to understand the effects of Pd nanoparticle structure on their activity as catalysts for olefin hydrogenation Marc R. Knecht & Dennis B. Pacardo Received: 24 November 2009 / Revised: 25 January 2010 / Accepted: 26 January 2010 / Published online: 16 February 2010 # Springer-Verlag 2010 Abstract Recent developments in nanotechnology have led to the production of new materials with a wide array of applications, particularly in catalysis. Because of their small size, nanoparticles have a maximized surface-to-volume ratio, thus making them attractive targets for use as catalytic structures; however, the number of analytical techniques available to fully characterize materials on such a size scale is quite limited. As a result, a complete understanding of the entire nanoparticle structure remains unclear, especially when con- sidering the active structural motif from which the specific activity arises. Metallic Pd materials have been widely studied due to their immense potential as catalysts for reactions such as olefin hydrogenation and CC bond synthesis. These materials require surface passivants to act as ligands and stabilize the nanoparticles against aggregation and bulk formation. These ligands have the added value to function as gates that selectively allow reagents to reach the active surface of the Pd nanoparticles for chemical turnover. This accounts for the observed selectivities of the catalysts with the corresponding changes in the turnover frequency values. Here we present a broad overview of recent advances in the use of Pd nano- particles for the industrially important hydrogenation reaction with a focus on characterizing and understanding the base structural effects that give rise to the catalytic activity. Keywords Pd nanoparticles . Hydrogenation . Nanocatalysts . Materials characterization . Structurefunction relationship Current trends in catalysis The study of chemical catalysis has seen a renaissance in the last decade, particularly because of the onset of nanotechnol- ogy. The development of new synthetic methods to produce functional materials with nanoscale dimensions paved the way for the fabrication of nanoparticle catalysts that are highly efficient, selective, environmentally friendly, and can be used in a wide variety of reactions [15]. The nanoscale dimensions of these materials make them attractive for catalytic applications because of their large surface-to-volume ratio, which max- imizes the amount of catalytically active materials exposed to solution. For optimum materials, the nanoparticles must maintain their structural stability while mediating the specific catalytic reaction. This level of activity is typically controlled by the ligands used to passivate the surface [6], which prevent particle degradation while allowing for reagent interactions with the catalytic particles [1, 5]. Different ligands or stabilizers such as polymers [7, 8], dendrimers [1], and peptides [2, 9] have been developed, all of which can be used to fine-tune the surface structure of the materials for the desired application. Beyond stability considerations, the ligands can be used to determine the functionality of the particles by acting as selective filters and mediators that allow for specific molecular orientations for reactivity [1012]. This enables the development of stable and selective catalysts, which are desired for reactivity, selectivity, and for the design Electronic supplementary material The online version of this article (doi:10.1007/s00216-010-3516-z) contains supplementary material, which is available to authorized users. M. R. Knecht (*) : D. B. Pacardo Department of Chemistry, University of Kentucky, 101 Chemistry-Physics Building, Lexington, KY 40506-0055, USA e-mail: mrknec2@email.uky.edu Anal Bioanal Chem (2010) 397:11371155 DOI 10.1007/s00216-010-3516-z of enhanced systems that are both energy-efficient and environmentally friendly. Surprisingly, there are limited analytical characterization techniques that can be used to fully probe the structure of nanomaterials, especially for particles within the 110 nm size range, because the materials are too large to be studied by many traditional molecular approaches and too small to be probed by many solid-state methods. As a result, the level of detail known about the surface structure, metallic composition, and the interactions between these two levels is incomplete. This level of information is important to identify the structural characteristics that give rise to the final activity. While methods are available, for example electron microscopy [13], X-ray absorption spectroscopy [1420], and diffraction techniques [21], they are unable, individually, to fully probe the complete structure with atomic level resolution. Instrumental advances are currently being developed; however, the availability of such new techniques is limited. Furthermore, it is fundamentally important to use these characterization methods to probe the ligand surface, as this region is likely to play a significant role in the activity of the materials, especially for catalytic capabilities. Nanoparticle catalysts typically fall into a variety of categories; however, two main groups are normally repre- sented. First, homogeneous catalysts are those that are dispersed into solution and remain independent species before, during, and after the reaction [1, 2, 4, 12, 2226]. The second group, termed heterogeneous catalysts, is usually attached to a solid support and remains undissolved in the reaction medium [4, 2730]. While differences in reactivity are prevalent for both types of catalytic species, the advantage of heterogeneous catalysts lies in their facile removal for product purification. Additionally, for these insoluble species, modulations in their reactivity over their dispersible counterparts can arise from interactions with the solid support, which can change the electronic makeup of the catalytic system. Beyond these classifications, the actual size and structure of the nanocatalyst can have a dramatic effect on their reactivity [5, 8, 28, 31]. By forcing the size towards smaller particles, the surface-to-volume ratio is greatly maximized, which enhances the reactive surface area for the catalytic process [28, 31]; however, the degree of difficulty of characterization at these smaller sizes dramatically increases. Additionally, upon altering the particle shape, changes in reactivity have been noted [5, 7, 8, 32]. This change is likely to arise from surface coordinatively unsaturated metal atoms that exist in higher energy states. Under such conditions, these metal atoms, which typically lie at particle defect sites, are able to strongly bind and interact with reagents in solution in attempts to lower their individual energy states. This can result in driving the specific chemical reactions at faster rates. While the initial structures of the materials play important roles in functionality, two possible catalytic mechanisms