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Top Catal (2008) 49:126135 DOI 10.

1007/s11244-008-9077-0

ORIGINAL PAPER

Colloid Science of Metal Nanoparticle Catalysts in 2D and 3D Structures. Challenges of Nucleation, Growth, Composition, Particle Shape, Size Control and Their Inuence on Activity and Selectivity
Gabor A. Somorjai Jeong Y. Park

Published online: 27 June 2008 Springer Science+Business Media, LLC 2008

Abstract Recent breakthroughs in the synthesis of nanosciences have achieved the control of size and shape of nanoparticles that are relevant for catalyst design. In this article, we review advances in the synthesis of nanoparticles, fabrication of two- and three-dimensional model catalyst systems, characterization, and studies of activity and selectivity. The ability to synthesize monodispersed platinum and rhodium nanoparticles 110 nm in size permitted us to study the inuence of composition, structure, and dynamic properties of monodispersed metal nanoparticles on chemical reactivity and selectivity. We review the importance of the size and shape of nanoparticles to determine reaction selectivity in multi-path reactions. The inuence of metalsupport interaction has been studied by probing the hot electron ows through the metaloxide interface in catalytic nanodiodes. Novel designs of nanoparticle catalytic systems are also discussed. Keywords Platinum Rhodium Nanoparticle Reaction selectivity Multi-path reactions Nanoscience Metaloxide interface Catalytic nanodiode Bimetallic nanoparticles Enzyme Homogeneous Heterogeneous catalysis

1 Introduction: Evolution of Catalyst Model System It rarely happens in the history of catalysis that new catalyst materials and structures are invented that lead to the development of new catalytic reactions and new chemical and energy conversion processes. Nanoscience and the synthesis of monodispersed nanoparticles present this opportunity. Most industrial heterogeneous catalysts are highly dispersed metal nanoparticles supported on porous oxides [15]. Recent breakthroughs in synthesis in nanosciences have achieved the control of size and shape of nanoparticles [1, 611]. The inuence of composition, structure, and dynamic properties of monodispersed metal nanoparticles on chemical reactivity and selectivity have been studied to bridge the so-called materials gap [46, 9, 10, 1214]. In this article, we review the evolution of model catalysts over the past 10 years that are moving from studies of single crystal surfaces to nanoparticles fabricated by colloid synthesis. The evolution of model catalyst systems are shown in Fig. 1. Single crystal surfaces have served as model catalytic systems that have shed light on many surface phenomena. However, single crystal surfaces inherently lack the complexity needed to uncover many of the factors important in catalytic turnover and selectivity of industrial catalysis. To consider these factors, such as metalsupport interactions and the importance of metallic cluster size, new catalytic model systems have been suggested. Figure 1 shows two emerging model systems made up of colloid nanoparticles, where size and shape are controlled on two or three dimensional supports. To fabricate two-dimensional (2D) or three-dimensional (3D) nanoparticle arrays, we deposit nanoparticle arrays on the planar support or encapsulate them in the 3D mesoporous support, and carry out characterization and catalytic

G. A. Somorjai (&) J. Y. Park Department of Chemistry, University of California, Berkeley, CA 94720, USA e-mail: somorjai@berkeley.edu G. A. Somorjai J. Y. Park Materials Sciences Division and Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA

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Fig. 1 Schematic showing the evolution of the catalyst model system from the single crystal metal surface to the 2D and 3D nanoparticle arrays that are composed of colloid synthesized nanoparticles and 2D and 3D oxide supports

studies on these model systems. The nanoparticles are synthesized using colloid techniques by the reduction of a platinum or rhodium precursor in alcohol in the presence of a polymer capping agent to prevent aggregation [10, 11, 15, 16]. As the particles nucleate and grow they are kept with a polymer that is porous enough to allow growth to various sizes from 1 to 8 nm, as shown in Fig. 2a. Not only can we control the particle size by the monomer concentration but, with suitable changes of the growth parameters, we can change the shape of these particles from hexagonal
Fig. 2 (a) TEM images of Pt nanoparticles with various sizes capped with PVP poly (vinylpyrrolidone). Size of nanoparticles can be controlled in the range of 1.77.1 nm. The scale bars refer to 10 nm. (b) TEM image of Pt nanoparticles with different shapes (cube, cuboctahedra, and porous particles) stabilized with CTAB. The scale bar in the images refer to 20 nm

