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Nanoparticulated Gold: Syntheses, Structures, Electronics, and Reactivities
Günter Schmid*[a] and Benedetto Corain[b]
Keywords: Gold / Nanoparticles / Synthetic methods / Quantum dots / Self-assembly / Heterogeneous catalysis
This microreview deals mainly with the synthesis and the electronic and chemical properties of gold nanoparticles. Modern synthetic routes, based on physical and on chemical procedures, as well as structural and optical features, are described. The bulk-to-molecule transition is discussed by studying size-controlled quantum-size effects, resulting in the determination of discrete electronic energy levels in Au55 clusters. Conductivity measurements of three- and two-dimensionally organized ligand-protected Au55 clusters are described, as well as the current techniques for the generation of ordered monolayers and artificial patterns of quantum dots. Finally, some aspects of the chemical activity of gold nanoparticles are discussed by considering ligand-exchange processes and, last but not least, the expanding role of gold nanoparticles in catalysis is considered. ( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Gold: quintessence of beauty and nobility among the metals. Some time during the Stone Age man discovered and learned to appreciate gold not only for its beauty but also for its resistivity against corrosion. Moreover, because of its relative scarcity, gold has been considered a substance of great value over millennia and today it still serves as monetary parity in many countries. The Old Testament is full of stories dealing with gold and numerous wars have been started because of gold. The early historical use of gold has also to do with its natural deposits as nuggets, which meant that no chemical processes were needed to be able to use it.
Universität Duisburg-Essen, Universitätsstrasse 5Ϫ7, 45117 Essen, Germany E-mail: email@example.com ` di Padova, Dipartimento di Chimica Inorganica, Universita Metallorganica ed Analitica, Via Marzolo 1, 35131 Padova, Italy
Due to its softness it could be hammered into articles of jewellery even in ancient times. Numerous civilizations therefore had already started gold mining by at least the 4th millennium BC. However, the mines operated by the Egyptians in Nubia surpassed all of them by far. Gold became a decisive reason for the power of the Egyptian rulers. It was, and still is, synonymous of wealth. In contrast to the long history of gold, the development of its chemistry was retarded because of its noble character. It can only be dissolved in oxidising media like aqua regia or by complexing species such as cyanides under air. Nowadays, the chemistry of gold is rather broad, beginning with classical complex chemistry via novel organometallic chemistry up to solid-state chemistry where so-called aurides give evidence of the high electronegativity of this unique metal. Long before the development of modern gold chemistry the special appearance of gold was appreciated by mankind: its ruby red colloids were used to color glasses and cer-
Günter Schmid studied chemistry at the University of Munich. He received his Diploma in 1962 and his Doctor’s Degree in Inorganic Chemistry in 1965, both at the University of Munich. In 1966 he moved to the University of Marburg, Germany, and finished his Habilitation in 1969. In 1971 he got a professorship at the University of Marburg and he then moved to the University of Essen, Germany, where he became the director of the Institute for Inorganic Chemistry (1977). His main research interests include the synthesis and investigation of large transition metal clusters and colloids, the generation of three-, twoand one-dimensional arrangements of quantum dots, and heterogeneous catalysis. Benedetto Corain graduated in Chemistry at the University of Padova in 1965. After serving as Assistant Professor and Associate Professor in Padova, he moved to the University of L’Aquila in 1993 as full Professor of Chemistry and he was called back with the same status from his previous University in 1999 (Faculty of Sciences). He spent one year as a Research Assistant at the Department of Chemistry, Imperial College, London in 1966 and as a Visiting Professor (Humboldt fellow) at TU Munich in 1981 and 1998 and at the University of Essen in 2002. His present research interests include basic and applied metal coordination chemistry and macromolecular chemistry, with particular emphasis on reactive and functional cross-linked polymers as supports for metal nanoclusters. MICROREVIEWS: This feature introduces the readers to the authors’ research through a concise overview of the selected topic. Reference to important work from others in the field is included.
Eur. J. Inorg. Chem. 2003, 3081Ϫ3098
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Photograph of a nanoporous alumina membrane. for instance by electrostatic repulsion. They simply tell us that a particle consists of an assembly of atoms. Corain called plasmon resonance. Improvements were obtained by the so-called ‘‘laser-induced size reduction’’. Colloidal gold is still applied to treat arthritis. B. Numerous modifications of this established technique have been successfully applied in the past and will not be repeated in this article.1 Physical Methods Metal vapours usually consist of atoms.) Two examples shall elucidate the change of bulk properties when the nanosize regime is reached: the melting point and the color. Surface atoms have lower coordination numbers than inner atoms and therefore become mobile more easily. Scientifically. the size distribution of the resulting particles is usually rather broad. 2003. (In principle these consequences are also valid for other metals. Some of these opportunities will be discussed as part of the synthetic routes. which is quantitatively described by the Mie theory. Only some more recent and promising results shall be discussed. especially in combination with alcohol. in the size range between 1 and usually not more than 50 nm. In special cases the colloidal metals can be studied in the gas phase. This is based on the well expressed plasmon resonance of www.MICROREVIEW amics. An important aspect is the stabilization of the particles to avoid coalescence between them. the vapours have to be condensed into a dispersing medium. In this particular case the particles are embedded in the pores of a transparent alumina membrane. Chem. ligand molecules or embedding in nanocapsules such as micelles. The reason for the special color of metal nanoparticles is the so3082 2003 Wiley-VCH Verlag GmbH & Co. Syntheses The number of procedures for generating gold nanoparticles is almost indeterminable. Laser ablation methods have become commonly used techniques. however. The term ‘‘colloid’’ has meanwhile been mostly substituted by ‘‘nanoparticle’’ or ‘‘cluster’’. whereas chemical routes use gold compounds as a starting material. 3081Ϫ3098 Figure 1.[10Ϫ14] However.eurjic. from a few up to several hundred thousands or millions. linked with reduction steps. when Michael Faraday performed his famous experiments to generate gold colloids. Physical methods are defined as those by which gold nanoparticles are directly generated from bulk gold via atoms by various distribution techniques.7] Figure 2. This has to do with the increasing number of surface atoms with decreasing particle size. Schmid. Most of them have been known for decades. Weinheim . The miniaturization of gold to the nanometer range has dramatic consequences for its physical and chemical properties. steric hindrance. He was the first to point out that the properties of metal particles in the nanometer range are predominantly determined by surface atoms and he concluded that those nanoparticles. Solutions of colloidal gold were also used as tonics and elixirs.org Eur. filled with 10 Ϯ 5 nm gold nanoparticles 2. Both expressions are not very precise. should exhibit novel properties with respect to bulk particles. 20 to 2 nm in diameter. For this reason only some relevant and general synthetic techniques shall be discussed here briefly. Two main routes to gold nanoparticles are available: a physical and a chemical one. He reduced tetrachloroaurate using white phosphorus to yield deep-red gold sols.[6. in order to obtain them as matter. a well understood phenomenon. the beginning of the chemistry of gold colloids dates from the middle of the nineteenth century. The simplest way of obtaining nanoparticles is therefore the generation of metal atoms in the gas phase followed by their controlled condensation to nanoparticles. G. Figure 2 shows the typical color of 10 Ϯ 5 nm gold particles. the melting point drops below that of bulk gold (1064 °C) if the particle radius is less than 10 nm. This is the well-known metal-vapour synthesis. Relationship between particle size and melting point of gold nanoparticles As we can see. This stabilization can occur in many different ways. 2. called colloids. Inorg. Figure 1 shows the melting points of gold nanoparticles from ca. Gold. At the beginning of the 20th century it was Wilhelm Ostwald who contributed decisively to the further development of colloid science. KGaA. J. however. is an outstanding example.
