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When Gold Is Not Noble
When Gold Is Not Noble
CHEMICAL
When Gold Is Not Noble: Catalysis by
RECORD Nanoparticles
MASATAKE HARUTA
Research Institute for Green Technology, National Institute of Advanced Industrial Science and
Technology (AIST), 16-1 Onogawa, Tsukuba 305-8569, Japan
ABSTRACT: Bulk gold is chemically inert and is generally regarded as a poor catalyst. However,
when gold is in very small particles with diameters below 10 nm and is deposited on metal oxides
or activated carbon, it becomes surprisingly active, especially at low temperatures, for many reactions
such as CO oxidation and propylene epoxidation. The catalytic performance of Au is defined by
three major factors: contact structure, support selection, and particle size. The role of the perimeter
interfaces of Au particles as the sites for reactions is discussed as well as the change in chemical reac-
tivity of Au clusters composed of fewer than 300 atoms. © 2003 The Japan Chemical Journal Forum
and Wiley Periodicals, Inc., Chem Rec 3: 75–87; 2003: Published online in Wiley InterScience
(www.interscience.wiley.com) DOI 10.1002/tcr.10053
Introduction
In spanning well over a century of the history of heterogeneous The intrinsic catalytic capabilities of group VIII metals can
catalysis, a variety of metal oxides, metal sulfides, and metals be ascribed to the optimum degree of d-band vacancy. The ele-
have been used in inorganic chemical syntheses, petroleum ments of group Ib, the so-called “coinage metals,” Cu, Ag, and
refinery and other chemical processes, and environmental pro- Au have fully occupied d-bands. Owing to relatively low ion-
tection. Metal catalysts are most widely used for a variety of ization potentials, Cu and Ag readily lose electrons to yield d-
reactions,1 including hydrogenation, complete and partial oxi- band vacancies. In fact, in the chemical industry Cu is used for
dation, and reduction of NOx with hydrocarbons.2 The cata- methanol synthesis and Ag is used for ethylene oxide synthesis.
lysts are usually dispersed in the form of small particles on In contrast, Au has a high ionization potential and accordingly
stable metal oxides such as Al2O3 and SiO2. Elements used as has a poor affinity towards molecules of other elements.
metallic catalysts are actually limited to 12, which belong to Surface science investigation3–5 and density functional
groups VIII and Ib of the Periodic Table. Most widely used are theory calculations6 have proved that no dissociative adsorp-
the 3d metals of Fe, Co, Ni, and Cu, the 4d metals of Rh, Pd, tion of H2 and O2 takes place over the smooth surfaces of Au
and Ag, and a 5d metal, Pt. Ruthenium (4d) and Ir (5d) have at temperatures below 473K, indicating that Au should be cat-
only limited applications. Osmium is usually excluded as a alytically inactive for hydrogenation and oxidation reactions.
catalyst component because its oxide is toxic. Gold (5d) is
the only exception in this list and has been regarded as almost
inactive as a catalyst. Correspondence to: M. Haruta; e-mail: [email protected]
T1/2 (K)
This is partly because the melting point of Au is much lower
than those of Pd and Pt (Au: 1336K, Pd: 1823K, Pt: 2042K).
Due to the quantum-size effect, the melting point of 2-nm
diameter Au particles is estimated to be lower, at 600K,8 and
these relatively small Au nanoparticles tend to coagulate to
form much larger Au particles during calcination of the cata-
lyst precursors. Accordingly, we were not able to determine
whether the rough surfaces or the nanoparticles of Au having DHf per one oxygen atom (kcal)
a substantial number of steps, edges, and corners were catalyt-
ically inactive. Fig. 1. Catalytic activity of metal oxides for H2 oxidation as a function of
The first hint that Au might not always be poorly active their heat of formation per one oxygen atom. T1/2 is the temperature for 50%
conversion of H2 obtained by a fixed bed flow reactor in a stream of 1 vol.%
when dispersed as small particles appeared in the 1970s. Bond H2 in air under a space velocity of 2 ¥ 104 h-1/ml◊g-cat.