exist that can alter the framework of the materials. In the first mechanism, the catalytic reaction occurs directly on the metallic surface of the materials [1, 31, 33]. As a result, minimal changes to the overall particle structure are expected, assuming that the capping ligands are able to accommodate this functionality. In the second mechanism, an atom-leaching effect is employed to drive the catalytic reaction [3, 24, 34]. To that end, during the reaction, Pd atoms are released from the nanoparticles into solution, where they act as the catalytic species. Upon completion, the nanoparticles are regenerated from the leached Pd atoms, thus using the nanoparticles as a reservoir of catalytically active species. This second mechanism, which is expected to drastically alter the nanoparticle structure, is rather difficult to characterize, especially for changes at the particle surface and structure during the reaction. While these general concepts tend to hold true for nanocatalysts, different reactions and their specific mecha- nisms can be altered by the composition and architecture of the materials, which controls the electronic properties of the nanosystem [35]. Below is a broad overview and descrip- tion of the current state of nanocatalysts and how their structure can directly alter their reaction capabilities for olefin hydrogenation [36]. A significant focus is on analytical characterization of the materials and how their configuration affects the hydrogenation process. This reaction was chosen because of its broad application in both academic and industrial settings. Furthermore, the hydrogenation reaction has also been used extensively as a model system for characterizing and understanding nano- catalytic effects to determine the efficiency of new materials, thus increasing its relevance to basic research. Synthesis of monometallic nanoparticle catalysts Noble metals nanoparticles such as Pd [2, 3, 5, 10, 22, 24, 2729, 31, 34, 3739], Pt [33, 4042], and Au [4345] have been widely studied as catalysts because of their chemical reactivity. While many strategies have been developed to fabricate these nanoparticles, ranging from extraction-based methods to those using thermal decompo- sition, most synthetic conditions currently employ the reduction of metal-ions, obtained via inorganic salts, in the presence of a ligand or stabilizing agent [1, 2, 4, 6, 46, 47]. In most cases, the dissolved metal salt binds to the selected functional group of the ligand through a variety of interactions, for example electrostatics or covalent bonding. The molecular structure and composition of the metal ion ligand complex can then control the composition, size, shape, and structure of the final nanomaterial. Upon 1138 M.R. Knecht, D.B. Pacardo reduction using NaBH 4 or comparable reagents, the metal ions are fully reduced to the zero valent state, from which nucleation and particle growth can ensue to produce the catalytically reactive metallic materials. The final compos- ite architecture of the materials is directly controlled by the concentration of reagents in solution, the strength of the reductant, the degree of the interaction between the metal ions and the ligands, the metal ion-to-ligand ratio, and the strength of the interaction between the ligands and the zero valent metal surface for nanoparticle passivation [6]. While most reactions typically result in the production of spherical particles, which is thermodynamically preferred, as shown in Fig. 1, production of other shapes such as rods, cubes, tetrahedra, and wires have been achieved by modulating the reaction conditions and through the use of seeding-based reaction schemes [7, 8, 48, 49]. Furthermore, the shape of the nanostructure can be controlled by the interactions of the passivant ligands with the growing surface; some ligands preferentially bind to different crystallographic facets, which can alter their growth rates compared with other, non-bound surfaces, thus resulting in shaped nano- material fabrication. For the basic synthesis of Pd nanomaterials, which is a fundamentally important component for numerous catalytic reactions, reduction of Pd 2+ or Pd 4+ in the presence of appropriate monodentate coordinating ligands typically produces spherical zero valent Pd particles [47, 50, 51]. The final structure of the materials is a metallic core that is passivated on the surface with numerous ligands. The identity of the binding moiety is chosen on the basis of hardsoft acidbase theory [52] to produce optimally passivated surfaces, which typically employ amines and thiols for Pd. It is from the molecular structure of the ligand that a variety of nanoparticle properties are derived, including optical traits, solubility, and chemical reactivity. Zamborini et al. have used this approach to prepare Pd nanoparticles of diameters <2 nm that were extensively characterized using 1 H NMR and TEM imaging [47]. In this study, hexanethiolate (C 6 ) and dodecanethiolate (C 12 ) ligands were employed and the size of the particles generated was inversely proportional to the Pd-to-ligand ratio used. To that end, as the specific ratio increased, the size of the nanoparticles decreased; using a C 6 ligand-to-Pd ratio of 1/2, 1, and 2, nanoparticles with dimensions of 3.0, 2.2, and 1.6 nm, respectively, were prepared [47]. To further characterize this system, 1 H NMR spectroscopy was employed. For this analysis, detection of resonances associated with specific protons within the carbon chain backbone was dependent upon their proximity to the nanoparticle surface. For instance, for the C 6 materials prepared with a ratio of 1/2 (3.0 nm), the terminal CH 3 and internal methylene protons were readily observed with Fig. 1 TEM images of Pd nanomaterials of various shapes including (a) spherical DENs (adapted with permission from Ref. [23]; copyright 2004 American Chemical Society), (b) nanorods (adapted with permission from Ref. [49]; copyright 2007 American Chemical Society), (c) nano- cubes (adapted with permission from Ref. [49]; copyright 2007 American Chemical Society), and (d) nanowires (adapted with permission from Ref. [48]; copyright 2009 American Chemical Society) Employing high-resolution materials characterization to understand the effects of Pd nanoparticle structure 1139 somewhat broad resonances; however, the protons bound to the -carbon next to the surface-attached thiol could not be observed. As the particle size decreased with increasing ratios, these peaks tended to become less broad and the - carbon protons could be observed [47]. This is likely to be because of the small sizes of the clusters, which were not observable using standard TEM methods. Furthermore, some of these smaller particles may form organometallic- based clusters, which would be small enough to minimize the peak broadening effects observed with the larger nanoparticles. Beyond simple monodentate ligands, other polydentate ligands have been explored to prepare Pd