to cubic, as well as to an intermediate shape called cuboctahedra, which is a cube with truncated vertices as shown in Fig. 2b [8, 17]. Once we have obtained monodispersed particles with the desired size and shape, we can put it in a Langmuir trough and squeeze it with a certain surface pressure to deposit different densities of monolayer lms of these nanoparticles. The average inter-particle spacing can be tuned by varying surface pressure, as shown in Fig. 3 [10, 11, 18]. This approach has the advantage of controlling the size and shape of the nanoparticles synthesized via this colloidal route and the formation of an oxidemetal interface between the nanoparticles and substrate. Various surface techniques, such as X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM), can be utilized to characterize the chemical composition and morphology of 2D nanoparticle arrays before and after the chemical reactions. Colloid nanoparticles can also be used in 3D model catalysts. The 3D nanoparticle systems have high surface areas of *1 m2/g, oxide/metal interfaces that closely resemble industrial systems, and controllable size and shape. We can encapsulate the nanoparticles with mesoporous support, such as SBA-15 silica. Figure 4 shows the TEM image of Pt nanoparticles (2.6 nm) assembled into SBA-15 silica support via the synthesis method called capillary inclusion. In this method, monodispersed Pt nanoparticles and mesoporous SBA-15 silica are mixed in a water/ethanol solution with low power sonication to

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20

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Surface Pressure (mN/m)

16 12 8 4 0

crystals at 798 K and a total pressure of 20 atm of a stoichiometric mixture of hydrogen and nitrogen, and found that the (111) face is the most active face. This structure sensitivity leads to an increase in turnover rate for ammonia formation as the iron nanoparticle size is

5 15 10 Average interparticle spacing (nm)

20

Fig. 3 Plot of surface pressure as a function of average interparticle spacing of monodispersed Pt nanoparticle arrays. The surface density of nanoparticles is controlled by the surface pressure. The scale bars in the TEM images are 20 nm

SBA-15 (9.0 nm) sonication Room Pt-PVP particle temperature (2.9 nm) 3h O2 flow 450 C, 12 h

Pt/SBA-15

10 nm

20 nm

10 nm

Pt(2.6 nm)-PVP

0.90% Pt(2.6 nm)/SBA-15

Fig. 5 Turnover rate for the synthesis of ammonia as a function of Fe particle size. Rate of turnover rate of ammonia synthesis was measured at 673 K, atomospheric pressure, and stoichiometric mixture of 0.15. The KMI and KMH catalysts are promoted, unsupported iron. The sites were counted by chemisorption of H2, CO, or N2 as indicated
8.0 14.0

Fig. 4 TEM images of Pt nanoparticles (2.6 nm) assembled into SBA-15 silica support by capillary inclusion method

ethylene hydrogenation
Pt(111) 12.0 10.0 8.0 6.0

TOF (C2H6 /Pt site/s)

promote nanoparticle entry into the SBA-15 pore structure by capillary inclusion and mechanical agitation [10]. The other method of 3D catalyst synthesis involves the hydrothermal synthesis of SBA-15 silica in a solution containing polymer-stabilized Pt nanoparticles. This method, referred to as nanoparticle encapsulation (NE), leads to Pt/SBA-15 catalysts with particles located within the silica pore structure [11].