and Sermon9,10 reported on the hydrogenation of alkenes and
alkynes at temperatures below 473K over Au/SiO2. Paravano
and co-workers11,12 reported on oxygen and hydrogen transfer
reactions over Au/MgO and Au/Al2O3 catalysts. Landmark posite oxides of Ag or Au formed with other metals situated
studies conducted up until 1981 concerning catalysis by Au on the right-hand side of a volcano-like relationship (Fig. 1)
were reviewed by Schwank.13 In contrast, Ozin and col- might lead to active oxidation catalysts owing to the moderate
leagues14 reported that atomic Au species reacted with a solid strength of metal-oxygen bonding.16 It was later revealed that
matrix of CO and O2 at 10K to form a complex, which sub- these active gold catalysts were composed of Au nanoparticles
sequently decomposed at temperatures above 30K to produce homogeneously dispersed on metal oxide supports such as
CO2. Fe2O3, Co3O4, and NiO.17–19 This finding followed by the first
In 1987, we reported that some composite oxides of Au commercial application in 1992—that of a toilet deodorizer—
with 3d transition metals prepared by coprecipitation exhib- has gradually evoked renewed interest in Au catalysts.20–25
ited surprisingly high catalytic activity for CO oxidation even The present article describes the methods used to deposit
at 200K.15 This report was based on the hypothesis that com- Au nanoparticles on metal oxides, their fine structures, and
Masatake Haruta has been Director of the Research Institute for Green Technology at the
National Institute of Advanced Industrial Science and Technology, Japan, since April 2001. He
was born in 1947 and graduated from Nagoya Institute of Technology in 1970. He received
his doctor’s degree from Kyoto University in 1976 and was granted a tenure position at Osaka
National Research Institute (ONRI). From 1981 until 1982 he was a visiting scientist at the
Université Catholique de Louvain, Belgium. In 1990 he was promoted to Head of the cataly-
sis section and in 1994 he became a chief senior researcher organizing a new interdisciplinary
basic research laboratory for research exploring the potential of gold catalysts. In 1994 he stayed
at the Technical University of Vienna as a guest professor. He became Director of the Energy
and Environment department of ONRI in 1999. From 1994 to this date, he has also been an
adjunct professor at Osaka University. His honors include the Osaka Science Prize, the Science
Award of the Catalysis Society of Japan, and the Henry J. Albert Award of International Pre-
cious Metals Institute.
76 © 2003 The Japan Chemical Journal Forum and Wiley Periodicals, Inc.
Catalysis by Nanoparticles
© 2003 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. 77
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Table 1. CO oxidation over Pt/TiO2 and Au/TiO2 prepared by different methods [7].
78 © 2003 The Japan Chemical Journal Forum and Wiley Periodicals, Inc.
Catalysis by Nanoparticles
© 2003 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. 79
THE CHEMICAL RECORD
Table 2. Product yields of the reaction among C3H6, O2, and H2 over Au, Pd, and Pt supported on TiO2 [46].
CH3CH¶CH2 + H2O
CH3CH¨CH2 + O2 + H2 O
CH3CH2CH3 + O2
80 © 2003 The Japan Chemical Journal Forum and Wiley Periodicals, Inc.
Catalysis by Nanoparticles
TOF s-1)
icosahedron into the cubo-octahedron with an increase in the
reaction temperature.
Heiz and co-workers prepared model catalysts by deposit-
ing size-selected Au anion clusters onto a single crystal of
MgO. Although the sizes and structures of the deposited Au
clusters were not observed by STM, it was reported that there
was appreciable size dependency of CO adsorption and that
the highest reactivity to CO was observed for the anion clus-
ters consisting of 11 atoms.66 It was also reported that 8 and
11 are the smallest and the second-smallest number of atoms
to exhibit catalytic activity for CO oxidation over the MgO 1000/T (K-1)
support. The higher activity of Au clusters on defect-rich MgO
than on defect-poor MgO was observed. Ab initio simulations Fig. 6. Arrhenius plots of the turnover frequency (TOF) for CO oxidation
over noble metal catalysts. The data for Pt group metals are taken from Ref.
indicate that partial electron transfer from the surface of the 69.
Au clusters and oxygen-vacancy defects in the support play an
essential role for the genesis of catalytic activity.67,68
© 2003 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. 81
THE CHEMICAL RECORD
300K
C16O2 C 18 O 16 O
Absorbance
5 mbar 18 O 2
+
10 mbar C 16 O
C 18 O 2 Çmin. later
Çmin. later
C 18 O
Fig. 8. Schematic representation for CO oxidation pathways over Au/TiO2.