nanoparticles [8]. Using these species, chelate effects can be used to impart a higher level of surface coordination between the individual ligand and the nanoparticle. To that end, polymers such as poly-(N-vinyl-2-pyrrolidone) (PVP) are optimum structures as they present numerous amines that can bind and passivate the surface [8, 34]. Using nearly identical synthetic techniques as described above, but replacing the ligands with appropriate multidentate species, nanoparticles of 2.10.1 nm can readily be produced, as characterized by extensive TEM measurements [34]. As further monitored by Narayanan and El-Sayed using analytical TEM analysis, changes to the particle size were noted for the materials after multiple uses as catalysts for Suzuki C-coupling reactions [34]. After the first reaction, the particle size shifted to 2.90.3 nm, which suggests a change in the particle morphology as a result of the catalytic reaction. Furthermore, when these same particles were employed for a second reaction, their diameters shifted to 2.20.2 nm [34]. Based upon statistical analysis, these particle sizes suggest that an atom leaching and deposition mechanism may be responsible for the Suzuki reaction. The changes in the diameter are likely to arise from the deposition of Pd atoms on to remaining nanoparticles on completion of the reaction. These atoms would likely be deposited on the nearest particle, resulting in particle size shifts, rather than evenly on to all particles in solution to maintain the initial particle size. This level of information, which is highly important in understanding catalytic mechanisms, is obtained from TEM measurements. Furthermore, for such an analysis, it is important to ensure that a statistically relevant nanoparticle population is studied to ensure the validity of the results. For instance, for the Suzuki-based analysis, the diameters of 1800 particles per sample were determined to guarantee that the changes in size were statistically accurate [34]. Beyond the approach of employing ligands to passivate the surface of Pd nanoparticles, other approaches have been studied that employ templates to grow and protect nano- particles within the structure [1, 46, 5355]. A unique example of this fabrication method uses polyamidoamine (PAMAM) dendrimers as a nanoreactor/template for the production of nearly monodisperse nanoparticles with a variety of metallic compositions, including Pd and Pt [16, 38, 46]. PAMAM dendrimers are monodisperse and highly branched polymers that are grown radially from an ethyl- enediamine core [56]. The final size of the polymer is determined at the synthetic level, because different branch lengths can be controllably grown using traditional organic synthetic routes. The final structure can present chemical functionalities, for example amines, alcohols, and carbox- ylic acids, to the solution whereas the interior of the dendrimer possesses numerous tertiary amine and amide groups that are able to chemically coordinate metal ions [1, 56]. Additionally, based upon the branched structure, an internal void volume is present within the dendrimer that can accommodate various chemical loads, including nano- particles to prepare dendrimer-encapsulated nanoparticles (DENs) [57]. PAMAM dendrimers are able to template the formation of nanoparticles in a two-step manner [1, 15, 5861], which is shown schematically in Fig. 2. First, metal ions are mixed in the presence of the templates from which the ions can be extracted from solution into the interior of the dendrimer. This process is facilitated by the metal-ions covalently binding to the tertiary amines to form a dendrimermetal ion complex. Second, the metal ions are reduced by NaBH 4 , which results in their coalescence within the dendrimer to form the zerovalent nanoparticle. Based upon this synthesis, a high level of control can be gained over the final size of the materials. Using PAMAM dendrimers, a 1:1 ratio of Pd 2+ ions to tertiary amines can be achieved so that the number of amines within the template controls the upper limit of particle size [16, 37, 46, 62]. For instance, the sixth Fig. 2 Schematic representation of the synthesis of dendrimer- encapsulated nanoparticles 1140 M.R. Knecht, D.B. Pacardo generation PAMAM dendrimer possesses 256 tertiary amines; therefore, the structure is capable of producing metal nanoparticles that possess 250 metal atoms [56]. Addition- ally, the average number of atoms per particle can be controlled by reaction stoichiometry, thus enabling produc- tion of Pd nanoparticles with selected average numbers of metal atoms at sizes <4 nm [31]. Furthermore, metallic nanoparticles prepared in this manner are not passivated on their exposed surface, because of the template-based struc- ture [15, 63]; therefore, much of the metallic surface is presented to the solution for catalytic studies. An extensive number of characterization techniques have been employed to confirm the complex structure of DENs ranging from microscopy to spectroscopy [1, 15, 16, 31, 46, 58, 59]. Initial characterization of Pd DENs has used UV visible spectroscopic measurements. From this, a ligand-to- metal charge-transfer (LMCT) band is observed at 224 nm [46]. This is consistent with the binding of Pd 2+ ions to the interior tertiary amines to form the precursor complex. Using a titration analysis, it has been determined that a 1:1 ratio of interior amines-to-Pd 2+ binding is possible, which was elucidated using UVvisible; therefore, the upper threshold of the number of atoms per particle is limited by the number of amines [46]. Upon reduction, the size and morphology of the metallic Pd materials has been exten- sively characterized using TEM [31]. From this process, nanoparticles ranging from 1.02.5 nm have been generated where the stoichiometric ratio of Pd-to-dendrimer con- trolled the final particle dimensions. To that end, the particle size correlated quite well with a particle composed of the number of atoms used in the stoichiometry [31]. While the above characterization methods possess the ability to probe the metallic composition, elucidation of the interactions of the dendrimer with the nanoparticle surface required the use of high-resolution techniques such as extended X-ray absorbance fine structure (EXAFS) [1519] and 1 H NMR spectroscopies [63, 64]. Using these techniques, atomic level information can be obtained concerning the metallicligand surface, which is exceed- ingly difficult to probe. From both spectroscopic methods, it has been determined that minimal to no interactions between the dendrimer template and the metallic surface, specifically Au for these studies, are present [18, 63], which suggests that the surface is able to interact with reagents in solution. Furthermore, from the EXAFS studies, an AuAu coordination number (CN) of 9.0 was achieved for Au DENs with an average of 147 atoms [18], which corre- sponds well with the expected theoretical value of 8.98 for