7.0 6.0 5.0 4.0 3.0 2.0

Activation Energy (kcal/mol)

4.0 Pt(111) 2.0 0.0 0 2 4 6 8

2 Chemical Activity Studies of 2D and 3D Nanoparticle Systems We have carried out several studies of catalytic activity in 2D and 3D nanoparticle systems. Ammonia synthesis is very structure sensitive [19, 20]. Spencer et al. studied ammonia formation on ve different faces of iron single

1.0 0.0

Particle Size (nm)


Fig. 6 Turnover rate and activation energy of ethylene hydrogenation over Pt nanoparticles and single crystals as a function of particle size. All data were taken at or corrected to 298 K, 10 Torr C2H4, 100 Torr H2

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0.4 0.35 0.3 Pt(111) 80
0.9 Pt(111) 25.0 Pt(100) Pt(111) 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 0 2 4 6 8 10 12 0.0 5.0 10.0

129

Total TOF (molecule/Pt site/s)

70 60 50 40

0.8

Activation Energy (kcal/mol)

Activation Energy (kcal/mol)

20.0 Pt(100) 15.0

TOF (CH4 /Pt/s)

0.25 0.2

C2 H6 hydrogenolysis
0.15 0.1 0.05 0 0 2 4 6 8 Pt(111) 30 20 10 0

Particle Size (nm)


Fig. 7 Turnover rate and activation energy of C2H6 hydrogenolysis over Pt nanoparticles and single crystals as a function of particle size. All data were taken at or corrected to 658 K, 20 Torr C2H6, 200 Torr H2

Particle Size (nm)


Fig. 9 Turnover rate and activation energy over Pt nanoparticles as a function of particle size in crotonaldehyde hydrogenation. Total turnover rate refers to the sum of product molecules per Pt site per second. All data of (a) were taken at 393 K, 1 Torr C4H6O, 100 Torr H2

increased, as shown in Fig. 5, because the (111) surface is preferential as the particle size increases [1921]. Song et al. studied the dependence of turnover rate and activation energy on the Pt particle size under ethylene hydrogenation and ethane hydrogenolysis. Monodisperse platinum nanoparticles of 1.77.1 nm have been synthesized by alcohol reduction methods and incorporated into mesoporous SBA-15 silica during hydrothermal synthesis. Figure 6 shows the plot of turnover rate and activation energy of ethylene hydrogenation over Pt nanoparticles and single crystals as a function of particle size under ethylene hydrogenation, indicating that the turnover rates are unchanged with changing the size of Pt nanoparticle, along with the activation energy, which also remains constant. All data were taken at or corrected to 298 K, 10 Torr C2H4,
Fig. 8 Turnover rate and activation energy over Pt nanoparticles as a function of particle size in (a) cyclohexene hydrogenation and (b) dehydrogenation. All data of (a) were taken at 310 K, 10 Torr C6H10, 200 Torr H2, steady state, and (b) were taken 448 K, 10 Torr C6H10, 200 Torr H2, steady state

100 Torr H2 [11, 22]. For ethane hydrogenolysis to methane, the turnover rate declines with particle size, while the activation energy increases, as shown in Fig. 7 [11]. Turnover frequencies decrease by 2 orders of magnitude over the size range, while the apparent activation energy increases. Coordinatively unsaturated surface atoms in small particles have a higher reactivity and subsequently a smaller barrier for hydrogenolysis than highly coordinated surface atoms of larger particles. For cyclohexene hydrogenation to cyclohexane over platinum nanoparticles, again the turnover rate and the activation energy remains unchanged with increasing particle size (Fig. 8a). However, for cyclohexene dehydrogenation to benzene, the turnover rate declines markedly and activation

(a)

+ H2

(b)

+ 2H2

Cyclohexene hydrogenation
30 12.0 30

Cyclohexene dehydrogenation
12.0

Activation Energy (kcal/mol)

Activation Energy (kcal/mol)

TOF (C6H12 /Pt site/s)

TOF (C6H12 /Pt site/s)

25 20 15 10 5 0 0 2 4 6 8

10.0 8.0 6.0 4.0 2.0 0.0

25 20 15 10 5 0 0 2 4 6 8

10.0 8.0 6.0 4.0 2.0 0.0

Particle Size (nm)

Particle Size (nm)

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130
Preparation chamber (sample cleaning) (s

Top Catal (2008) 49:126135

(a)

STM chamber (high pressure cell)