Wave number (cm-1)
Fig. 7. FT-IR spectra for the introduction of C16O at 300K to Au/TiO2 after
preadsorption of 18O2.70 The bold line corresponds to 3 min. and the dotted-
line 2 min. after the introduction of C16O.
scanning tunneling spectroscopy, whereas the catalytic activity
was measured for an entire Au/TiO2 model catalyst specimen
with a mean diameter of all Au clusters. A maximum in the
There are other arguments as well regarding the active catalytic activity with respect to the mean diameter of the Au
species of Au, especially in the case of Au/Fe2O3. These include clusters was observed where the transition of the electronic
oxidized Au species, Au+,76 Aud+,77 or metal oxide support sur- state of the specific Au cluster occurred from metallic to non-
faces with modified reducibility by the interaction with Au metallic. This result can be more reasonably explained by
nanoparticles.78,79 It is unlikely that oxidic Au species are the assuming that metallic Au surfaces are necessary for CO
major catalytically active phases because the most active sup- adsorption and that the peripheries act as reaction zones with
ported Au catalysts are prepared by calcination in air at 573K, O2. A maximum total surface area or number of step sites63 of
where Au precursors (hydroxides or organo complexes) are metallic Au clusters is obtained at a thickness of 2 atoms, where
mostly transformed into metallic particles. A certain fraction the transition to the nonmetallic state begins.
of Au species remain as atomically dispersed species in the Based on the above arguments, the most probable
matrix of the support, as proved by EXAFS,23,77,80,81 XPS,78 pathway for CO oxidation over supported Au catalysts can be
Mössbauer,79,82 and IR of CO adsorbed.70,76 However, no cor- depicted as shown in Figure 8.
relation between the amount of oxidic Au species and catalytic
activity has yet been presented. It is speculated that the samples
primarily consisting of oxidic Au probably exhibited high cat- Reactions Catalyzed by Gold and Applications
alytic activity because the oxidic Au species are transformed
into metallic particles during reaction or storage of the sample Gold catalysts with selected support materials can also promote
after preparation. many reactions other than CO oxidation and propylene
Although metallic Au particles are indispensable, a ques- epoxidation. Table 3 lists such reactions, which usually take
tion arises as to why the periphery of Au particles can activate place at much lower temperatures or with much higher degrees
O2 molecules at low temperatures. As proposed by Bond and of selectivity over Au catalysts than over other metal catalysts.
Thompson,83 it is probable that the perimeter interfaces For the complete oxidation (combustion) of hydrocar-
contain oxidic Au species, most probably Au(OH)3 or bons, Co3O4, which is the most active among base metal
Au(OH), under usual conditions wherever H2O is present at oxides, causes the highest level of catalytic activity of Au.84,85
concentrations above 1 ppm. These hydroxides might be sta- For the oxidative decomposition of nitrogen-containing
bilized and reversibly formed and decomposed by the aid of hydrocarbons, ferric oxides and nickel ferrites cause the highest
the metal oxide supports. level of catalytic activity owing to their strong affinities to
An argument proposed by Goodman and co-workers36,60 nitrogen.86 The oxidative decomposition of trimethylamine,
is that the nonmetallic nature of Au clusters leads to high cat- which is a typical odor-producing compound, proceeds over
alytic activity. This conclusion is questionable as far as CO oxi- Au/NiFe2O4 at temperatures below 373K, yielding mostly N2
dation is concerned. The transition of the electronic state was and CO2, while N2O is mostly produced over Pd and Pt cat-
measured for one specific Au cluster of a defined diameter by alysts even at higher temperatures. Gold deposited on Fe2O3,
82 © 2003 The Japan Chemical Journal Forum and Wiley Periodicals, Inc.
Catalysis by Nanoparticles
Temperature
Type of reaction Reactant (K) Support Notes Ref.
