Before mass produced automotive fuel cell technology can be made practical, the oxidative instability of the carbons currently, used as the catalyst support at the oxygen electrode, must be addressed. This article describes a method for coating carbon (Vulcan XC-72) with protective barriers of titanium dioxide (titania) and provides the results of physical characterization tests on those materials. By combining the sol-gel coating process with high intensity ultrasonication and choosing the appropriate precursor, either the anatase or rutile phases of titania can be produced. More complete coverage of the carbon was provided by the anatase process. Accelerated gas-phase oxidation tests showed that platinized, anatase-coated carbon oxidized at the rate of untreated carbon while the rutile phase showed a mass loss of that of untreated carbon.
Issue Section:
Research Papers
1.
Stevens
, D. A.
, and Dahn
, J. R.
, 2005, “Thermal Degradation of the Support in Carbon-Supported Platinum Electrocatalysts for PEM Fuel Cells
,” Carbon
0008-6223, 43
, pp. 179
–188
.2.
Raman
, R. K.
, Murgia
, G.
, and Shukla
, A. K.
, 2004, “A Solid-Polymer Electrolyte Direct Methanol Fuel Cell With a Methanol-Tolerant Cathode and its Mathematical Modelling
,” J. Appl. Electrochem.
0021-891X, 34
, pp. 1029
–1038
.3.
Tada
, T.
, Vielstich
, W.
, Lamm
, A.
, and Gasteiger
, H. A.
, 2003, Handbook of Fuel Cells, Fundamentals, Technology and Applications
, Wiley
, New York
, Vol. 3
, p. 481
.4.
Wilson
, M. S.
, Garzon
, H. G.
, Sickafus
, K. E.
, and Gottesfeld
, S.
, 1993, “Surface Area Loss of Supported Platinum in Polymer Electrolyte Fuel Cells
,” J. Electrochem. Soc.
0013-4651, 140
, pp. 2872
–2877
.5.
Darling
, R. M.
, and Myers
, J. P.
, 2003, “Kinetic Model of Platinum Dissolution in PEMFCs
,” J. Electrochem. Soc.
0013-4651, 150
, pp. A1523
–A1527
.6.
Roen
, L. M.
, Paik
, C. H.
, and Jarvi
, T. D.
, 2004, “Electrocatalytic Corrosion of Carbon Support in PEMFC Cathodes
,” Electrochem. Solid-State Lett.
1099-0062, 7
, pp. A19
–A22
.7.
Knights
, S. D.
, Colbow
, K. M.
, St-Pierre
, J.
, and Wilkinson
, D. P.
, 2004, “Aging Mechanisms and Lifetime of PEFC and DMFC
,” J. Power Sources
0378-7753, 127
, pp. 127
–134
.8.
Panchenko
, A.
, Dilger
, H.
, Kerres
, J.
, Hein
, M.
, Ulrich
, A.
, Kaqz
, T.
, and Roduner
, E.
, 2004, “In-Situ Spin Trap Electron Paramagnetic Resonance Study of Fuel Cell Processes
,” Phys. Chem. Chem. Phys.
1463-9076, 6
, pp. 2891
–2894
.9.
Kangasniemi
, K. H.
, Condit
, D. A.
, and Jarvi
, T. D.
, 2004, “Characterization of Vulcan Electrochemically Oxidized Under Simulated PEM Fuel Cell Conditions
,” J. Electrochem. Soc.
0013-4651, 151
, pp. E125
–E132
.10.
Cheng
, X.
, Chen
, L.
, Peng
, C.
, Chen
, Z.
, Zhang
, Y.
, and Fan
, Q.
, 2004, “Catalyst Microstructure Examination of PEMFC Membrane Electrode Assemblies Versus Time
,” J. Electrochem. Soc.
0013-4651, 151
, pp. A48
–A52
.11.
Ioroi
, T.
, Siroma
, Z.
, Fujiwara
, N.
, Yamazaki
, S.
, and Yasuda
, K.
, 2005, “Sub-Stoichiometric Titanium Oxide-Supported Platinum Electrocatalyst for Polymer Electrolyte Fuel Cells
,” Electrochem. Commun.
1388-2481, 7
, pp. 183
–188
.12.
Konno
, H.
, Kinomura
, T.
, Habazaki
, H.