3 Catalyst Characterization Under Reaction Conditions Surface science techniques allow us to determine reaction intermediates at catalytic reaction conditions, along with the surface mobility [14, 23]. The high pressure scanning tunneling microscopy allows us to look at surface mobility (Fig. 10a) [2428], while sum frequency generation vibrational spectroscopy allows us to measure the vibrational spectra of adsorbed molecules [2931] (Fig. 10b). Figure 11a shows that during cyclohexene hydrogenation/ dehydrogenation the three species on the catalytically active surfaces are 1,3 cyclohexadiene, p-allyl and 1,4 cyclohexadiene [32]. During the reaction, scanning tunneling microscopy at high pressure shows no sign of order on the catalytic reactive surface. The mobility of the adsorbate must be greater than 100 A per millisecond to make it impossible to exhibit ordered structure (Fig. 11b). However, when the reaction is poisoned by the introduction of carbon monoxide, an ordered structure forms and the catalytic turnover stops (Fig. 11c) [26]. Thus, mobility is an important feature of the catalytically reactive surface, as the adsorbate has to be mobile in order to turn over. Not only the adsorbates are mobile, but the substrate metal is mobile. We found that the (110) surface of platinum undergoes restructuring in different ways in the presence of atmospheric hydrogen, oxygen or carbon monoxide [33]. The restructuring of the surface coincides with the mobility of the adsorbate, thus the surface, both the metal and the

Mass spectroscopy LEED

(b)
IR

vis SFG

window Metal catalyst heater High pressure cell

Fig. 10 Schematic of (a) high pressure STM and (b) high pressure SFG spectroscopy

energy increases with particle size (Fig. 8b). Crotonaldehyde hydrogenation shows steady state turnover with increasing particle size along with unchanged activation energies (Fig. 9).

(a)
2
483 K

(b) 25
Pressure (mTorr)
20 15 10 5 0 0
Cyclohexane Benzene Cyclohexene

SFG intensity (a. u.)

453 K 403 K
1,3 - cyclohexadiene (C6 H8)

1
373 K 343 K 323 K

10

20

30

Time (hrs)

(c) 25
- allyl c-C6H9

Pressure (mTorr)

20 Cyclohexene 15 10 5 0 0 2 4 6 Benzene Cyclohexane

303 K

0 2600 2700 2800 2900 3000 3100

Wavenumber (nm 1)

1,4 - cyclohexadiene (C6H8 )

Time (hrs)

Fig. 11 (a) SFG spectrum of the Pt (111) surface during cyclohexene hydrogenation revealing reaction intermediates, 1,4-, 1,3-cyclohexadienes and p-allyl c-C6H9.techniques. (b) Mass spectrometer study showing the evolution of cyclohexane and benzene at 350 K produced by the hydrogenation and dehydrogenation of cyclohexene. The inset shows 7.5 nm 9 7.5 nm image of catalytically active Pt(111) at

300 K in 200 mTorr H2 and 20 mTorr cyclohexene. (c) Mass spectrometer study showing the evolution of cyclohexane and benzene at 350 K on CO poisoned Pt (111) surface. The inset shows 7 nm 9 7 nm image of CO poisoned Pt(111) at 300 K (in 200 mTorr H2, 20 mTorr of cyclohexene, and 5 mTorr CO)

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1 1

adsorbate, has to be dynamic for catalytic reactions to occur.


Cyclohexane (C6H12 selectivity)