30] This compound will be Eur. if no other stabiliser is used. acetone dicarboxylate) can act as protecting agents. especially the newer ones. 2. The method is based on the so-called solvated metal atom dispersion technique (SMAD). By varying the thiol concentration. A dramatic effect on the narrowing of the gold particles was obtained by digestive ripening of the gold-toluene dispersion at 120 °C.[15Ϫ20] Very narrowly distributed gold nanoparticles with a diameter of 1.5 nm. Water-soluble phosphanes have been successfully used to shield gold colloids. Particles of 1Ϫ40 nm in size were narrowed down to 4Ϫ4. the Turkevitch route still is one of the most applied procedures.Nanoparticulated Gold MICROREVIEW gold nanoparticles around 520 nm and was used to change the size and geometry of the particles. the particles sizes can be controlled between 2 and 5 nm.26] Dozens of variations have meanwhile been found.[32.org 3083 . Weinheim www. Citrate itself and its oxidation products (e.[29. For instance. they were then reacted with dodecanethiol and this enabled good dispersion in toluene. This is not possible with weakly binding stabilisers such as citrate. phosphanes can usually be substituted by thiols. it is also observed that the size of the original gold particles may change during the exchange process. The use of stronger ligands than citrate was a major improvement for the synthesis and handling of gold sols. Since they bind more strongly to gold than phosphanes do. High-resolution transmission electron microscopic (TEM) image of a ligand-protected 11 ϫ 13 nm gold nanoparticle. A few of the more relevant procedures. Phosphorus was the agent he used for the reduction of [AuCl4]Ϫ ions. In order to attain further stabilization. Gold nanoparticles in the size range of about 10 to 30 nm or more have been synthesized by the NaBH4 2003 Wiley-VCH Verlag GmbH & Co.2 Chemical Routes As already mentioned. Figure 3 shows a TEM image of an individual gold nanoparticle where the envelope of stabilizing phosphanes can be observed. 2003. Besides phosphanes. Inorg. Among the so-called salt reduction methods. It is an accepted assumption that the use of thiols leads to the formation of RSϪ thiolates that form strong covalent AuϪS bonds.eurjic. However. A well-known reactor was used to generate atoms from a piece of bulk gold. PPh3 acts as a rather good ligand for 1. Sodium citrate reduces [AuCl4]Ϫ in hot aqueous solution to give colloids of 15Ϫ20 nm. The ionic [B12H11SH]ϪNaϩ transforms the CH2Cl2-soluble phosphane-stabilized clusters into water-soluble ones. Recently. are mentioned below. stabilized by acetone molecules. Phosphanes and thiols turned out to be excellent stabilisers due to rather strong AuϪP bonds and even better AuϪS bonds. P(C6H4SO3Na)3 stabilises gold particles of 15Ϫ20 nm to such an extent that they become isolable as golden leaves that can be redispersed in deionized water with the typical purple-red color.33] [B12H11SH]ϪNaϩ  and SH-functionalized silsesquioxanes such as (cyclopentyl)7Si8O12(CH2)3SH have been successfully applied to remove phosphanes quantitatively from the surface of Au55 clusters. KGaA.7 and 3.4 nm were obtained with a 532 nm pulsed laser irradiation of gold metal plates in diluted sodium dodecylsulfate solutions.[25. J. The latter is easily obtained by reduction of Ph3PAuCl by gaseous B2H6 in benzene or toluene at elevated temperatures. 3081Ϫ3098 Figure 3.5 nm particles. It is readily soluble in CH2Cl2 however. thiols are the most important type of stabilizing molecule for gold nanoparticles of any size.g. Michael Faraday was the first to study the formation of gold sols from a scientific point of view. whereas the alkyl terminated silsesquioxane makes the same particle soluble in apolar solvents such as hexane or pentane.4 nm Au55 clusters in Au55(PPh3)12Cl6. As we shall see from the following examples. One of the most popular modern methods for preparing gold nanoparticles of various sizes comes from Brust et al. thiol-stabilized gold nanoparticles have become available following a seeding growth approach starting with 3. The particle size can be varied by changing the seed-particle-to-metal-salt ratio. Chem. A gram-scale synthesis of thiol-stabilized gold nanoparticles by solvated metal atom dispersion and digestive ripening was recently reported. In the course of the last century numerous easier to handle reducers were found. wet-chemical routes to generate gold nanoparticles are much more versatile. These molecules allow the isolation of gold nanoparticles as solid materials that can be redispersed in appropriate solvents. it can also be transformed into a watersoluble species by exchanging PPh3 with Ph2PC6H4SO3Na or Ph2PC6H4SO3H. the polycrystalline gold core and the protecting shell of P(C6H4SO3Na)3 molecules can clearly be distinguished the focus of attention of the following chapters because of its particular electronic properties. It uses NaBH4 to reduce gold salts in the presence of alkanethiols to yield gold particles of 1Ϫ3 nm. The Au atoms were frozen at 77 K in acetone vapour and were then warmed up to give gold colloids.