, and Aramata
, M.
, 2005, “Formation of Oxidation Resistant Graphite Flakes by Ultrathin Silicone Coating
,” Surf. Coat. Technol.
0257-8972, 194
, pp. 24
–30
.13.
Graetzel
, M.
, Thampi
, K. R.
, and Kiwi
, J.
, 1989, “Methane Oxidation at Room Temperature and Atmospheric Pressure Activated by Light via Polytungstate Dispersed on Titania
,” J. Phys. Chem.
0022-3654 B, 93
, pp. 4128
–4132
.14.
Rhee
, C. H.
, Bae
, W. B.
, and Lee
, J. S.
, 2005, “Template-Free Hydrothermal Synthesis of High Surface Area Nitrogen-Doped Titania Photocatalyst Active Under Visible Light
,” Chem. Lett.
0366-7022, 34
, pp. 660
–661
.15.
Yu
, J. C.
, Yu
, J. G.
, Ho
, W. K.
, and Zhang
, L. Z.
, 2001, “Preparation of Highly Photocatalytic Active Nano-Sized TiO2 Particles via Ultrasonic Irradiation
,” Chem. Commun. (Cambridge)
1359-7345, 2001
, pp. 1942
–1944
.16.
Ovenstone
, J.
, and Yanagisawa
, K.
, 1999, “Effect of Hydrothermal Treatment of Amorphous Titania on the Phase Change From Anatase to Rutile During Calcination
,” Chem. Mater.
0897-4756, 11
, pp. 2770
–2774
.17.
Li
, Y.
, Li
, X.
, Li
, J.
, and Yin
, J.
, 2005, “TiO2-Coated Active Carbon Composites With Increased Photocatalytic Activity Prepared by a Properly Controlled Sol-Gel Method
,” Mater. Lett.
0167-577X, 59
, pp. 2659
–2663
.18.
Wang
, Y.
, and Ying
, J. Y.
, 1999, “Sol-Gel Synthesis and Hydrothermal Processing of Anatase and Rutile Titania Nanocrystals
,” Chem. Mater.
0897-4756, 11
, pp. 3113
–3120
.19.
Song
, L.
, Song
, S.
, and Gao
, Z.
, 2004, “Formation of TiO2 Modified Film on Carbon Steel
,” J. Mater. Sci. Technol.
0861-9786, 20
, pp. 599
–601
.20.
Yamashita
, H.
, Harada
, M.
, Tanii
, A.
, Honda
, M.
, Takeuchi
, M.
, Ichihashi
, Y.
, Anpo
, M.
, Iwanoto
, N.
, Itoh
, N.
, and Hirao
, T.
, 2000, “Preparation of Efficient Titanium Oxide Photocatalysts by an Ionized Cluster Beam (ICB) Method and Their Photocatalytic Reactivities for the Purification of Water
,” Catal. Today
0920-5861, 63
, pp. 63
–69
.21.
Barringer
, E. A.
, and Bowen
, H. K.
, 1982, “Formation, Packing, and Sintering of Monodisperse TiO2 Powders
,” J. Am. Ceram. Soc.
0002-7820, 65
, pp. c199
–c201
.22.
Ding
, Z.
, Hu
, X.
, Yue
, P.
, Lu
, G.
, and Greenfield
, P.
, 2001, “Synthesis of Anatase TiO2 Supported on Porous Solids by Chemical Vapor Deposition
,” Catal. Today
0920-5861, 68
, pp. 173
–182
.23.
Kahn
, A.
, 2003, “Titanium Dioxide Coated Activated Carbon. A Regenerative Technology for Water Recovery,” Master's thesis, University of Florida.24.
Yoneyyama
, H.
, Torimoto
, T.
, Iwata
, N.
, Kanemoto
, H.
, Mendicino
, S. C.
, Rajeshwar
, L.
, and Fenton
, J.
, eds., 1st International Symposium on Environmental Issues in the Electronics/Semiconductor Industries and Electrochemical-Photochemical Methods for Pollution Abatement
, Springer
, Berlin
, p. 188
.25.
Huang
, Q.
, and Gao
, L.
, 2003, “Immobilization of Rutile TiO2 on Multiwalled Carbon Nanotubes
,” J. Mater. Comm.
, 13
, pp. 1517
–1519
.26.