+ H2
Benzene (C6H6 selectivity)
0.8 0.8

4 Reaction Selectivity on Nanoparticle Systems In the 21st century, catalysis science focuses on reaction selectivity. That is, if there are several thermodynamically stable products, we only want to form the one desired product and none of the undesired products. We have investigated the selectivity of typical multipath reactions; benzene, cyclohexene and crotonaldehyde hydrogenations. The reaction selectivity is much less understood than the reaction activity of single product catalytic reactions, such as ammonia synthesis or ethylene hydrogenation. A very small change in competing potential energy barriers due to structure or the use of additives changes the product selectivity dramatically. We studied this reaction in the form of benzene hydrogenation which produces two molecules: cyclohexane and cyclohexene on the platinum (111) surface while only one molecule (cyclohexene) on the (100) face. What we nd is that nanoparticles, when they are cuboctahedra, give rise to two products just like (111) single crystal surfaces, but when they are cubes, they give rise to one product like the (100) single crystal surface (Fig. 12) [17]. The reaction selectivity for cyclohexene hydrogenation/dehydrogenation favors cyclohexene formation as the particle size increases, while benzene formation declines (Fig. 13). The reason for this is that while the activation energy for hydrogenation of cyclohexene to cyclohexane is constant as a function of particle size and remains unchanged, the activation energy for dehydrogenation to benzene increases with increasing particle size that results in declining benzene concentrations. Figure 14a shows the schematic of a multi-path reaction, of crotonaldehyde hydrogenation. As shown in Fig. 14b, the sum total of butyraldehyde and crotyl alcohol, the two products of crotonaldehyde hydrogenation, is constant, while the selectivity changes with particle size, as small nanoparticles of platinum favor butyraldehyde while larger particle sizes favor the formation of crotyl alcohol.
Fig. 12 Structural dependence of selectivity in benzene hydrogenation. CHA and CHE refer to cyclohexane and cyclohexene molecules produced under benzene hydrogenation

0.6

0.6

0.4

0.4

0.2 Cyclohexene 0 0 2

- H2
Benzene

0.2

0 4 6 8

Particle size (nm)


Fig. 13 The size dependence of Pt nanoparticles on the selectivity of cyclohexene hydrogenation/dehydrogenation

5 Novel Nanoparticle Assembly for the Nanocatalysis Characterization and formation of either 2D or 3D assemblies are the basis for nanocatalysis followed by studies of reaction selectivity and activity. Nanoparticle synthesis studies indicate the formation of bimetallic nanoparticles, and several of these are shown in Fig. 15. We can make palladium/platinum bimetallic nanoparticles using platinum nanoparticles as seeds (Fig. 15a) [34]. Iron platinum (Fig. 15b) and cobalt platinum (Fig. 15c) bimetallic nanoparticles have been synthesized [35, 36]. These structures can be synthesized by using monodispersed nanoparticles as seeds for nucleating the second component of the nanoparticle. The bimetallic nanoparticle structure allows for the maximization of the density of interface sites and permits tailoring the composition of multicomponent catalytic systems with a high level of precision. Such structures can exhibit interesting properties by assembling two different catalysts into one nanoscale unit with a

(a)
0.30

(b)
0.10

TOF (molecule/site/s)

0.25 0.20 0.15 0.10 0.05 0.00 300 320 340

CHA Pt(111) CHA Pt(100)

TOF (molecule/site/s)

0.08 0.06 0.04 0.02 0.00 300 320

CHA cubes

CHA cuboctahedra CHE cuboctahedra (10)


340 360 380 400

CHE Pt(111)
360 380 400

Temperature, K

Temperature, K

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132 Fig. 14 (a) Schematics of crotonaldehyde hydrogenation, which is a multi-path reaction, and (b) size dependence of Pt nanoparticle on the selectivity in crotonaldehyde hydrogenation

Top Catal (2008) 49:126135

(a)

Butyraldehyde
H H3C O

(b) 0.8
Butyraldehyde 0.6

H H3C O

H 3C

OH

1-Butanol

Selectivity

0.4 Crotyl alcohol 0.2

Crontonaldehyde

H3C

OH

1-Butanol Propene 0 1 3 5 7

Crotyl alcohol
H3C CH2 + CO

Propene

Particle size (nm)

Fig. 15 Bimetallic nanoparticles with various shapes. (a) TEM image of palladium nanoparticles using platinum nanoparticles as seeds. (b) FePt nanoparticle and (c) CoPt3 nanoparticle

well-dened and easily accessible boundary between two materials. There is another type of nanoparticles called core shell structures, which is based on the Kirkendall effect. That is, when two substances diffuse to form a compound, one diffuses much faster than the other one. For example, zinc

and copper form brass, but zinc diffuses much faster than copper, leaving behind zinc vacancies [37]. Nanoparticles of cobalt can be made hollow by forming a sulde or an oxide as the shell. The cobalt diffuses out faster than the sulfur and oxygen diffuses in, forming a hollow nanocrystal as shown in Fig. 16 [38]. We can use this