10.MICROREVIEW method using mercaptosuccinic acid for stabilization. B. KGaA. and structure. TEM image of a monocrystalline core-shell-structured gold-palladium particle Figure 4. All results indicate an hcp structure.[49. We can conclude that since Faraday’s time the syntheses have been improved. The smallest particle in this sense is ligand-stabilized Au55 which has been investigated not only by TEM.[56. The smallest ligand-stabilized.5 to 0.6 nm were isolated as water-redispersable powders. particles of 10. it should www. They used diblock co-polymers exhibiting regularly organized micelles into which tetrachloroaurates were transported.57] An Au39 cluster has also been characterized by X-ray diffraction. J. These three examples illustrate the development of the bulk state from a molecular level. The carboxylic functions were then treated with trifluoroacetic anhydride to give the corresponding carboxylic anhydrides which are highly reactive and can. 3081Ϫ3098 . contributed decisively to this modern field of nanoscience. 2003. just like in the bulk state.8. 12.5. and 33.2. but. 3. Micelles can be considered appropriate chemical reactors. Structures and Optics Transmission electron microscopy (TEM) is by far the most valuable tool for studying particle size. for instance.eurjic. gold is the most electronegative one and consequently it can be generated from its salts by a huge number of reducing species. indicating the transition to bulk structure. Finally Au55(PPh3)12Cl6 fully reached the bulk structure. By varying the succinic-acid-to-HAuCl4 ratio from 2. distribution.[41Ϫ45] Figure 4 shows one of those nanoparticle arrangements in a diblock co-polymer. These have been shown to build up icosahedra. An elegant and valuable route is the generation of gold nanoparticles inside ‘‘nano-reaction vessels’’. Corain hydrogen. hydroxylamine. 3084 2003 Wiley-VCH Verlag GmbH & Co. but any kind of organic species with some reducing character is suited to produce gold nanoparticles from salts. Weinheim 20 nm gold core and a palladium shell is shown in Figure 5. can be used. there is an interesting transition with respect to the development of bulk structures. A so-called ‘‘green chemistry’’ has evolved in recent years. Inorg. A full overview of all known synthesis techniques would exceed this microreview by far. Schmid. From thousands of TEM investigations we know that gold nanoparticles exhibit either a mono. EXAFS and Mössbauer spectroscopy. 11-Mercaptoundecanoic acid was also used to cover gold nanoparticles generated by the Brust method. hydrazine. It consists of a distorted hexagonal close-packed core. However.[29.4. followed by a reductive step with hydrazine or NaBH4 and formation of the nanoparticles.8. Figure 5. for instance.50] An example with a ca. especially with respect to a better control of the particles size.51Ϫ55] However. Möller et al. protected by 14 PPh3 and 6 Cl ligands. the control of growth by ligand concentration or other experimental conditions is not required. Amongst all transition metals. alcohols etc. The purpose of this article is simply to report some novel improvements of well-known methods. be used to anchor the nanoparticles on silica supports. Even bimetallic core-shellstructured nanoparticles can be identified by various imaging contrasts and by Energy Dispersive X-ray Analysis (EDX) of individual particles. G. meaning that gold nanoparticles can be generated by natural organic materials via reduction. Not only classical reducers such as hydrides. TEM image of 4 nm gold particles in micelles of diblock co-polymers It must be stated that the above-mentioned examples of synthetic strategies for generating gold nanoparticles are very incomplete.47] Even different types of fungi have been found to work up gold salts into elemental gold. the chemical principles are still just the same: it is the facile reduction of AuIII or AuI. Due to their limited size.or a polycrystalline structure of hexagonal close-packed (hcp) atoms.org Eur.[46. Chem. also by X-ray diffraction. however. consists of only one central and 12 gold atoms in a first shell (Au13). so-called full-shell cluster. 19.
4 nm Au55 clusters. as already mentioned. Therefore. we will learn that such statements cannot be generalised. In spite of this restriction it can be stated that the 1. This red-shift is caused by the change in the refractive index from air to toluene. Figure 6. is: how large or how small should a metal particle be in order for us to observe molecular or metallic properties? In relation to optical properties this question has to be formulated as: when does the plasmon resonance disappear if miniaturization proceeds? In this context.[7. quantitatively described by the Mie theory. respectively. since toluene has almost the same refractive index as alumina. whereas small molecular clusters do not show any kind of plasmon resonance. Additional effects have been observed using unpolarised and polarised light with different polarization angles. In the temperature range of 100Ϫ800 °C particles with diameters of 4. Ligand-stabilized Au13 and Au55 clusters were investigated and in both cases the vanishing of the Mie resonance was observed. An example of a membrane prepared in this manner has already been shown in Figure 2. but both peaks are red-shifted to 500 and 675 nm. ligand-stabilized Au55 clusters play an important role. On the contrary. To conclude these considerations we have to accept that Au55(PPh3)12Cl6 and its variations do not possess enough mobile electrons to exhibit plasmon resonance. due to the increasing melting point of larger particles (see Figure 1). J. the size of the gold nanoparticles increases with increasing decomposition-temperature. respectively Eur. Plasmon resonance is a size-dependent phenomenon of several metals. The use of preformed nanoparticles has the advantage of narrower size distribution and allows one to observe changes by repeated filling. the following section will deal exclusively with the electronic properties of this compound. On immersing the sample in toluene. The plasmon resonance is initiated by the interaction of the electric field of visible light with the confined electron-gas of the particle. The low-energy absorbance is probably caused by the excitation of the plasmon resonance along the axis of the wire-like arranged particles.5 Ϯ 1.61Ϫ63] support the interpretation of the experimental observations. only one plasmon resonance peak at 525 nm is observed because of the lack of wire-like arrangements. As expected.Nanoparticulated Gold MICROREVIEW In air.4 nm particles in 50 nm pores in two different media. Figure 6 shows the extinction spectra of a composite consisting of 4. This is due to the lack of quasi delocalized electrons that are necessary for the interaction with light. since it shows not only the influence of the particle size on the plasmon resonance. in the case of gold usually in the region of 500Ϫ600 nm. This effect is caused by a plasmon resonance. A decisive question. Of course. If 50 nm pores are filled once with 15 nm gold colloids. since the method of investigation. from an optical point of view. but also on the particles’ arrangement and the nature of the surrounding medium.eurjic. temperature and other experimental parameters play a decisive role with respect to what we ‘‘see’’.5 up to 11 nm were observed in sectioned membranes by means of TEM. This is known for thousands of oligonuclear organometallic cluster compounds. namely in air and in toluene.4 nm gold nanoparticles in 50 nm alumina pores in air and in toluene. However. alumina is ideally suited to study the optical properties of nanosized particles inside its pores. two absorption peaks are observed at 480 and 600 nm. However. Owing to its transparency. Two approaches for placing gold nanoparticles in nanopores are available: the thermal decomposition of Au55(PPh3)12Cl6 clusters inside the pores to generate larger particles and the use of preformed particles to be filled into the pores by vacuum induction of solutions. Conclusions on the situation in bare clusters are not possible. not only does the intensity of the peaks increase. This effect can be seen even by the naked eye: when viewed perpendicularly to the membrane’s surface the color is deep red (Figure 2). 3081Ϫ3098 www. indicating initial formation of wire-like arrangements. which will also be the focus of attention of the following chapters. For that purpose nanoporous alumina was filled with various gold nanoparticles. UV/Vis extinction spectra of 4. These facts are quite well understood and will not be discussed here. Chem. these findings are related to the special electronic situation in the Au55 cluster core. belong rather to the molecular world than to the metallic one. 2003. using the generalized Mie theory. the electrons between metal atoms in small clusters are localised. A characteristic of all gold colloids is the color which can vary between light red via purple-red to bluish-red. For example. depends on the size of the particle and on the shape and the dielectric properties of the surrounding medium. Weinheim be emphasized that these findings are only valid for ligandstabilized particles. Repeated filling broadens out and shifts the signal to 580 and 590 nm. 2003 Wiley-VCH Verlag GmbH & Co. whereas the increase in intensity comes from the reduction of scattering effects. Inorg. Theoretical calculations. KGaA. The wavelength. Bulk metals reflect light.org 3085 . whereas the edge of the membrane looks blue. a recent result shall briefly be mentioned. Again we should remember that the observed effects always include the existence of ligand shells on the particles.5 Ϯ 1.