Anpo
, M.
, Ichihashi
, Y.
, Takeuchi
, M.
, and Yamashita
, H.
, 1998, “Design of Unique Titanium Oxide Photocatalysts by an Advanced Metal Ion-Implantation Method and Photocatalytic Reactions Under Visible Light Irradiation
,” Res. Chem. Intermed.
0922-6168, 24
, pp. 143
–149
.27.
Nozawa
, M.
, Tanigawa
, K.
, Hosomi
, M.
, Chikusa
, T.
, and Kawada
, E.
, 2001, “Removal and Decomposition of Malodorants by Using Titanium Dioxide Photocatalyst Supported on Fiber Activated Carbon
,” Water Sci. Technol.
0273-1223, 44
, 127
–133
.28.
Matsumoto
, A.
, Tsutsumi
, K.
, and Kaneko
, K.
, 1992, “Titania Coating of a Microporous Carbon Surface by Molecular Adsorptio-Deposition
,” Langmuir
0743-7463, 8
, p. 2515
.29.
Chen
, Q.
, Qian
, Y.
, Chen
, Z.
, Zhou
, G.
, and Zhang
, Y.
, 1995, “Preparation of TiO2 Powders With Different Morphologies by an Oxidation-Hydrothermal Combination Method
,” Mater. Lett.
0167-577X, 22
, pp. 77
–80
.30.
Murakami
, Y.
, Matsumoto
, T.
, and Takasu
, Y.
, 1999, “Salt Catalysts Containing Basic Anions and Acidic Cations for the Sol-Gel Process of Titanium Alkoxide: Controlling the Kinetics and Dimensionality of the Resultant Titanium Oxide
,” J. Phys. Chem. B
1089-5647, 103
, pp. 1836
–1840
.31.
Inagaki
, M.
, Kojin
, F.
, Tryba
, B.
, and Toyoda
, M.
, 2005, “Carbon-Coated Anatase: The Role of the Carbon Layer for Photocatalytic Performance
,” Carbon
0008-6223, 43
, pp. 1652
–1659
.32.
Jitianu
, A.
, Cacciaguerra
, T.
, Benoit
, R.
, Delpeux
, S.
, Beguin
, F.
, and Bonnamy
, S.
, 2004, “Synthesis and Characterization of Carbon Nanotubes—TiO2 Nanocomposites
,” Carbon
0008-6223, 42
, pp. 1147
–1151
.33.
Suslick
, K. S.
, 1998, Ultrasound: Its Chemical, Physical and Biological Effects
, VCH
, Weinheim
.34.
Suslick
, K. S.
, Choe
, S. B.
, Cichowlas
, A. A.
, and Grinstaff
, M. W.
, 1991, “Sonochemical Synthesis of Amorphous Iron
,” Nature (London)
0028-0836, 353
, pp. 414
–416
.35.
Srivastava
, D. N.
, Perkas
, N.
, Zaban
, A.
, and Gedanken
, A.
, 2002, “Sonochemistry as a Tool for Preparation of Porous Metal Oxides
,” Pure Appl. Chem.
0033-4545, 74
, pp. 1509
–1517
.36.
Srivastava
, D. N.
, Pol
, V. G.
, Palchik
, O.
, Zhang
, L.
, Yu
, J. C.
, and Gedanken
, A.
, 2005, “Preparation of Stable Porous Nickel and Cobalt Oxides Using Simple Inorganic Precursor, Instead of Alkoxides, by a Sonochemical Technique
,” Ultrason. Sonochem.
1350-4177, 12
, pp. 205
–212
.37.
Srivastava
, D. N.
, Perkas
, N.
, Gedanken
, A.
, and Felner
, I.
, 2002, “Sonochemical Synthesis of Mesoporous Iron Oxide and Accounts of its Magnetic and Catalytic Properties
,” J. Phys. Chem. B
1089-5647, 106
, pp. 1878
–1883
.38.
Landau
, M. V.
, Vradman
, L.
, Herskowitz
, M.
, Koltypin
, Y.
, and Gedanken
, A.
, 2001, “Ultrasonically Controlled Deposition-Precipitation Co—Mo HDS Catalysts Deposited on Wide-Pore MCM Material
,” J. Catal.
0021-9517, 201
, pp. 22
–36
.39.