a cuboctahedral Au nanoparticle of 147 atoms [14]. Interestingly, contraction of the AuAu bond length was determined spectroscopically using EXAFS2.832 for the DENs versus 2.87 for bulk Au; this suggests that a high degree of surface tension is present in the system and causing these changes [18]. This evidence is important in understanding the catalytic functionality of the materials on the basis of the exposed reactive sites. For instance, these results indicate that a significant fraction of the metallic and catalytically active surface is not bound by the interior dendrimer functionalities and is freely available for reac- tivity. This is a unique feature associated with dendrimer- based materials, which required highly sensitive and not readily available spectroscopic techniques to confirm this surface structural feature. Monometallic olefin hydrogenation Hydrogenation is an increasingly important reaction for industrial applications, including the production of pharma- ceuticals, polymers, and petroleum products. In this reaction, H 2 gas is added to the system and used as a reductant to produce the final product [36]. Traditional chemical moieties and functional groups that are targeted for hydrogenation reactivity include alkenes, alkynes, carboxylic acids, aldehydes, and ketones [36]. A degree of selectivity in these reactions is desired to produce enantio- merically pure products, and to proceed at one reactive moiety within a substrate molecule when multiple points of reactivity exist in the same species. Targeting specific moieties, rather than fully hydrogenating the entire chem- ical compound, can reduce certain functional groups within the molecule without removing necessary chemical struc- tures and functionality. Here we focus on the use of Pd nanocatalysts used in olefin hydrogenation and further discuss how their structure alters their reactivity. This reaction is an efficient probe of the catalytic capabilities of nanomaterials and can be done using relatively simple and inexpensive experimental analyses. To achieve maximum hydrogenation reactivity, a high surface area is desirable; however, to achieve such conditions, the particle size should be approximately 1 10 nm [31]. Unfortunately, in this size range, the surface energies of the Pd system are such that aggregation and formation of bulk Pd black precipitate are expected. To overcome this issue, surface passivants are required that may lower the reactivity by binding and poisoning reactive sites [6, 47]. To avoid this effect, DENs are ideal catalyst candidates [1]. In this structure, the guest nanoparticles are encapsulated within the dendrimer hosts where minimal surface binding has been observed between the template and the metallic surface [15, 63]. Using this method, nanoparticles of <500 atoms are routinely prepared, which places them in the optimized 13 nm diameter size range for reactivity by maximizing the surface-to-volume ratio. DENs demonstrate catalytic activity by allowing substrates to penetrate the dendrimer periphery, to react at the exposed Employing high-resolution materials characterization to understand the effects of Pd nanoparticle structure 1141 metallic surface, then letting the products diffuse back into solution [10, 22, 23, 31, 33, 37, 38]. To differentiate between DENs of different sizes, GX-OH(Pd Y ) notation will be used to describe Pd nanoparticles synthesized within X generation of hydroxyl-terminated PAMAM dendrimers that contain, on average, Y Pd atoms. Initial studies using G4-OH(Pd 40 ) DENs, which had an average particle size of 1.30.3 nm measured by TEM analysis [38, 46], indicated high turnover frequencies (TOFs) for the catalytic hydrogenation of allyl alcohol to 1-propanol [38]. To analytically quantitate this reaction, and obtain data that can be used for direct comparison of reactivity, an aqueous DENs solution is saturated with H 2 , to which the olefin-containing substrate, allyl alcohol, is injected. By monitoring the change in gas volume above the reaction, product yields can be calculated to determine TOFs. For this reaction, a TOF of 218 mol product (mol Pdh) 1 was observed [38]. Interestingly, as the generation of the dendrimer increased, a decrease in the TOF was observed. For instance when G6-OH(Pd 40 ) or G8- OH(Pd 40 ) DENs were used, TOF values of 201 and 134 mol product (mol Pdh) 1 , respectively, were determined [38]. These changes were attributed to the increased steric effects of branch crowding at the dendrimer periphery, shown in Fig. 3, which is a consequence of large dendrimers [38]. As a result, the rate of substrate partitioning into the dendrimer is slower for larger generations of dendrimers. These differ- ences in TOFs can also be used to characterize the nanoparticle structure, where the reactivity further supports the encapsulated nanoparticle structure over a surface passivated motif. This is a unique example where catalysis can be used to probe the structure of the catalytic material. This effect was further tested to determine the degree of selectivity of DENs [10]. In this regard, rather than solely changing the dendrimer generation, the molecular size of the catalytic substrate was also modulated to determine if size- based gating could be achieved using various generations of dendrimers. This is attractive because of the cost of higher- generation dendrimers [56], and the degree of selectivity for the lower generations may allow for more reactivity. In this study, G4-OH(Pd 40 ), G6-OH(Pd 40 ), and G8-OH(Pd 40 ) were all tested across five different allyl alcohol derivatives that were increasingly larger in molecular size, as shown in Table 1 [10]. Consistent with the previous study [38], as the generation increased, the TOF values decreased, because of the surface steric crowding at the dendrimer periphery (Fig. 3); however, as the molecular size increased, the TOF values again decreased for particles prepared using the same dendrimer generation. To that end, when G4-OH(Pd 40 ) was employed as the catalyst, a TOF of 480 mol H 2 (mol Pdh) 1 was achieved using substrate 1, but when the largest molecules were used as substrate, species 5, a TOF value of 100 mol product (mol Pdh) 1 was observed [10]. This decrease is likely to have been caused by the larger molecular size lowering its ability to penetrate and diffuse through the dendrimer structure. Similar trends are observed for G6-OH (Pd 40 ) and G8-OH(Pd 40 ), with lower TOFs compared with the G4-OH(Pd 40 ) species [10]. While the DENs possessed significant catalytic reactiv- ity, their controlled structure at very small sizes (<4 nm) Fig. 3 Effects of dendrimer generation on the catalytic activity of Pd DENs, as studied by Niu et al. [10]. As the generation size gets larger, steric crowding at the dendrimer periphery increases to act as a size- selective gate to control the catalytic reactivity of the materials 1142 M.R. Knecht, D.B. Pacardo enables more quantitative analysis