Complete oxidation CO 200–400 Be(OH)2, Mg(OH)2, acidic metal oxides are excluded as 51
Mn2O3, Fe2O3, etc. a support. 17, 19, 44, 105
HCHO 300–450 TiO2 regenerable by sun light 119
CH3OH 300–450 TiO2 regenerable by sun light 119
CH4, C3H8 450–650 Co3O4 as active as Pd, Pt catalysts 84, 85
trimethylamine 330–500 Fe2O3, NiFe2O4 commercialized for odor eater 86
Oxidative chlorofluorocarbon 550–823 Co3O4, Al2O3, LaF3 Laf3 for HCN Eynthesis 108, 109
decomposition o-chlorophenol 450–550 Fe2O3 integrated with Pt/SnO2 + Ir/La2O3 110
dioxin 400–500 Fe2O3 integrated with Pt/SnO2 + Ir/La2O3 110
Reduction or NO + C3H6 450–800 Al2O3 to N2, mixed with Mn2O3 96–98
decomposition of N2O (+ O2 + H2O) 500– Co3O4 to N2 101
NOx
Oxidation or CO + H2O 400–500 TiO2, ZrO2, CeO2 to CO2 + H2 102–104
Reduction of COx CO + 2H2 400–500 ZnO to methanol 92
CO2 + 3H2 400–500 ZnO to methanol 92, 93
CO2 + 3H2 400–500 TiO2 to CO 92
Selective oxidation C3H6 + H2 + O2 300–500 TiO2 (anatase), Ti-SiO2 to propylene oxide 46, 53–59
C3H8 + O2 + H2 300–400 TiO2 (anatase) to aceton 46
C4H10 + O2 + H2 300–400 TiO2 (anatase) to butanol 46
glycols room temp. activated carbon to a-hydroxy acids, liquid phase 35, 94, 95
Selective CH∫CH 400–500 Al2O3 to ethylene 88
hydrogenation CH2 =CH–CH=CH2 400–500 Al2O3, SiO2, TiO2 to butenes 9, 10, 87
crotonaldehyde 500–550 ZnO to crotyl alcohol 90
acrolein 513–593 ZrO2 to allylalcohol 91
Hydrochlorination CH∫CH 373–393 AuCl3/activated carbon to vinyl chloride 107
which was supported on a zeolite wash-coated honeycomb, has synthesis by the hydrogenation of CO and CO2, ZnO, which
been commercially used as an deodorizer in modern Japanese has been used as a support for commercial Cu catalysts, also
toilets since 1992. works as the best support.92,93
A characteristic feature of Au catalysts for the hydrogena- Prati and Rossi35 have found that Au supported on acti-
tion of unsaturated hydrocarbons is that partial hydrogenation vated carbon, g-Al2O3, or TiO2, is more active and selective
takes place very selectively: butadiene to butene and acetylene than other noble metal catalysts for oxidation in a
to ethylene.9,10,87,88 Hydrocarbon hydrogenations are known to MeOH–H2O (6 : 4) solvent of diols to a-hydroxy acids, which
be structure-insensitive processes, proceeding at approximately are used in the cosmetics and food industries.35,94,95
the same TOF on metal particles of various sizes.89 This The reduction of NO with hydrocarbons to N2 in the
was also the case of the hydrogenation of butadiene over Au co-presence of excess O2 and H2O is an important reaction in
catalysts as far as Al2O3, SiO2, and TiO2 were concerned as a the treatment of exhaust gases in gasoline and diesel engines.
support.87 The turnover frequency (TOF) differed by only a This reaction takes place over some supported Au catalysts.96,97
factor of three among Au particles with mean diameters Alkenes (C2H4, C3H6) are more effective as reductants than are
ranging from 3.5–7 nm, which were deposited on Al2O3, SiO2, alkanes (CH4, C2H6, C3H8) because the former adsorb to a
or TiO2. In the hydrogenation of a, b unsaturated aldehyde greater degree on Au surfaces. The optimum temperature and
such as crotonaldehyde, selectivity to the hydrogenation of maximum efficiency for NO reduction depend on the kind of
C¨O as opposed to that of C¨C (to form crotylalcohol) has metal oxide supports. They increase in the order of a-Fe2O3
been recently reported to reach 80% when Au particles are (523K, 12%), ZrO2 (523K, 32%), ZnO (523K, 49%), TiO2
deposited on ZnO.90 Allylalcohol was produced with selectiv- (623K, 30%), MgO (623K, 42%), and Al2O3 (673K, 80%).
ity above 40% from acrolein over Au/ZrO2.91 For methanol The degree of NO conversion to N2 obtained over Au/Al2O3
© 2003 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. 83
THE CHEMICAL RECORD
84 © 2003 The Japan Chemical Journal Forum and Wiley Periodicals, Inc.
Catalysis by Nanoparticles
To increase the effectiveness of recent attempts to combine [7] Bamwenda, G.R.; Tsubota, S.; Nakamura, T.; Haruta, M.
experimental work using real and model catalysts with Catal Lett 1997, 44, 83.
theoretical calculations,116 the effect of moisture should also be [8] Buffet, Ph.; Borel, J.-P. Phys Rev A 1976, 13, 2287.
considered. Most work in surface science occurs in an ultra- [9] Bond, G.C.; Sermon, P.A. Gold Bull 1973, 6, 102.