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phenomenon to provide a shell of cobalt oxide around a platinum seed. Iron oxide shells around gold or iron have been all synthesized by a three-step process [38], as shown
Co2(CO)8
180 C Trioctylphosphine Oxide (TOPO) Oleic acid

Cobalt Nanocrystals

180 C

Sulfur, time < 1 sec

Cobalt Sulfide Hollow Nanocrystals

Fig. 16 TEM images of cobalt sulde hollow nanocrystals synthesized with Kirkendall Effect. Uniform cobalt nanocrystals can be synthesized by the rapid pyrolysis of cobalt carbonyl in a hot solvent. The sulde grows mainly by the outward diffusion of cobalt cations. Hollow cobalt sulde nanocrystals form with similar size distribution Fig. 17 Schematic of synthesis of Pt/CoO nanoreactors, and TEM images of Pt and Pt/CoO nanoreactors. The scale bar in TEM images refers to 50 nm

in Fig. 17. Platinum particles were synthesized rst, followed by injection and decomposition of Co2(CO)8 to form Pt/Co coreshell nanoparticles, and the introduction of oxygen to transform the Co into CoO hollow structures. The resulting material is a hollow CoO shell with a Pt nanoparticle in the interior. Formation of hollow nanostructures via the Kirkendall effect was observed for a number of materials, including Co/Co9S8, Co/CoO, Pt/ CoO, Ag/Au, and Fe/FexOy. In most cases the hollow exterior shell is polycrystalline, and selected small molecules are thought to enter the internal cavity via grain boundaries and pinholes. When encapsulated in this manner, the interior nanoparticles retain their catalytic activity, as was demonstrated by Yin et al for the ethylene hydrogenation reaction [38]. Encapsulated catalyst nanoparticles should be much more resistant to aggregation and sintering. Small average diameter of the pinholes for reactant access and product removal provides a means for molecular shape selectivity. Size and shape selectivity is expected for molecules with average cross-sections less than the pinhole diameter. By performing reactions in a conned medium, we also expect to improve the selectivity of hydrocarbon conversion reactions used in making liquid fuels. The core-shell nanoparticles combining oxides and transition metals can be synthesized in a similar manner. Metal oxides such as ZnO, MnO2, TiO2, Fe3O4 can be combined with transition metals (Pt, Pd, Ru, Ni, Co, Fe, Au, Cu) and used to investigate the catalytic activity and selectivity. The metaloxide interface is known to be the active site responsible for increased reaction rates in many industrial catalysts [39, 40]. However, characterization and control of these interfaces has been challenging, limiting

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134 Fig. 18 (a) The typical IV curves measured on Pd/TiOx diode. (b) The plot of chemicurrent and turnover rate measured on the Pd/TiOx diode during CO oxidation (100 Torr of O2 and 40 Torr CO) as a function of the temperature

Top Catal (2008) 49:126135

(a) 2

(b) 7
Ln [turnover rate (/Pd site/s)]
6 5 4 3 2 1 0 -1 0.0015
0.002
Turnover rate chemicurrent

7 6 5 4 3 2 1 0 -1 0.0025

I (mA)

-2

-1

Vs(V)

1/T (1/K)
t Bu t Bu

prospects for optimizing catalytic activity. The development and investigation of well-dened, multicomponent nanoparticle system with the control of size and shape by colloidal chemistry techniques are key issues in nanocatalysis.