3081Ϫ3098 . It should be mentioned that many of the investigations during the last two decades involved other metals as well as gold. This example demonstrates that the decision ‘‘metal or not’’. Chem. Here. Electronics 4. This can be performed by bringing an individual particle. As shown. Corain diameter 1. It was found that the electronic relaxation-speed. 2003. induced by laser pulses of 200 fs of an energy of 250 µJ/pulse at 780 nm.eurjic. Relaxation behavior of gold nanoparticles of different sizes after excitation by femtosecond laser pulses As we can see. Au13(dppm)6(NO3)4 (dppm ϭ Ph2P-CH2-PPh2) (core diameter 0.7 nm). Inorg. the relaxation speed increases from the 15 nm particles to Au55. Weinheim G. and the increase of the electronic collision-rate on the surface. Au55(Ph2PC6H4SO3Na)12Cl6  (core 3086 2003 Wiley-VCH Verlag GmbH & Co. and we have just learnt that it is not yet a molecule! Probably the most informative method for studying the electronic situation inside a nanoparticle is to measure its current-voltage characteristics under different conditions. If we cut off a small piece of that wire we reach the zero-dimensional (0D) situation where the remaining electrons are constrained in such a way that they begin to occupy discrete energy levels. KGaA. also compared to the bulk.MICROREVIEW 4. of course. It is the general opinion of experts that nanotechnology will decisively influence man’s life in the following century. It would exceed this article by far to mention and to discuss all of them. It was the enormous interest in these novel properties that brought nanoscience to such a level that a wide public. bearing a non-conducting protecting shell (usually the liwww. also with semiconductors. Schmid.2 Physical Tools There are many physical methods to investigate quantum-size effects. Some hints have already been given by the optical phenomena discussed in section 3. J. This cluster behaves like a molecule. ‘‘artificial atoms’’. varies characteristically with the particle size.4 nm) and 15 nm colloids were tested. since quantum-size effects can be studied with any kind of metal. In a thought experiment we can proceed with a continuous reduction of dimensions. From a 3D situation with its typical bulk behavior we turn to a film of only a few atoms’ thickness (2D). whereas Au55 represents the very last ‘‘metal’’ before the typical molecular region begins. and. However.1 The Quantum Size Effect In a bulk piece of metal the valence electrons of the participating atoms occupy energy bands instead of discrete levels. onedimensionality (1D) of the electronic degree of freedom is enforced. That is why such pieces of matter are also called ‘‘quantum dots’’ or. Pieces of metals following these conditions must exhibit very different physical and chemical properties compared to bulk ones and to typical molecular ones. Back to the facts. as we know from atoms and molecules. optically Au55 is definitely no longer a colloid.org Eur. One important contribution to this major problem was made by the observation of electron-phonon coupling in gold particles of different size. with a somewhat more popular expression. B. to cause metallic behavior or how small should a piece of metal be in order to see metallic properties disappearing? 4. we have to repeat the question we asked in the previous section in a more general way: how many atoms do we need. cannot be precisely answered. Figure 7 shows the results. This relation informs us on the interplay between the rate of energy transfer from electrons to lattice and the number of atoms in the particle. This effect is explained by the weakening of the electron-plasmon interaction. the electrons can only move in two dimensions. gold played once again an important role in the process of our understanding. A particle of such size no longer follows classical physical laws and has to be described by the quantum mechanical rules used to describe atoms. For Au13 it decreases due to the existence of localized electrons. economic and political interest arose. Figure 7. therefore only a few shall be selected to explain what happens when particles size is continuously reduced. whereas in a wire of only a few atoms in diameter.
 This method allows one to acquire not only tunnelling spectra. as we can see in Figure 9. when measured at 4. however at 7 K under ultra high vacuum (UHV) conditions. which is the same size for both positions. due to Coulomb repulsion.Nanoparticulated Gold MICROREVIEW show well-expressed Coulomb blockades already at room temperature. J. Figure 10. However. as is indicated in Figure 8. The insulating barrier is necessary to make tunnelling of individual electrons observable. At 295 K the particle exhibits a linear current-voltage (IϪV) relationship and therefore indicates metallic behavior (Ohm Law). Sketch of a tunnelling contact consisting of an STM tip. into contact with two electrodes to which a variable voltage is applied. Inorg.eurjic. kBT ϭ thermal energy). a ligand-protected metal nanoparticle and a conducting substrate Figure 9. Room temperature IϪV characteristics of an individual Au55(PPh3)12Cl6 cluster indicating a well-expressed Coulomb blockade The barrier conditions are responsible for the electron transport. uncontrolled electron transitions occur. tunnelling of a single electron onto the particle blocks the transfer of a second one.4 nm. The light dots in Figure 11 indicate the positions of the phenyl rings of the PPh3 ligands and a and b show two different sites where the STM tip was positioned for recording the tunnelling spectra: a above a C6H5 ring. The same Au55 species have very recently been studied by the same technique. the positions a and b indicate where the measurements have been performed to yield the IϪV characteristics in Figure 11 Eur. KGaA. the thermal energy should be small in order to observe Single Electron Tunnelling (SET). they depend on the temperature. Figure 11A shows the Coulomb blockade. Chem. This fact was demonstrated by placing a ligand-protected 17 nm Pd particle next to two platinum tips. Weinheim 3087 . STM image of an individual Au55(PPh3)12Cl6 cluster at 7 K under UHV conditions together with a full-space model. The result is very exciting: these particles indeed This means that these 1. Au55(PPh3)12Cl6 clusters on gold substrates have been investigated by bringing individual particles into contact with an STM tip so that information on IϪV characteristics can be gained. Figure 10 shows one of them together with a space-filling model in the corresponding orientation. C ϭ capacity of the island between the electrodes. gands). but also detailed images of individual particles. indicating that the ligands do not visibly contribute to the tunnelling process. If not. the light dots indicate phenyl rings. 2003. b on the side of the ring. Among others. 3081Ϫ3098 www.2 K. a so-called Coulomb gap is observed: if kBT is small enough. but with the same distance from the gold surface. until an appropriate voltage is reached.org 2003 Wiley-VCH Verlag GmbH & Co. Figure 8. ligand-protected particles behave as single electron-switches at room temperature! This opens up unexpected future applications in nanoelectronics. Owing to the relationship EC ϭ e2/2C ϾϾkBT (EC ϭ electrostatic energy.