Wang
, Y.
, Tang
, X.
, Yin
, L.
, Huang
, W.
, Hacohen
, Y. R.
, and Gedanken
, A.
, 2000, “Sonochemical Synthesis of Mesoporous Titanium Oxide With Wormhole-Like Framework Structures
,” Adv. Mater. (Weinheim, Ger.)
0935-9648, 12
, pp. 1183
–1186
.40.
Tsurumi
, K.
, Sugimoto
, H.
, Nobuo
, Y.
, Nakamura
, T.
, and Stonehart
, P.
, 1992, US98520.41.
Sing
, K. S. W.
, Everett
, D. H.
, Haul
, R. A. W.
, Moscou
, L.
, Pierotti
, R. A.
, Rouquerol
, J.
, and Siemieniewska
, T.
, 1985, “Preparation of Photocatalytic TiO2 Coatings of Nanosized Particles on Activated Carbon by AP-MOCVD
,” Pure Appl. Chem.
0033-4545, 57
, pp. 1700
–1708
.42.
Spurr
, R. Y.
, and Myers
, H.
, 1957, “Quantitative Analysis of Anatase-Rutile Mixtures With an X-Ray Diffractometer
,” Anal. Chem.
0003-2700, 29
, pp. 760
–762
.43.
Martinez-Escandell
, M.
, Carreira
, P.
, Rodriguez-Valero
, M. A.
, and Rodriguez-Reinoso
, F.
, 1999, “Self-Sintering of Carbon Mesophase Powders: Effect of Extraction/Washing With Solvents
,” Carbon
0008-6223, 37
(10
), pp. 1662
–1665
.44.
Zhang
, X.
, Zhou
, M.
, and Lei
, L.
, 2005, “Preparation of Photocatalytic TiO2 Coatings of Nanosized Particles on Activated Carbon by AP-MOCVD
,” Carbon
0008-6223, 43
, pp. 1700
–1708
.45.
Wagner
, C.
, and Muilenbergy
, G.
, eds., Handbook of X-ray Photoelectron Spectroscopy
, Perkin-Elmer Corporation
, Weinheim
, p. 38
.46.
Liu
, F. M.
, and Wang
, T. M.
, 2002, “Surface and Optical Properties of Nanocrystalline Anatase Titania Films Grown by Radio Frequency Reactive Magnetron Sputtering
,” Appl. Surf. Sci.
0169-4332, 195
, pp. 284
–290
.47.
Viparelli
, P.
, Ciambelli
, P.
, Volta
, J. C.
, and Herrmann
, J. M.
, 1999, “In Situ Electrical Conductivity Study of Titania-Supported Vanadium-Niobium Oxide Catalysts Used in the Oxidative Dehydrogenation of Propane
,” Appl. Catal., A
0926-860X, 181
(1
), pp. 165
–173
.48.
Suslick
, K. S.
, Choe
, S. B.
, Cichowlas
, A. A.
, and Grinstaff
, M. W.
, 1991, “Sonochemical Synthesis of Amorphous Iron
,” Nature (London)
0028-0836, 353
, pp. 414
–416
.49.
Gutierrez
, M.
, Henglein
, A.
, and Dohrmann
, J.
, 1987, “Hydrogen Atom Reactions in the Sonolysis of Aqueous Solutions
,” J. Phys. Chem.
0022-3654, 91
, pp. 6687
–6690
.50.
Alegria
, A. E.
, Lion
, Y.
, Kondo
, T.
, and Riesz
, P.
, 1989, “Sonolysis of Aqueous Surfactant Solutions: Probing the Interfacial Region of Cavitation Bubbles by Spin Trapping
,” J. Phys. Chem.
0022-3654, 93
, pp. 4908
–4913
.51.
Suslick
, K. S.
, and Hammerton
, D. A.
, 1986, “The Site of Sonochemical Reactions
,” IEEE Trans. Sonics Ultrason.
0018-9537, SU-33
, 143
–147
.52.
Suslick
, K. S.
, and Price
, G. J.
, 1999, “Applications of Ultrasound to Materials Chemistry
,” Annu. Rev. Mater. Sci.
0084-6600, 29
, pp. 295
–326
.Copyright © 2008
by American Society of Mechanical Engineers
You do not currently have access to this content.