[10] Bond, G.C.; Sermon, P.A. J C S Chem Comm 1973, 444.
high vacuum, while measurements of the activity of real cata-
[11] Cha, D.Y.; Parravano, G. J Catal 1970, 18, 200.
lysts are conducted in a fixed bed flow reactor using reactant
[12] Galvano, S.; Parravano, G. J Catal 1978, 55, 178.
gas containing a moisture level of at least 1 ppm, usually 10 [13] Schwank, J. Gold Bull 1983, 16, 4, 103.
ppm. The catalyst surfaces are covered with OH groups and [14] Huber, H.; McIntosh, D.; Ozin, G.A. Inorg Chem 1977, 16,
water molecules at room temperature. For CO oxidation, 975.
which does not produce H2O and proceeds at temperatures [15] Haruta, M.; Kobayashi, T.; Sano, H.; Yamada, N. Chem Lett
below 373K, moisture markedly changes the catalytic activity 1987, 405.
of the metal oxides and the Au catalysts. Under dry conditions [16] Haruta, M.; Sano, H. Studies Surf Sci Catal 1983, 16, 225.
with an H2O concentration of 80 ppb, CO oxidation can occur [17] Haruta, M.; Yamada, N.; Kobayahsi, T.; Iijima, S. J Catal
over Co3O4 without Au even at 210K,117,118 while supported 1989, 115, 301.
Au catalysts prefer moisture.50 [18] Haruta, M.; Tsubota, S.; Kobayashi, T.; Kageyama, H.; Genet,
M.J.; Delmon, B. J Catal 1993, 144, 175.
[19] Haruta, M.; Kobayashi, T.; Iijima, S.; Delannay, F. Proc 9th
Int Congr Catal, Calgary, Canada, July 1988, p 1206.
Conclusions [20] Haruta, M.; Catal Today 1997, 36, 153.
[21] Haruta, M. Catal Surveys from Japan 1997, 1, 61.
1) There are three factors for the genesis of unique catalysis [22] Bond, G.C.; Thompson, D.T. Catal Rev Sci Eng 1999, 41,
by gold: strong contact between Au particles and the 319.
support, selection of the support, and the size of the Au [23] Osaka National Research Institute Activity Report No. 393,
1999.
particles.
[24] Haruta, M.; Daté, M. Appl Catal A: General 2001, 222, 427.
2) Perimeter interfaces provide the sites for reaction, while [25] Haruta, M. CATTECH 2002, 6, 3, 102.
metallic Au surfaces are still required as reservoirs for a [26] Haruta, M.; Tsubota, S.; Okumura, M. Advances in Catalyst
reactant. Preparation (in Japanese). eds. Y. Ono et al. Association for the
3) Very low apparent activation energies and enhancement by Promotion of Catalyst Preparation Chemistry: Tokyo 2000,
moisture contribute to the advantages of using Au catalysts 39.
in environmental applications, which often prefer low- [27] Kobayashi, T.; Haruta, M.; Tsubota, S.; Sano, H. Sensors and
temperature operation. Actuators B1 1990, 222.
4) Gold is the best sample for fundamental studies on the [28] Shibata, M.; Kuwata, N., Matsumoto, T., Kimura, H. Chem
effect of size below 2 nm through model catalysts and the- Lett 1985, 1605.
oretical calculations. [29] Tsubota, S.; Haruta, M.; Kobayashi, T.; Ueda, A.; Nakahara,
Y. Studies Surf Sci Catal 1991, 63, 695.
5) The methods of preparation and the mechanisms that
[30] Okumura, K.; Tanaka, M.; Ueda, A.; Haruta, M. Solid State
induce the high catalytic activity of Au are applicable to Ionics 1997, 95, 143.
other metals. [31] Okumura, M.; Tsubota, S.; Iwamoto, M.; Haruta, M. Chem
Lett 1998, 315.
[32] Yuan, Y.; Kozlova, A.P.; Asakura, K.; Wan, H.; Tsai, K.;
The author thanks Dr. Daté of AIST, Kansai, for drawing Iwasawa, Y. J Catal 1997, 170, 191.
the figures and for critical reading. [33] Okumura, M.; Haruta, M. Chem Lett 2000, 396.