probably via hydrophobic-hydrophobic and π-π interactions. So. most of them in the size regime of a few. 3081Ϫ3098 Figure 11. a and b indicate equivalent Coulomb blockades although measured at different positions on the cluster’s surface. 50Ϫ150 nm apart and 25 nm in height. Schmid. Due to charging effects of the electron beam (10 keV. were checked by scanning electron microscopy (SEM). as it turned out. still better. This is why numerous groups worldwide are dealing with this problem. Figure 12 illustrates these results. prevent formation of extended ordered layers due to the lack of flexibility of the particles. there is a vast amount of reports. Weinheim . A) IϪV characteristic of an individual Au55(PPh3)12Cl6 cluster at 7 K under UHV conditions.[70Ϫ72] The acidified cluster gives hexagonal and square structured 2D arrangements on poly(ethyleneimine) (PEI) films. Still more interesting is the high resolution of the blockade region by using dI/dV instead of I (B).and in some respect also the one-dimensional organization of metal nanoparticles is very relevant since one can think about the use of these particles in nanoelectronics only in an organized form. As a consequence of these unique properties it seems interesting to study the electron-transfer processes between the quantum dots. 5. J. After numerous attempts. Corain tween cluster-cluster distance and activation energy to be observed. 2003. rather extended self-assembled monolayers of Au55(Ph2PC6H4SO3H)12Cl6 and of Au55(PPh3)12Cl6 became available. 10 s) the layers become conductive in the pA region in contrast to a not measurable conductivity without irradiation. The average level spacing in vicinity to the Fermi level is about 170 meV. These weak forces between the clusters and the supports enable the formation of perfect arrangements since the particles are only weakly attracted and are allowed to find the best order.MICROREVIEW they simply act as distance holders. if spacer molecules linking the particles via covalent SϪAu bonds are used. Although there is no doubt that PEI acts as a basic surface towards the SO3H-modified Au55 cluster. supported by a layer of poly(vinylpyrrolidone) (PVP) or. as has been discussed in section 4. if irradiation occurs on only one of the electrodes and part www. like those between the acidified cluster and PEI. Approaches to Two-Dimensional Organizations The two. mainly on regular 2D arrangements of gold nanoparticles. The occupied as well as the unoccupied levels are visible. since they are of promising electronic nature. but also the nature of the interlinking species and the kind of linkage. Here we will only focus on recent results of organized Au55 clusters. up to 15 and 20 nm.eurjic. there is indeed only a simple linear relation be3088 2003 Wiley-VCH Verlag GmbH & Co. whereas the neutral species is best organized at the phase transition between water and dichloromethane. G.org Eur. Inorg. On the contrary. Chem. and prepared on PVP films. PVP and PPE interact only weakly with the PPh3-covered cluster. it is not the distance that contributes decisively to the activation energy. respectively. it is not only the distance between the nanoclusters which determines the activation energy for the charge transfer. Figure 13 shows TEM images of cut-outs of square planar (a) and hexagonal (b) arrangements of Au55 clusters. respectively. An interesting electrical behavior of these ordered monolayers was observed when conductivity measurements were carried out. However. However. Monolayers deposited between two tungsten electrodes on silica surfaces. of poly(p-phenylene ethynylenes) (PPE). KGaA. generated on PEI and PPE. It is again gold that plays an important role because of the easy availability of gold nanoparticles and their resistivity to air. If the clusters are simply separated from each other by ligand shells of different thickness or by non-covalently binding spacer molecules (ionic interactions). the role of PVP and PPE in connection with Au55(PPh3)12Cl6 is somewhat more delicate. B) dI/dV characteristic of the same particle indicating discrete electronic energy levels (arrows) in the Au55 cluster core This experiment now justifies the expression ‘‘artificial atom’’ for those quantum dots and proves the assumptions of paragraph 4. This was done for three-dimensionally organized Au55 clusters with variable distances.1 that on the way from bulk to molecule at some point a situation arises where the electronic band structure begins to form discrete energy levels. Relatively strong interactions. but the chemical nature of the spacers. On the contrary. due to conductivity oscillations. The arrows indicate conductivity signals which coincide precisely for both positions. as described above. For the very first time the existence of discrete energy levels inside the Au55 core could be proven. B.
org 2003 Wiley-VCH Verlag GmbH & Co. Chem. Weinheim 3089 . covalently and non-covalently linked Eur. 2003. 3081Ϫ3098 www. J.Nanoparticulated Gold MICROREVIEW Figure 12.eurjic. Inorg. KGaA. Activation energies for Au55 clusters of varying distances.
and of course any other structure could be created. Diode behavior of Au55(PPh3)12Cl6 monolayers. 3081Ϫ3098 . it is necessary to create artificial architectures. whereas the deactivation takes much more time. Weinheim www. The COOH groups are used to add silane molecules to CϭC double bonds which can then be transformed to thiolfunctionalized derivatives. The IϪV characteristics depend on the contact distances. This activation makes the particles order themselves so as to reach a minimum energy arrangement with a maximum delocalization of the additional electrons. How- Figure 14. in contact with tungsten electrodes on SiO2. The total process is sketched in Figure 15. In all cases the systems relax in the course of 24Ϫ36 h after switching off the voltage. diode-like behavior is observed. J. the expo- sure time and finally on the irradiated area. Chem. As we can see from Figure 16. There is no doubt that these structures offer great advantages compared with self-assembled arrangements.eurjic. trapped in the silica layer. It is based on the generation of appropriately modified surfaces. Figure 14 shows a typical diode curve (a) gained with a set-up of electrodes of 122 nm distance (b) and an exposure time of 5 s at 16 keV. In order to explain this unusual behavior we assume that electrons from irradiation. Schmid. A metallized AFM tip was used as a tool for transforming methyl groups of a self-assembled monolayer into carboxylic functions by electrical pulses under air. Finally.org Eur. have been created. for practical use with respect to future data storage or related applications. However. indicating that there is no chemical change with respect to the starting situation. arranged dots of clusters (a). water-soluble Au55(Ph2PC6H4SO3Na)12Cl6 clusters are chemisorbed from solution by the thiol functions. However. B. KGaA. as well as single gold clusters between wires made of single rows of particles (b). TEM images of square planar (a) and hexagonal (b) monolayers of ligand-stabilized Au55 clusters of the monolayer. Inorg. the irradiation time. The width of the traces simply depends on the quality of the tip. Self-organization of quantum dots must be considered only as a first step for collecting information on their electronic interchange. reactivation is possible. The rearrangement of the clusters may happen very quickly due to the electron irradiation. Corain Figure 13. after partial irradiation with an electron beam 3090 2003 Wiley-VCH Verlag GmbH & Co. create so-called image charges in the cluster layer. 2003.MICROREVIEW G. the energy of the electron beam. A first approach as to how this high goal might be reached will be described below.