of the hydrogenation reaction mechanism. From an understanding of how the reaction proceeds, optimized structures can be elucidated and integrated into more complex systems to maximize the reactivity for future catalysts. By being able to select the average number of metal atoms per cluster by reaction stoichiometry, the numbers of surface atoms, face atoms, and defect atoms can be directly determined [31]. Here, defect atoms refer to atoms along crystallographic edges and vertices of the metallic structure. The numbers of these specific atoms change with increasing particle sizes; therefore, it can be analytically determined how these substitutions alter the reactivity based upon the near monodispersity of DENs of this size. For this analysis, G6-OH dendrimers were used to prepare DENs with 55, 100, 147, 200, and 250 Pd atoms per cluster on average [31]. The DENs were analyzed by TEM, which demon- strated particle sizes of 1.3, 1.4, 1.5, 1.7, and 1.9 nm, respectively, which correlated with the expected values [31]. Figure 4a displays the calculated values of surface, defect, and face atoms for these nanoparticles over sizes between 1.0 and 2.0 nm [31]. Because the reaction is likely to occur on the nanoparticle surface, normalization of TOF values to the mols of the various types of atoms at controlled positions can occur. Through this process, identical TOFs are expected when the catalytic active site is used to normalize the data. As presented in Fig. 4b, when the TOF values for the various sized DENs are normalized by the surface atoms, defect atoms, or number of particles in solution, a linear trend with a positive slope is observed [31]. This indicates that these values do not accurately represent the active site; however, when the data are normalized to the number of face atoms on the nanoparticle surface, identical values are achieved for DENs with sizes 1.5 nm [31]. This suggests that the hydrogenation reaction occurs preferentially at face atoms of the metallic compo- nent. Interestingly, at sizes<1.5 nm, different normalization trends are observed and are attributed to electronic effects that are expected at these smallest of sizes [31]. In a unique recent study, Mizugaki et al. used Pd nanoparticles as a core material to bind PAMAM dendrons to the metallic surface [65]. The dendrons are grown from the primary amine of 4-picolylamine, thus leaving the pyridine ring available for nanoparticle surface binding. The dendrons are grown from the first generation (G1), to the second generation (G2), to the third generation (G3). Additionally, each generation of dendrons are terminated with either C 6 or C 12 aliphatic chains, thus rendering the materials soluble in organic solvents [65]. Regardless of the surface function- alities, when dissolved in solution employing organic solvents, the dendrons self-assemble into micelle-like frame- works with similar average diameters ranging between 9.4 and 11.8 nm, as measured by dynamic light scattering (DLS) Table 1 TOF values for Gn-OH(Pd 40 ) DENs using allyl alcohol and structural analogues. (Adapted with permission from Ref. [10]; copyright 2001 American Chemical Society) Fig. 4 Catalytic effects of particle size of Pd DENs. (a) Comparison of the ratio of atoms within the Pd nanoparticles. (b) Comparison of the TOF values normalized to the respective Pd atoms. (Adapted with permission from Ref. [31]; copyright 2006 American Chemical Society) Employing high-resolution materials characterization to understand the effects of Pd nanoparticle structure 1143 [65]. Size and assembly-based characterization of the dendrons in solution is important to understanding the synthetic mechanism for materials production. From this information, a template-based synthetic scheme can be developed, where comparison with sizes after nanoparticle formation can be addressed to qualitatively describe the effects of the ligand structural surface on the reactivity. At the center of the micelle-like scaffold, Pd 2+ can be sequestered; upon reduction, this produces nanoparticles that are weakly bound by the pyridine ring. The formation of the Pd core does not change the size of the micellular structure; however, Pd nanoparticles with diameters of 6.82.0 nm, 5.31.7 nm, and 5.11.9 nm are grown employing the G1- C6, G2-C6, and G3-C6 dendrons, respectively [65]. Inter- estingly, similar effects are observed with the C 12 terminated materials, but when using these dendrons, smaller Pd nanoparticles are prepared with diameters of 4.61.9 nm, 3.61.3 nm, and 3.51.3 nm for the G1-C12, G2-C12, and G3-C12 dendrons, respectively [65]. Based upon this synthetic strategy, it is likely that the pyridine rings of the core branching point interact with the Pd surface to stabilize the nanomaterials. Catalytic analysis of the materials for hydrogenation produced size-dependent reaction effects; however, for these materials, as the generation of the dendron increased, the TOF of the materials for 1,3-cyclooctadiene to cyclo- octene increased also. This effect is in contrast with the size-dependent catalytic reactivity of the DENs discussed above and is rationalized from the degree of surface binding by the dendrons in the nanocomposite structure [65]. For all of the dendrons, regardless of generation, G1, G2, or G3, or surface functionality, C 6 or C 12 , nearly similar sized self- assembled micelles are prepared, which was ascertained using DLS characterization. As a result, it is likely to take fewer G3 dendrons to produce the micelles compared with the G1 materials. From this, fewer pyridine rings are associated with the G3 micelle interior to bind to the Pd nanoparticle; therefore, more exposed metallic surface is available from these materials to drive the hydrogenation reaction, which results in the higher TOF values. Identical trends are observed by transitioning from C 6 to C 12 surface functionalities, which can alter the number of dendrons within the micelle structure. It is based upon the character- ization of the materials structure, ascertained from a combination of DLS and TEM studies, that a functional mechanism to understand the catalytic properties of the materials can be achieved. Without this level of structural detail, determination of base causes for the different reactivities would be challenging. The naturally occurring cage-like protein ferritin also functions as a template and stabilizer for metal nano- particles similar to synthetic dendrimers [66]. The X-ray crystal structure of ferritin, shown in Fig. 5, has 24 subunits that self-assemble to form a caged framework with a cavity for iron-storage in cells [66]. The structure of these proteins includes hollow channels that allow metal ions to traverse to the protein core; on reduction these produce nano- particles of sizes selected by the metal-to-protein ratio [12, 66, 67]. By using this biomimetic method, spherical Pd nanoparticles with sizes of 2.00.3 nm are formed at the cavity of the protein, as