[34] Grunwaldt, J.-D.; Kiener, C.; Wögerbauer, C.; Baiker, A. J
Catal 1999, 181, 223.
REFERENCES [35] Prati, L.; Rossi, M. Green Chemistry: Challenging Perspec-
tives. Tundo P, Anastas P, Eds. Oxford, 2000. p 183.
[1] Ponec, V.; Bond, G.C. Catalysis by Metals and Alloys; [36] Valden, M.; Pak, S.; Lai, X.; Goodman, D.W. Catal Lett 1998,
Elsevier: Amsterdam, 1996. 56, 7.
[2] Iwamoto, M. Studies Surf Sci Catal 2000, 130, 23. [37] Wallace, W.T.; Whetten, R.L. J Phys Chem 2000, B104,
[3] Sault, A.G.; Madix, R.J.; Campbell, C.T. Surf Sci 1986, 169, 10964.
347. [38] Kishi, M.; Daté, M.; Haruta, M. Surf Sci 2001, 486,
[4] Saliba, N.; Parker, D.H.; Koel, B.E. Surf Sci 1998, 410, 270. L475.
[5] Koel, J.; Wang, B.E. J Phys Chem 1998, A102, 8573. [39] Larsson, C.E.; Baum, T.H.; Jackson, R.L. J Electrochem Soc
[6] Hammer, B.; Nørskov, J.K. Nature 1995, 376, 238. 1987, 134, 266.
© 2003 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. 85
THE CHEMICAL RECORD
[40] Akita, T.; Tanaka, K.; Tsubota, S.; Haruta, M. J Electron [69] Peden, C.H.F. Surface Science of Catalysis. In Situ Probes and
Microscopy 2000, 49, 657. Reaction Kinetics, ACS Symp Ser 482. D.J. Dwyer,
[41] Ichikawa, M.; Akita, T.; Okumura, M.; Tanaka, K.; Haruta, Hoffmann, F.M. eds., Am Chem Soc: Washington, DC, 1992,
M. Proc 7th Intern Symp Advanced Physical Fields, Noda ed. p. 143.
National Institute of Materials Science: Tsukuba, Japan, [70] Boccuzzi, F.; Chiorino, A.; Manzoli, M.; Lu, P.; Akita, T.;
November 2001, p 369. Ichikawa, S.; Haruta, M. J Catal 2001, 202, 256.
[42] Akita, T.; Lu, P.; Ichikawa, S.; Tanaka, K.; Haruta, M. Surf [71] Ruggiero, C.; Hollins, P. Surf Sci 1997, 377–379, 583.
Interface Anal 2001, 31, 73. [72] Olea, M.; Kunitake, M.; Shido, T.; Iwasawa, Y. Phys Chem
[43] Ertl, G. Chem Record 2001, 1, 33. Chem Phys 2001, 3, 627.
[44] Torres Sanchez, R.M.; Ueda, A.; Tanaka, K.; Haruta, M. J [73] Schubert, M.M.; Hackenberg, S.; van Veen, A.C.; Muhler, M.;
Catal 1997, 168, 125. Plzak, V.; Behm, R.J. J Catal 2001, 197, 113.
[45] Chem Eng News, July 5,1999, p 33. [74] Liu, H.; Kozlov, A.I.; Kozlova, A.P.; Shido, T.; Asakura, K.;
[46] Hayashi, T.; Tanaka, K.; Haruta, M. J Catal 1998, 178, 566. Iwasawa, Y. J Catal 1999, 185, 252.
[47] Liu, Z.M.; Vannice, M.A. Catal Lett 1997, 43, 51. [75] Okumura, M.; Coronado, J.M.; Soria, J.; Haruta, M.; Conesa,
[48] Tsubota, S.; Nakamura, T.; Tanaka, K.; Haruta, M. Catal Lett J.C. J Catal 2001, 203, 168.
1998, 56, 131. [76] Minicò, S.; Scirè, S.; Crisafulli, C.; Visco, A.M.; Galvagno, S.
[49] Okumura, M.; Nakamura, S.; Tsubota, S.; Nakamura, T.; Catal Lett 1997, 47, 273.
Azuma, M.; Haruta, M. Catal Lett 1998, 51, 53. [77] Hao, Z.; An, L.; Wang, H.; Hu, T. React Kinet Catal Lett
[50] Daté, M.; Haruta, M. J Catal 2001, 201, 221. 2000, 70, 153.