the water-soluble phosphane P(C6H4SO3Na)3 can easily re 2003 Wiley-VCH Verlag GmbH & Co. but also by ClϪ ions and acetone dicarboxylate. Without any other stabilizing species the gold particles are covered by excessive citrate. One major problem will be to study individual quantum dots and to connect them with the outer world.org 3091 . but many efforts will be necessary to reach this goal. Therefore. Inorg. an oxidation product of citrate. As an example we should remember the famous citrate route for the generation of 15Ϫ20 nm gold colloids. J. Weinheim 6.Nanoparticulated Gold MICROREVIEW Figure 15. they can easily be substituted by stronger binding molecules. KGaA. Chemical Activity Two main aspects concerning chemical activity of gold nanoparticles will be treated in this chapter: ligand-exchange reactions and catalytic activity. a. Sketch of the generation of SH-functionalized patterns on a Si wafer to trap Au55 clusters Figure 16.2. For instance. Chem. 6. rather detailed discussion of catalytic properties will be found in this section. it is also clear that there is still a lot of work to be done to develop a working system. Ligand-exchange reactions are quite common and are used to change solubility or to introduce special functions. coalescence would quickly occur. 3081Ϫ3098 www. 2003. These species bind strongly enough to keep the colloids in solution for a long time. However. There are ideas on how to do this. b Patterns of Au55 clusters deposited on chemically modified surfaces as shown in Figure 15 ever.eurjic. wet chemical syntheses of gold nanoparticles are always linked to the presence of protecting ions or molecules since without them.1 Ligand-Exchange Reactions As discussed in chapter 2. a Eur. Catalytic properties of gold nanoparticles are currently developing into an attractive and important field in gold chemistry.
3081Ϫ3098 . Corain The high mobility of phosphanes on gold-particle surfaces can be used to substitute them with stronger ligands. G. is also based on that ligand mobility. The excess dendrimer obviously re- Figure 17. This is due to the fast exchange processes between free and coordinated PPh3 molecules.5 ppm). Chem. We must assume that phosphane molecules on the surfaces of gold nanoparticles are rather mobile in solution. whereas the dichloromethane-soluble Au55(PPh3)12Cl6 becomes water-soluble if reacted with Na2[B12H11SH]. the thiol-functionalized silsesquioxane (cyclopentyl)7Si8O12(CH2)3SH.34] The alkyl-terminating silsesquioxane. as well as the anionic thiol [B12H11SH]2Ϫ. above all by thiols. Sketch of synthetic routes to Au55(PPh3)12Cl6 and some of its derivatives 3092 2003 Wiley-VCH Verlag GmbH & Co. readily soluble in apolar solvents such as pentane or hexane. Gradual addition of free PPh3 to cluster solutions causes a shift of the 31P signal from δ ϭ 34 ppm towards that of free phosphane (δ ϭ Ϫ5.2. Figure 17 illustrates these transfer reactions that indicate that the same cluster particle can change its solubility from dichloromethane to pentane or even to water. The formation of the water-soluble compound Au55(Ph2PC6H4SO3Na)12Cl6. transfers the water-soluble cluster Au55(Ph2PC6H4SO3Na)12Cl6 into the pentane-soluble derivative with silsesquioxane ligands. Schmid. As already mentioned in section 2. Inorg. Weinheim www.org Eur. A very special kind of ‘‘phosphane substitution’’ in Au55(PPh3)12Cl6 is observed when the latter is reacted with an excess of a fourth-generation dendrimer bearing 96 terminal SH functions. This was shown long ago by 31P NMR investigations of Au55(PPh3)12Cl6 with excess PPh3. coalescence processes are inhibited. J. The mobility of ligand molecules is also the reason why Au55(PPh3)12Cl6 is rather labile in solution (due to the loss of PPh3). B. dissolved in dichloromethane. quantitatively substitute phosphanes in Au55 clusters with the help of phase transitions.MICROREVIEW move the original ions and molecules to form such a strong ligand-shell that these gold nanoparticles can even be isolated as solid products.eurjic. from Au55(PPh3)12Cl6. 2003. KGaA. The fact that the water-soluble derivative is formed in quantitative amounts is due to the phase transfer from CH2Cl2 to H2O and to the somewhat better coordination of Ph2PC6H4SO3Na compared to PPh3.[35. and as a consequence.
