. 48, Issue 81 https://doi.org/10.1039/c2cc34885c	journal	January 2012
Au–metal oxide support interface as catalytic active sites Wu, Yi Y.; Mashayekhi, Neema A.; Kung, Harold H. Catalysis Science & Technology, Vol. 3, Issue 11 https://doi.org/10.1039/c3cy00243h	journal	January 2013
Effect of potassium addition to the TiO2 support on the structure of V2O5/TiO2 and its catalytic properties in the oxidative dehydrogenation of propane Courcot, Dominique; Grzybowska, Barbara; Barbaux, Yolande Journal of the Chemical Society, Faraday Transactions, Vol. 92, Issue 9 https://doi.org/10.1039/ft9969201609	journal	January 1996
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT Ravel, B.; Newville, M. Journal of Synchrotron Radiation, Vol. 12, Issue 4 https://doi.org/10.1107/S0909049505012719	journal	June 2005
Selective oxidation of propylene over gold deposited on titanium-based oxides Haruta, M.; Uphade, B. S.; Tsubota, S. Research on Chemical Intermediates, Vol. 24, Issue 3 https://doi.org/10.1163/156856798X00276	journal	March 1998

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