[51] Cunningham, D.A.H.; Vogel, W.; Kageyama, H.; Tsubota, S.; [78] Horváth, D.; Toth, L.L. Guczi, Catal Lett 2000, 67, 117.
Haruta, M. J Catal 1998, 177, 1. [79] Wagner, F.E., Galvagno, S., Milone, C., Visco, A.M.; Stievano,
[52] Lipkowski, J.; Ross, P.N.Jr. Electrocatalysis, Frontiers in L.; Calogero, S. J Chem Soc Faraday Trans 1997, 93, 3403.
Electrochemistry. VCH: New York,1997, Vol. 5. [80] Kageyama, H.; Kamijo, N.; Kobayashi, T.; Haruta, M. Physica
[53] Haruta, M.; Uphade, B.S.; Tsubota, S.A. Miyamoto, Res 1989, B158, 183.
Chem Intermed 1998, 24, 329. [81] Tsubota, S.; Cunningham, D.A.H.; Haruta, M. Studies Surf
[54] Kalvachev, Y.A.; Hayashi, T., Tsubota, S.; Haruta, M. J Catal Sci Catal 1995, 91, 227.
1999, 186, 228. [82] Kobayashi, Y.; Nasu, S.; Tsubota, S.; Haruta, M. Hyperfine
[55] Uphade, B.S.; Akita, T.; Nakamura, T.; Haruta, M. J Catal Interactions 2000, 126, 95.
2002, 209, 331. [83] Bond, G.C.; Thompson, D.T. Gold Bull 2000, 33, 41.
[56] Stangland, E.E.; Stavens, K.B.; Andres, R.P.; Delgass, W.N. J [84] Haruta, M. Now and Future 1992, 7, 13.
Catal 2000, 191, 332. [85] Walters, R.D.; Weimer, J.J.; Smith, J.E. Catal Lett 1995, 30,
[57] Mul, G.; Zwijnenburg, A.; Linden, B.; Makkee, M.; Moulijn, 181.
J.A. J Catal 2001, 201, 128. [86] Ueda, A.; Haruta, M. Shigen Kankyou Taisaku (Resources and
[58] Qi, C.; Akita, T.; Okumura, M.; Haruta, M. Appl Catal A: the Environmental Technology) 1992, 28, 1035.
General 2001, 218, 81. [87] Okumura, M.; Akita, T.; Haruta, M. Catal Today 2002, 74,
[59] Sinha, A.; Seelan, S.; Akita, T.; Tsubota, S.; Haruta, M. Appl 265.
Catal A General, in press. [88] Jia, J.; Haraki, K.; Kondo, J.N.; Domen, K.; Tamaru, K. J Phys
[60] Valden, M.; Lai, X.; Goodman, D.W. Science 1998, 281, Chem 2000, B104, 11153.
1647. [89] Xu, Z.; Xiao, F.-S.; Purnell, S.K.; Alexeev, O.; Kawi, S.;
[61] Haruta, M. Catalysis and Electrocatalysis on Nanoparticles, A. Deutsh, S.E.; Gates, B.C. Nature 1994, 372, 346.
Wieckowski, E.R. Savinova, Vayenas, C.G. eds. Marcel [90] Bailie, J.E.; Abdullah, H.A.; Anderson, J.A.; Roechester, C.H.;
Dekker: New York, 2003, 240, 243. Richardson, N.V.; Hodge, N.; Zhang, J.-G.; Burrows, A.;
[62] Iizuka, Y.; Tode, T.; Takao, T.; Yatsu, K.; Takeuchi, T.; Tsubota, Kiely, C.J.; Hutchings, G.J. Phys Chem Chem Phys 2001, 3,
S.; Haruta, M. J Catal 1999, 187, 50. 4113.
[63] Mavrikakis, M.; Stoltze, P. Nørskov, J.K. Catal Lett 2000, 64, [91] Mohr, C.; Hofmeister, H.; Lucas, M.; Claus, P. Chemie Inge-
101. nieur Techn 1999, 71, 869.
[64] Vogel, W.; Cunningham, D.A.H.; Tanaka, K.; Haruta, M. [92] Sakurai, H.; Haruta, M. Appl Catal A: General 1995, 127, 93.