 However. Figure 18. in the course of the seventies.3. 6. KGaA.[86. TiO2.81] The first documented exhibition of catalytic activity of bulk gold occurred at the beginning of the past century when Bone and Wheeler showed in 1906 that gold foils catalyse the combustion of dihydrogen and dioxygen to give water. it can be suggested that these gold full-shell clusters might act as special oxidation catalysts. it was later observed that the reaction occurs even at 200 K. with no effect on the potentially concomitant double bond migration reaction. the main part of the particles remaining unchanged. Eur. They observed. It was believed for a long time that the inability of Au0 to activate (chemisorb) O2 in any catalytic oxidation reaction was a straight manifestation of its thermodynamic reluctance to form metal oxides (∆H0 f of Au2O3 ϭ ϩ19. as can clearly be followed from the X-ray photoelectron spectra. Indeed this was a prophetic observation! Among the many good review papers quoted in this report. could be effectively catalyzed by supported-Au0. b) Au0 supported on MgO or Al2O3 was found by Galvagno and Parravano to catalyse oxygen.[91. and Ͻ1 nm are all oxidized when deposited on top of a silicon wafer and exposed to atomic oxygen.05%) was found by Bond and Sermon to catalyse the hydrogenation of alkenes at 373 K. Figure 18 shows the Au-4f photoelectron spectra of the oxidized particles including Au55 clusters. However. the size at which metal nanoclusters start to exhibit quantum-size behavior. Finally. This phenomenon has led to the formulation that Au55 is ‘‘nobler than bulk gold’’.9. Consequently. Moreover naked Au55 clusters are formed in oxygen plasma by burning off the ligand shell. or Co3O4.eurjic. that the oxidation of CO to CO2. 1. AuϪAu interactions between the bare clusters occur and the coordination of dendrimers is not observed . three major observations were made: a) Au0 supported on silica (0.2. Owing to the non-availability of these particles. The relevant paper is remarkable in that the authors also collected good quantitative kinetic data on the same reaction. reported on a real breakthrough in this field of research.2. obtained in the decades following Bone and Wheeler’s observation. in fact. as indicated by the presence of a weak shoulder. As a consequence it can be predicted that other full-shell clusters such as Au147 or Au309 etc. 2003. Only traces of oxides appear.3 kcal·molϪ1 ). naked Au55 particles grow to regular microcrystals inside a matrix of dendrimers.01Ϫ0. bulk gold metal appeared for long time an essentially useless material for catalysis. It also became apparent that the optimal nanocluster diameter was ca.2 Nanoparticulated Gold in Modern Catalysis 6.and hydrogen-transfer reactions  and c) a green Au(O2) molecular species with side-on bonded dioxygen could be obtained at extremely low temperatures in a solid matrix. the 2002 review by Choudhary and Goodman as a general and critical reading on Au0 catalytic chemistry is particularly recommended. Inorg. a very unexpected behavior of naked Au55 clusters will be mentioned. Moreover. 2.2 Synthesis of Supported Gold(0) Catalysts The overall grey scenario of Au0 catalytic chemistry became suddenly lightened in 1989 when Haruta et al. was not considered very exciting. J.1 Historical Survey In contrast to the catalytic potential of its neighbors silver and platinum. but only when Au0 occurs as metal nanoparticles supported on suitable metal oxides. the extremely facile Au0-catalyzed oxidation of CO to CO2 by O2 is the most striking result in Au0-catalytic chemistry. this very remarkable molecule was found to react with CO at a suitable temperature to give eventually free Au0 and CO2. Information on the catalytic chemistry of Au0. this prediction cannot yet be proven .Nanoparticulated Gold MICROREVIEW 6. Chem. As an explanation of this unique behavior it is assumed that it is the special stability of Au55 as a closed-double-shell structure. Ironically.[80.92] 2003 Wiley-VCH Verlag GmbH & Co. While surfaces of bulk gold and particles of 7. all particles except for Au55 show well expressed gold oxide signals In all cases except for Au55 there are well-developed signals for gold oxides. a technologically relevant reaction under various circumstances.9. 1. bare Au55 resists these extreme oxidative conditions.6. However. 3 nm. It soon became apparent that the key to this success was twofold: a) the presence of gold nanoparticles in the gold catalysts and b) a strong co-catalytic role played by the support that had to be an inorganic oxide such as Fe2O3. It is excluded that a special electronic situation might cause this inertness.87] Most interestingly. Weinheim moves all the phosphanes from the clusters’ surface. 3081Ϫ3098 www.org 3093 . should also resist oxidation. X-ray photoelectron spectra of various gold particles after exposure to an oxygen plasma.
MICROREVIEW This discovery promoted an incredible amount of research and an avalanche of papers and patents in a manifestation of a modern-day ‘‘gold rush’’. KGaA.[93Ϫ99] Supported gold nanoparticles (1Ϫ5 nm) are currently prepared according to a dozen or so rather different methods. the preparation of an Au0/resin catalyst obtained from the chemical reduction of an AuI. We believe that the catalysis community was particularly stricken by Haruta’s discovery in that it represented an unprecedented example of both extreme catalyst structure-sensitivity and of an impressive co-catalytic role played by the metal-supporting microphase (vide infra). Figure 19. 50% of its atom constituents to the action of gaseous species that find possible reaction sites at the edge-.[100.org Eur. Moreover. 6.101] The precursor of Au0 is deposited or grafted onto the surface of the support. and subsequently left to be adsorbed by the surface of the desired support particles. Deposition precipitation procedure to give Au/S catalysts 3094 2003 Wiley-VCH Verlag GmbH & Co. on the nature of the support and on the detailed synthetic procedure. 3 nm) nanoparticles (Figure 19) that are believed to cause a particularly strong attractive force between a given nanoparticle and the crystal lattice of the support located just underneath it. In fact. which can be reduced in essence to three major procedures.e. still to be fully evaluated nowadays and. Weinheim . a rapid and quantitative oxidation to CO2 is observed even at 200 K. Schmid. The Au0 nanoparticles are pre-produced in a given solution where they are stabilized by soluble polymers or by kinetic conditions. 3081Ϫ3098 Scheme 1. Corain In fact. 2003.III/resin-macromolecular complex prepared simply by complexation of aqueous AuCl3 with a thioethereal gel-type resin. produces Au0/S catalysts. and subsequently thermally decomposed to give the Au0/S catalysts. theoretical calculations carried out by Lopez and Norskov revealed that isolated Au10 clusters are expected to catalyse CO oxidation even below room temperature. In this context. we might consider that the electronic and geometrical features of these potential activation sites are related to Au6Ϫ and to www. On the contrary. Consequently. exposes ca. in terms of both consensual and disputed literature observations and to other general as well as specific readings. Inorg. catalytic activity depends critically on the metal nanoparticles’ size. Dramatic effect of the Au0-support interaction on the CO oxidation reaction rate over spherical vs. which has been pre-formed from the gas or from the liquid phase. We would like to mention. J. the reader is referred to an authoritative review paper by Bond and Thomson who critically examined the matter in the year 2000. if a mixture of CO and O2 is allowed to interact with 2Ϫ5 nm gold particles dispersed on the same support. As anticipated above. the deposition precipitation (DP) procedure is generally widely considered the most suitable one (Scheme 1). in this connection. The metal nanoparticle’s size is controlled by the calcination temperature. The precursor of Au0 is mixed with the precursor(s) of the supports (or with the support itself) to give a system that. B.or stepsites of the nanoparticle surface. hemispherical nanoclusters. the issue of catalyst preparation and the full understanding of the role of the support appeared immediately very complex. DP turns out to be particularly suitable for producing hemispherical (ca.3 Nanoparticulated-Gold(0) on Metal Oxides: Facile Oxidation of Carbon Monoxide to Carbon Dioxide No measurable oxidation of CO by O2 on micro-sized (in fact ‘‘bulk’’) supported-Au0 is observed at ambient conditions. it is important to note the quite different effect of the nanoclusters’s shape on the action of Pt0 This phenomenon has two major consequences: i) a marked thermal stability of the Au0 nanoparticles (thus contrasting the particles’ coalescence) and ii) a peculiar local electronic situation at the lattice interface of the metal nanoparticles and the support. All these observations seem to provide an explanation of the established activity of the nanoparticles’ surface gold atoms in the CO oxidation.2. after controlled calcination.eurjic. i. under identical Au0 molar fraction. that is likely to be responsible for the particular mechanism of oxygen transfer to chemisorbed carbon monoxide to give carbon dioxide (see below). and lower temperatures seem to favor the formation of smaller particles. corner. G. Wallace and Whetten observed an effective formation of CO2 when CO and O2 were reacted with Au6Ϫ in the gas phase (Figure 20). in this respect a recent outcome from these laboratories. Chem. However. it is now widely accepted that at least for CO oxidation and for the water gas shift reaction. reality is more complex than that! An Au0 nanoparticle of 2Ϫ3 nm in size.