(a)

(b)

C6F5 N Cl

2.24

O1.85 N

Ti 2.28
Cl O

6 The Active Sites at the Oxide Metal Interface Studies indicate that when a catalytically active metal is covered with an oxide that carries out no catalytic reaction, the metal becomes much more active. These studies were initiated in the 1950s and 1960s and an explanation for this phenomenon is provided by the evidence of hot electron generation at metal surfaces [41]. It appears that when photons strike a metal surface in the femtosecond regime, hot electrons are generated and diffuse into the metal before they are equilibrated with lattice vibrations. The diffusion mean free path is around 510 nm. Also, when vibrationally excited molecules strike another surface they are rapidly deexcited because of hot electron formation [4244]. We fabricated a catalytic nanodiode where catalytically reactive platinum thin lms were deposited on an oxide to form a Schottky barrier and we made contact to both sides of this barrier of Pt or Pd on TiOx or GaN [4547]. Figure 18a shows the typical IV curves measured on a Pd/TiOx diode. We fabricated 18 of these diodes on a 4 in. silicon wafer and then loaded it into a catalytic reactor where we can measure both the current and the product distribution of the gas phase reaction, which in this case was carbon monoxide oxidation. As seen in Fig. 18b, the chemicurrent is proportional to the turnover rate of the catalytic reaction indicating that the two correlate and coincide [48]. Our early experiment also suggests that application of a electrostatic potential between the metal and the oxide under the reaction condition may inuence the turnover rate. The mechanism underlying the inuence of hot electron ow on

C6F5

t Bu t

Cytochrome C Size: ~4 nm, 100 amino acids Molecular weight: ~12,000 daltons

Bu

Single-Site Olefin Polymerization Catalyst

Fig. 19 (a) Cytochrome C which has a 4 nm size where the catalytic site outside the protein ligands are 1.4 nm in size. (b) A single site olen polymerization catalyst, which is homogeneous, has a 1.6 nm size

catalytic activity is being investigated. This provides a glimpse of the possibility that by using hot electrons ow we can control turnover, while the turnover of the exothermic reaction provides hot electron ows.

7 Future Perspective: Catalysts are all Nanoparticles Whether we look at enzyme catalysts, homogeneous catalysts or heterogeneous catalysts, they are all nanoparticles. Figure 19a shows cytochrome C which has a 4 nm size where the catalytic site outside the protein ligands is 1.4 nm in size. A single site olen polymerization catalyst (Fig. 19b), which is homogeneous, has a 1.6 nm size [49]. Platinum nanoparticles can be produced and are active in the 17 nm regime. This shows that nature and technology prefers catalysts which are in the nanoparticle size range. To understand them, we have to be able to study them under the same reaction condition, if at all possible, to learn the molecular ingredients that are responsible for the

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135 22. Zaera F, Somorjai GA (1984) J Am Chem Soc 106:22882293 23. Somorjai GA, Bratlie KM, Montano MO, Park JY (2006) J Phys Chem B 110:2001420022 24. Hendriksen BLM, Frenken JWM (2002) Phys Rev Lett 89: 25. Jensen JA, Rider KB, Salmeron M, Somorjai GA (1998) Phys Rev Lett 80:12281231 26. Montano M, Salmeron M, Somorjai GA (2006) Surf Sci 600:18091816 27. Osterlund L, Rasmussen PB, Thostrup P, Laegsgaard E, Stensgaard I, Besenbacher F (2001) Phys Rev Lett 86:460463 28. Tang DC, Hwang KS, Salmeron M, Somorjai GA (2004) J Phys Chem B 108:1330013306 29. Bratlie KM, Kliewer CJ, Somorjai GA (2006) J Phys Chem B 110:1792517930 30. Shen YR (1989) Annu Rev Phys Chem 40:327350 31. Su XC, Cremer PS, Shen YR, Somorjai GA (1996) Phys Rev Lett 77:38583860 32. Bratlie KM, Flores LD, Somorjai GA (2005) Surf Sci 599:93106 33. McIntyre BJ, Salmeron M, Somorjai GA (1993) J Vac Sci Technol A-Vac Surf Films 11:19641968 34. Habas SE, Lee H, Radmilovic V, Somorjai GA, Yang P (2007) Nat Mater 6:692697 35. Shevchenko EV, Talapin DV, Rogach AL, Kornowski A, Haase M, Weller H (2002) J Am Chem Soc 124:1148011485 36. Shevchenko EV, Talapin DV, Kotov NA, OBrien S, Murray CB (2006) Nature 439:5559 37. Aldinger F (1974) Acta Metall 22:923928 38. Yin YD, Rioux RM, Erdonmez CK, Hughes S, Somorjai GA, Alivisatos AP (2004) Science 304:711714 39. Tauster SJ, Fung SC, Garten RL (1978) J Am Chem Soc 100:170175 40. Hayek K, Fuchs M, Klotzer B, Reichl W, Rupprechter G (2000) Top Catal 13:5566 41. Schwab GM (1967) Angew Chem Int Ed 6:375 42. Gadzuk JW (2002) J Phys Chem B 106:82658270 43. Hellberg L, Stromquist J, Kasemo B, Lundqvist BI (1995) Phys Rev Lett 74:47424745 44. Huang YH, Rettner CT, Auerbach DJ, Wodtke AM (2000) Science 290:111114 45. Ji XZ, Zuppero A, Gidwani JM, Somorjai GA (2005) Nano Letters 5:753756 46. Park JY, Renzas JR, Contreras AM, Somorjai GA (2007) Top Catal 46:217 47. Park JY, Somorjai GA (2006) Chemphyschem 7:14091413 48. Park JY, Renzas JR, Hsu BB, Somorjai GA (2007) J Phys Chem C 111:1533115336 49. Tian J, Hustad PD, Coates GW (2001) J Am Chem Soc 123:51345135