characterized by traditional TEM [12]. Further characterization of the nanoparticle synthesis was conducted using gel electrophoresis. In this study, both the apo-ferritin and nanoparticle containing protein migrat- ed at the same rate, which indicated that minimal to no changes in the protein structure/size occurred as a result of encapsulation of the metallic nanoparticles. This was corroborated using negative staining-based TEM where the protein structure was clearly observed surrounding the metallic nanoparticle to characterize the general structure of the materials [12]. The catalytic activity of the Pd@ferritin nanoparticles for hydrogenation was evaluated using increasingly larger olefin substrates. As shown in Table 2, the TOF values of the Pd@ferritin nanoparticles for the hydrogenation of olefin containing compounds are lower than the values Fig. 5 Analysis of the ferritin protein used to prepare Pd nanoparticles: (a) full crystal structure, and(b) internal and external dimensions of the protein [12]. (Copyright WileyVCH. Reproduced with permission.) 1144 M.R. Knecht, D.B. Pacardo generated from Pd-DENs [12], which may be an effect of the surface passivant (protein versus dendrimer). Currently, the interactions of the protein interior with the nanoparticle surface have not been elucidated; therefore, no conclusions can be drawn about the degree of Pd metallic surface exposure. In this arrangement, however, the protein is likely to cover the Pd surface to a higher degree than the template PAMAM dendrimers, which is expected to reduce the reaction rates. While the overall values are lower for the Pd@ferritin materials, the system is again sensitive to molecular size with larger substrates producing decreased TOFs compared with smaller reagents [12]. This is likely to be the effect of the protein allowing smaller molecules to penetrate and interact with the metallic surface while sterically preventing larger species from reacting based upon pathways to the metallic catalyst; however, the charge of the substrate species may also control the degree of protein penetration. While the overall rates are lower for the biomimetic system, the advantage here is that the templates are prepared using biological techniques that are environ- mentally friendly, over the stringent organic synthesis required for PAMAM dendrimer fabrication [56]. While template-based methods to prepare homogeneous Pd materials represent good strategies to probe the structure-function relationship of nanocatalysts, the separa- tion of the catalytic species from the product post-reaction can be problematic. In many cases, both the catalysts and product molecules are highly soluble in the reaction medium, which requires the use of time-consuming separation techniques, some of which can be complicated. Furthermore, for industrial applications, such affects can become cost prohibitive. By transitioning from a homoge- neous to a heterogeneous system, such separation factors can be minimized while maintaining the desired degree of reactivity and selectivity from the catalyst. Bruening and coworkers have fabricated heterogeneous composite systems with high selectivity. As shown in Fig. 6, Table 2 Olefin hydrogenation TOF values for ferritin-encapsulated Pd nanoparticles employing variously sized substrate molecules [12]. (Copyright WileyVCH; reproduced with permission) Substrate TOF Pd@ferritin Pd particles CH 2 = CHCONH 2 720.7 585.9 CH 2 = CHCOOH 2 6.31.1 122.6 CH 2 = CHCONH-iPr 516.5 150.3 CH 2 = CHCONH-tBu 315.9 6.10.6 CH 2 = CHCO-Gly-Ome 6.33.8 282.6 CH 2 = CHCO-D,L-Ala-OMe not detected 230.3 Fig. 6 Synthetic scheme for production of Pd nanoparticles embedded within a multilayer polyelectrolyte film (MPF) on the surface of alumina beads, as developed by Bruening and coworkers [29] Employing high-resolution materials characterization to understand the effects of Pd nanoparticle structure 1145 for this system, multilayer polyelectrolyte films (MPFs) are deposited on to the surface of alumina beads, from which the Pd nanoparticles are grown within the polyelectrolyte film [2729, 39]. The films are grown by alternating the deposition of poly(acrylic acid) (PAA) and a Pd 2+ -containing polyethylenimine (PEI) on to the alumina surface. Subse- quent addition of NaBH 4 reduces the Pd 2+ to form zero valent Pd nanoparticles embedded within the structure, which can be fully separated from the solution by using filtration. Based upon the materials structure, traditional TEM imaging of the Pd nanoparticles on the alumina bead surface would be difficult; the background associated with the bead would prevent the ability to observe the Pd nanoparticles embedded within the MPF. To overcome this issue, a model system was employed in which the films and embedded nanoparticles were grown directly on a TEM grid. This enabled observa- tion of the Pd nanoparticles without interference from the beads. Using this method, 13-nm Pd particles are prepared within the polymeric film [39]. This arrangement of materials encapsulates the catalytic particles within a polymeric structure, similar to that observed with the DENs. Although these are not exactly the structures used for catalysis, they represent sufficient model systems of the likely structures attached to the bead surface. Initial catalytic analysis of the MPF materials for the hydrogenation reaction demonstrated a high degree of selectivity. These studies focused on the hydrogenation of allyl alcohol to form 1-propanol. For this reaction employing MPF materials coated with 3.5 bilayers of PAA/PEI, a TOF of 727128 mol product (mol Pdh) 1 was observed [39]. When the number of bilayers in the system was increased to 7.0, the TOF drastically reduced to a value of 14120 mol product (mol Pdh) 1 [39]. This suggests that the thickness of the polyelectrolyte layer controls the catalytic reactivity of the materials by minimizing interactions with the Pd metallic surface. Based upon the TEM evidence, the nanoparticles are indeed embedded within the polymeric surface; therefore, with a higher number of coatings, more Pd is buried deeper within the framework, thus possibly being unavailable for use for catalysis because of the steric effects of the additional polymer layers. A control analysis of commercially available 5% Pd on alumina without a polymeric coating demonstrated a TOF of 1300150 mol product (mol Pdh) 1 , which supports the gating-based hypothesis derived from the materials structure [39]. To further probe the size-selective capabilities of the heterogeneous materials, 1-penten-3-ol and 3-methyl-1- penten-3-ol were catalytically hydrogenated to form their reduced products. For these materials, with 3.5 polyelectrolyte bilayers, TOF values of 27823 mol product (mol Pdh) 1 and 6015 mol product (mol Pdh) 1 , respectively, were observed [39]. These values are directly in line with those that were expected, based upon a size gating effect suggested by the structure of the materials