88. O2 is activated by a combined action of the Au0 nanoparticle surface and of the nanoparticle-support interface surface (Scheme 2). Chem. catalyzed by supported gold(0) Eur. this synergic mechanism makes Au0/S catalysts uniquely active in CO oxidation to such an extent that Au0/S is able to catalyse CO oxidation even more rapidly than H2 oxidation.eurjic. 2003. A selection of reactions relevant to chemical processing. J. This observation is a fundamental Table 1.Nanoparticulated Gold MICROREVIEW Au10 molecular clusters. However. Scheme 2.org 2003 Wiley-VCH Verlag GmbH & Co. KGaA. Weinheim 3095 .99] provide evidence that. catalyzed by Au6Ϫ in the gas phase Apparently. this is probably not the case and several authors[93. 3081Ϫ3098 www. Reaction steps proposed for CO oxidation to CO2 by Au0/TiO2 Figure 20. Schematic illustration of the formation of CO2. Inorg. while CO is activated by its end-on coordination to the nanocluster surface.
i. 10% and this goal seems to be feasible on Au0/TiMCM48. are known to allow the removal of CO (ppm levels) from the dihydrogen stream that feeds the fuel cells at 60Ϫ100 °C (PROX reactor). 1987. supported on a zeolite wash-coated honeycomb. 3081Ϫ3098 . Besides their unique color. which was published in 1989. Franklin. a little-explored and quite promising sector of gold catalytic chemistry is the employment of Au0/S catalysts in liquid-phase synthetic processes. making these artificial atoms valuable candidates for future nanoelectronics once appropriate techniques allow the generation of artificial structures on surfaces. Other applications. CO-free dihydrogen has to be employed and various Au0/S catalysts. The brilliant results obtained by a few research groups. In this context. Suslik). A renaissance in gold catalysis seems to have started.) in 2002. Weinheim G. Washington D. but it also promoted a huge amount of research on a variety of possible applications of gold nanoparticles in pollution-control technologies and in chemical processing. Acknowledgments The Alexander von Humboldt Foundation is gratefully acknowledged for a Scholarship provided to one of us (B. The long-awaited direct epoxidation of propylene is expected to become an Au0-catalyzed synthetic technology once the yield in propylene oxide has been improved to ca. Phil. in particular Au0/Al2O3/MgO/ MnO. Gold quantum dots may act as single-electron switches and transistors. Composite films of Co2O3 nanocrystals (5Ϫ10 nm) are expected to form the basis for optical sensors able to simultaneously detect H2 and CO at 1% levels.119] Finally. 3096 2003 Wiley-VCH Verlag GmbH & Co.e. 147. It is apparent from Table 1 that the prospects for employing supported nano-sized-Au0 in industrial catalysis are excellent. Faraday. for example oxidation reactions. and fine and specialty chemicals. Corain Au0/S catalysts are likely to become key components of CO safety masks and of devices for the efficient removal of CO from contaminated atmospheres. B. Conclusions Nanoparticulated gold has turned out to play an important role in various fields of nanoscience. mainly around the problem of CO and O2 activation. The technical problem to be solved for a straight commercialization of PROX technology is the achievement of a suitable stability of the catalyst itself.eurjic. 2002). C. 6. Another developing field is sensorics where gold nanoparticles might play the most important role. The first steps in this direction look very promising. 6. with good prospects for using water as the solvent in oxidation processes. 1857. Well-expressed quantum-size effects have been observed for particles smaller than 2 nm even at room temperature. Soc.[96. Bond. KGaA. Roy. K. in the potential industrial synthesis of commodities.MICROREVIEW premise to the commercial development of fairly innovative dihydrogen-air PEM (Polymer Electrolyte Membrane) fuel cells for vehicle propulsion and auxiliary power units.: K. Au0/La2O3. This sophisticated setup catalyses effectively the oxidative decomposition of bad smelling alkylamines (with a minimal production of N2O) that are responsible for the unpleasant atmosphere in toilets (‘‘odour eaters’’).5 Ongoing and Future Applications of Gold(0)-Based Catalysis This topic is presented and discussed in references 93.. Chem. and a golden future lies ahead’’ (G. S. not only produced an explosion of interest for the catalytic chemistry of gold nanoparticles.4 Gold(0)-Based Catalysis for Chemical Processing Haruta’s discovery. The facile synthesis of H2O2 from O2 and H2 seems to be one of the major listed results that allow us to imagine the achievement of small-scale industrial facilities for the production of hydrogen peroxide. in High Energy Process in Organometallic Chemistry (Ed. A few recent examples of these valuable prospects are presented in Table 1. 99 and 119. both in the gas and the liquid phase.. the best may be yet to come. C. even in water.   M. not yet to be foreseen. Chem. Soc. (Table 1) are indeed promising. Trans. without a significant consumption of dihydrogen. ‘‘Although we are well past the beginning of the discovery of gold’s catalytic potential. C. J. quite in line with the emerging view of ‘‘Green Chemistry’’. A peculiar current application is provided by Au0 deposited on Fe2O3.org Eur. may come up and make the next decades a ‘‘golden age’’. semi-commodities.2. M. 96. The moderate chemical reactivity of gold atoms on particle surfaces allows them to act as catalysts for distinct reactions. Schmid. pp 246Ϫ259. there are several catalytic reactions where gold nanoparticles act as highly efficient catalysts. 145. 2003. T. Inorg. Indeed.2. It can be assumed that the use of particulated gold will dramatically increase in the near future in very different fields. www. Am. J. Klabunde. gold nanoparticles became of scientific and technological interest because of their stability to air which means that they can be used even in nanosized form for many applications. Gold nanoparticles in combination with biomolecules are already at a point where even commercial applications in medical diagnostics have become known. integrated with Pd/SnO2 and Ir/La2O3 is likely to become employed as a catalyst for the oxidative decomposition of dioxins coming from incinerator outlet gases at temperatures below 473 K. at the latest when silicon technology has reached its physical limits. Gold nanowires as conducting contacts in nanoelectronics will also contribute to the progress of nanotechnology.
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