catalytic activity. This, we believe, will be one of the major directions of research in the near future.
Acknowledgement This work was supported by the Director, Ofce of Science, Ofce of Basic Energy Sciences, Division of Materials Sciences and Engineering of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231.

References
1. Roucoux A, Schulz J, Patin H (2002) Chem Rev 102:37573778 2. Tian N, Zhou ZY, Sun SG, Ding Y, Wang ZL (2007) Science 316:732735 3. Bell AT (2003) Science 299:16881691 4. Rioux RM, Song H, Grass M, Habas S, Niesz K, Hoefelmeyer JD, Yang P, Somorjai GA (2006) Top Catal 39:167174 5. Somorjai GA, Rioux RM (2005) Catal Today 100:201215 6. Freund HJ, Kuhlenbeck H, Libuda J, Rupprechter G, Baumer M, Hamann H (2001) Top Catal 15:201209 7. Narayanan R, El-Sayed MA (2004) Nano Letters 4:13431348 8. Lee H, Habas SE, Kweskin S, Butcher D, Somorjai GA, Yang PD (2006) Angew Chem Int Ed 45:78247828 9. Niesz K, Grass M, Somorjai GA (2005) Nano Letters 5:2238 2240 10. Rioux RM, Song H, Hoefelmeyer JD, Yang P, Somorjai GA (2005) J Phys Chem B 109:21922202 11. Song H, Rioux RM, Hoefelmeyer JD, Komor R, Niesz K, Grass M, Yang PD, Somorjai GA (2006) J Am Chem Soc 128:3027 3037 12. Somorjai GA, Park JY (2007) Catal Lett 115:8798 13. Somorjai GA, Park JY (2007) Phys Today 60:4853 14. Somorjai GA, York RL, Butcher D, Park JY (2007) Phys Chem Chem Phys 9:35003513 15. Humphrey SM, Grass ME, Habas SE, Niesz K, Somorjai GA, Tilley TD (2007) Nano Letters 7:785790 16. Zhang Y, Grass ME, Habas SE, Tao F, Zhang T, Yang P, Somorjai GA (2007) J Phys Chem C 111:1224312253 17. Bratlie KM, Lee H, Komvopoulos K, Yang P, Somorjai GA (2007) Nano Letters 7:30973101 18. Song H, Kim F, Connor S, Somorjai GA, Yang PD (2005) J Phys Chem B 109:188193 19. Boudart M, Lofer DG (1984) J Phys Chem 88:57635763 20. Spencer ND, Schoonmaker RC, Somorjai GA (1982) J Catal 74:129135 21. Topse H, Topse N, Bohlbro H, Dumesic JA (1981) In: Seiyama T, Tanabe K (eds) Proceedings of the 7th international congress on catalysis, part A. Kodansha, Tokyo, p 247

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