observed via TEM characterization. When the film thickness was further increased to 7.0 bilayers, the TOF values decreased to 65 8 mol product (mol Pdh) 1 for 1-penten-3-ol, whereas the 3-methyl-1-penten-3-ol species demonstrated a low TOF value of 61 mol product (mol Pdh) 1 [39]. These decreasing values based upon substrate size and the poly- electrolye film thickness are attributed to the size-gating effects of the materials. Mixtures of these substrates confirmed the selectivity of the reaction [39]. Interestingly, when commercially available materials are used, significantly higher TOF values are recorded; however, the degree of selectivity is fully lost. The appropriate system should therefore be selected before the reaction, on the basis of the chemical functionality of the substrate and the desired product. While these materials demonstrate selectivity for the hydrogenation of multiple substrates in solution, the ability to reduce a single olefin within a molecular structure that possesses multiple double bonds is desirable. This capability has the potential to simplify synthetic schemes in which full hydrogenation of all olefins within a compound is undesirable. To study this ability, 1,5-heptadien-4-ol and 3,7-dimethyl-6- octadien-3-ol were used [27]. Using the first substrate, a TOF value of 183535 mol product (mol Pdh) 1 was observed, with 97% conversion to 2-hepten-4-ol product over the fully reduced product (4-heptanol) [27]. Studies of the second compound resulted in 97% conversion to 3,7-dimethyl-6- octen-3-ol; however, a much lower TOF was observed compared with the first substrate (700140 mol product (mol Pdh) 1 ) [27]. From this study, two key facts became evident about the reactivity of the MPFs. First, the more exposed olefin was preferentially reduced. Considering the structure of the nanomaterial, this suggests that the molecule can penetrate the surface of the polyelectrolyte film and reduce the exposed olefin in a more efficient manner compared with the second double bond, which is sterically protected. Second, the degree of substitution at the reducible double bond affects the TOF of the reaction. When bulkier substituents are in closer proximity, the ability of this region of the molecule to penetrate the polymer film is reduced, thereby reducing the reaction rate. Nevertheless, these results suggest high selectivity for molecules of different sizes, and the position of the olefin within the structure of the substrate, all of which is controlled by the architecture of the composite nanosystem that is mediated by the steric constraints of the polymeric framework. Most studies employing MPFs have focused on the effects of film thickness; however, changes to the structure and size of the individual catalytic particles embedded in the polymer film can also affect the reactivity. When using the alumina-based systemwith three PAA-PEI layers, increasing the concentration of Pd 2+ used during materials production resulted in the 1146 M.R. Knecht, D.B. Pacardo fabrication of larger nanoparticles, as extensively character- ized employing TEM. For this analysis, deposition of the Pd nanoparticle containing polymeric films on to TEM grids was used, as described above, to observe any changes in the particle size based upon the concentration of Pd 2+ in the system. To that end, when the Pd 2+ concentration was 1, 4, 8, or 15 mM, the average Pd particle size within the MPFs was 2.20.5, 2.90.5, 3.20.6, and 3.40.9 nm, respectively [28]. While a distribution of particle sizes is observed, the trend is maintained of larger dimensions as required for the analysis. Further characterization of the system was achieved by use of atomic-emission spectroscopy. In this method, the amount of Pd associated with each alumina bead-based system was quantitatively determined for use in the normal- ization of the catalytic studies. This is an important value to ensure validity of the comparison of the catalytic effects of the different sized Pd nanoparticles. When employing these materials for catalytic hydrogenation, three clear trends are observed: 1. the TOF values for monosubstituted alcohols decrease with increasing particle size; 2. the TOF values for disubstituted alcohols increase with increasing particle size; and 3. the selectivity of the catalysts decreases for larger particles [28]. As shown in Table 3, when hydrogenating allyl alcohol, the TOF values decrease from 2900570 mol product (mol Pdh) 1 to 76040 mol product (mol Pdh) 1 as the particle size increases over the range studied [28]. Isomer- ization of the products was also observed; however, this was not incorporated in the presented data. Interestingly, when employing the disubstituted alcohol 2-methyl-2-propenol as the substrate with catalytic materials of increasingly size, the TOF values increased from 121 mol product (mol Pdh) 1 to 29070 mol product (mol Pdh) 1 [28]. This is in direct contrast to the trend observed for allyl alcohol, a mono- substituted species. As a result, the selectivities of the catalysts for mono versus disubstituted alcohols ranged from 240 for the smallest particles to 2.6 for the largest materials [28]. An identical trend was observed when using crotyl alcohol as the disubstituted species [28]. Furthermore, similar trends were observed for polymer-coated homogeneous catalysts prepared using the same polyelectrolytes in solu- tion, suggesting that the observed effects were the result of the particles and not the MPFs. The changes in the reactivity and selectivity for the mono and disubstituted alcohols were attributed to geometrical aspects of the Pd nanoparticles, as determined via extensive TEM characterization. It is known that the number of defect atoms and sites on the nanoparticle surface increase for smaller particles, whereas the number of face/terrace atoms increases for larger particles [31]. It is rather difficult to visually observe such defects using traditional microscopy techniques; however, spectroscopic methods may enable such observation. The authors suggest that the reactivity of monosubstituted alcohols preferentially occurs at the defect sites, which would result in the higher TOFs for smaller particles, while the disubstituted alcohols react at the terrace sites that would yield higher TOFs with larger particles where the number of these atoms would increase [28]. Previous research by Wilson et al. has also indicated a preference for the hydrogenation reaction to occur along terrace/face atoms, which would support this hypothesis [31]. As a result of the reaction site requirements, which appear to be controlled directly by the metallic structure and the ligand interface, the controlled reactivity and selectivity of the system could be altered by particle size, thus yielding another structural/functionality tool for hydrogenation cata- lyst design. In a variant of the MPF system, Kidambi and Bruening prepared similar materials using alumina beads; however, they grew