Catal Lett 1996, 40, 175. [93] Baiker, A.; Kilo, M.; Maciejewski, M.; Menzi, S.; Wokaun, A.;
[65] Cunningham, D.A.H.; Vogel, W.; Haruta, M. Catal Lett 1999, Guzci, L. et al. eds. Proc 10th Int Congr Catal, Elsevier, Ams-
63, 43. terdam, 1993, p 1257.
[66] Heiz, U.; Schneider, W.-D. J Phys D: Appl Phys 2000, 33, [94] Bianchi, C.; Porta, F.; Prati, L.; Rossi, M. Topics in Catal 2000,
R85. 13, 231.
[67] Abbet, S.; Heiz, U.; Häkkinen, H.; Landman, U. Phys Rev [95] Porta, F.; Prati, L.; Rossi, M. Coluccia, S.; Martra, G. Catal
Lett 2001, 86, 5950. Today 2000, 61, 165.
[68] Heiz, U.; Sanchez, A.; Abbet, S.; Schneider, W.-D. J Am Chem [96] Ueda, A.; Haruta, M. Appl Catal B: Environmental 1996, 285,
Soc 1999, 121, 3214. 81.
86 © 2003 The Japan Chemical Journal Forum and Wiley Periodicals, Inc.
Catalysis by Nanoparticles
[97] Ueda, A.; Haruta, M. Gold Bull 1999, 32, 3. [109] Takita, Y.; Imamura, T.; Mizuhara, Y.; Abe, Y.; Ishihara, T.
[98] Ueda, A.; Haruta, M. Appl Catal B: Environmental 1998, 18, Appl Catal B: Environmental 1992, 1, 79.
115. [110] Okumura, M.; Haruta, M.; Wang, X.; Kajikawa, O.; Okada,
[99] Hinshelwood, C.N.; Prichard, C.R. Proc Roy Soc London O. Abstract 3rd Intern Conf Environmental Catal Tokyo, Dec
1925, 108A, 211. 2001, p 15.
[100] Stepanov, V.M.; Yagodovskii, V.D.; Agilar, H. Russian J Phys [111] Usami, Y.; Kagawa, K.; Kawazoe, M.; Matsumura, Y.; Sakurai,
Chem 1975, 49, 1335. H.; Haruta, M. Appl Catal A: General 1998, 171, 123.
[101] Yan, L.; Zhang, X.; Ren, T.; Zhang, H.; Wang, X.; Suo, J. [112] Shen, W.; Ichihashi, Y.; Okumura, M.; Matsumura, Y. Catal
Chem Comm 2002, 860. Lett 2000, 64, 23.
[102] Sakurai, H.; Ueda, A.; Kobayashi, T.; Haruta, M. J Chem Soc [113] Golunsky, S.; Rajaram, R.; Hodge, N.; Hutchings, G.; Kiely,
Chem Commun 1997, 271. C.J. Catal Today 2002, 72, 107.
[103] Andreeva, D.; Idakiev, V.; Tabakov, T.; Andreev, A. J Catal [114] Cosandey, F.; Madey, T.E. Surf Rev Lett 2001, 8, 73.
1996, 158, 91. [115] Bondzie, V.A.; Parker, S.C.; Campbell, C.T. Catal Lett 1999,
[104] Tabakova, T.; Idakiev, V.; Andreeva, D.; Mitov, I. Appl Catal 63, 143.
A: General 2000, 202, 336. [116] Schlögel, R. CATTECH 2001, 5, 146.
[105] Kahlich, M.J.; Gasteiger, H.A.; Behm, R.J. J Catal 1999, 182, [117] Cunningham, D.A.H.; Kobayashi, T.; Kamijo, N.; Haruta, M.
430. Catal Lett 1994, 25, 257.
[106] Schubert, M.M.; Hachenberg, S. van Veen, A.C.; Muhler, M.; [118] Haruta, M.; Yoshizaki, M.; Cunningham, D.A.H.; Iwasaki, T.
Plzak, V.; Behm, R.J. J Catal 2001, 187, 113. Ultraclean Technology (in Japanese) 1996, 8, 1.
[107] Nkosi, B.; Adams, M.D.; Coville, N.J.; Hutchings, G.J. J Catal [119] Daté, M.; Ichihashi, Y.; Haruta, M. Jpn Pat Appl 2000-
1991, 128, 333, 378. 158422.
[108] Aida, T.; Higuchi, R.; Niiyama, H. Chem Lett 1990,
2247.
© 2003 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. 87