the polyelectrolyte films without use of PAA [29]. In the PAA/PEI system, PAA was the first polymer deposited on to the alumina surface. In the new strategy, PdCl 4 2 was bound directly on to the alumina surface, which can subsequently bind PEI in a second step to form the polymeric layer [29]. This process is repeated multiple times (PdCl 4 2 binding followed by PEI deposition) to form the structure. Upon reduction, Pd nanoparticles are gener- ated within the deposited PEI film. The main difference between these materials and those previously prepared is the fact that no PAA is present within the system. To fully characterize the new PAA-free system, a battery of approaches was employed. First, UVvisible and X-ray photoelectron spectroscopies (XPS) were used to ensure that binding of the Pd 2+ ions to the subsequent PEI polymeric layer was occurring [29]. This was evident from the formation of the LMCT band in the UVvisible at 220 nm that increased proportionally to the number of layers deposited on the alumina bead surface. Based upon the XPS studies, the Pd-to-Cl ratio was <1; therefore, it is Table 3 TOF values for MPF-encapsulated Pd nanoparticles of various sizes employing allyl alcohol and structural analogues. (Adapted with permission from Ref. [28]; copyright 2009 American Chemical Society) Employing high-resolution materials characterization to understand the effects of Pd nanoparticle structure 1147 likely that the PEI is able to displace Cl and bind directly to the Pd ions to maintain the structure [29]. After reduction, TEM analysis was used to quantitate nanoparticle produc- tion. From this method, Pd nanoparticles are prepared with diameters between 1 and 3 nm that were embedded within the PEI film [29]. Further XPS studies of the materials after reduction indicated the generation of a fully reduced product, which was suitable for catalytic studies [29]. Catalytic hydrogenation employing these structures, how- ever, produced surprising results. Although these materials demonstrated size-dependent gating effects similar to those of other MPF materials, the films produced with only PEI demonstrated higher TOF values with increasingly thicker films. To that end, for n values of 1, 2, 3, and 4, where n represents the number of PdCl 4 2 /PEI layers deposited on the alumina surface, TOF values of 820, 750, 1990, and 1220 mol product (mol Pdh) 1 were observed [29]. This suggests that with thicker films, higher catalytic rates are possible. The authors reasoned that this was a structural effect that resulted from employing a single polymeric system over the double polymeric system used previously [29]. In this method, PdCl 4 2 is directly adsorbed on to the alumina surface; therefore, a large fraction of the initially deposited catalytic materials is likely to be buried within the pores of the metal oxide bead. As a result, these buried components may prove to be inactive, because it is unlikely that the substrate molecules are able to penetrate the polymer layers and the pores of the alumina to interact in this region. While the absolute amount of Pd metal trapped in the pores remains constant as the number of deposited layers increases, the fraction of the total metal that is entrapped within the pores will decrease for thicker films. To that end, the fraction of inactive Pd metal will decrease for the larger structures, thus increasing their TOF values. Similar results are observed for 1-penten-3-ol and 3- methyl-1-penten-3-ol; however, the relative TOFs between these two molecules decrease with the larger molecule, as expected [29]. As demonstrated above, the ability of the nanoparticle catalyst to affect the selectivity of the hydrogenation reaction is influenced by the substrate, support, and/or overall structure of the nanosystem. In the case of DENs or MPFs, the polymeric structure acts as a filter that regulates which molecules can reach the catalytically active surface resulting in a selective gate based upon size and olefin position. Thus, a sterically hindered molecule will take a longer time to diffuse through the network and reach the reactive sites. Other solid supports, for example carbon nanotubes (CNTs) have been employed; these are promis- ing materials for the development of bulk heterogeneous catalysts [30, 68, 69]. These materials are interesting as they possess a large surface area, which would be amenable to driving extensive catalytic reactions. Their selectivity may be lower than for other materials; however, such structures would be of interest for the hydrogenation of sterically constrained olefins, and other species. Karousis et al. demonstrated the synthesis of Pd nano- particles on the surface of CNTs with the aid of a surfactant, sodium dodecyl sulfate (SDS), which acts as both the solubilizing agent for the CNTs in polar solvents and the reductant of the metal ion, as shown in Fig. 7 [30]. The Pd/ CNT composite materials are fabricated by sonicating the bare CNTs in an aqueous solution of SDS. This disperses the materials and results in the interaction of SDS with the CNT surface. This step is the followed by heating of the materials under reflux in the presence of Pd(OAc) 2 for 6 h [30], which results in thermal reduction of the Pd 2+ ions to form Pd metal atoms that nucleate and grow into Pd nanoparticles on the CNT surface. The newly formed composite materials were then extensively characterized using TEM, UVvisible spectroscopy, thermogravimetric analysis (TGA), and XPS [30]. TEM images, presented in Fig. 8, reveal the deposition of 24 nm Pd nanoparticles on the CNTs. The nanoparticles seem to fully coat the tube surface, suggesting that homogeneous modification of the materials is possible to achieve a high density of catalytic materials [30]. Further Fig. 7 Schematic representation of the production of Pd nanoparticles on the surface of carbon nanotubes (CNTs), as developed by Karousis et al. [30] 1148 M.R. Knecht, D.B. Pacardo characterization by TGA confirmed that the surfactant and degradation products remained bound to the CNT surface after nanoparticle fabrication, and could be thermally removed at temperatures >150 C. This supports the hypothesized synthetic process and indicates that these molecules are likely to interact with the catalytic surface of the Pd nanomaterials once formed. Further analysis by XPS established the production of zero valent Pd nanoparticles and the interaction with the CNT surface [30]. Together, these results aided in confirmation of the composite/ heterogeneous structure, which was catalytically active. The catalytic activity of the Pd/CNT composites in the hydrogenation of olefins was studied using alcohol and aldehyde-containing olefins [30]. For methyl-9-octadecenoate, 2-methyl-3-buten-2-ol, and 2-methyl-2-pentenal, one equi- valent of H 2 was consumed in conversion of the materials into the expected final product; however when 3,7-dimethyl- 2,6-octadien-1-ol was used, which contains two olefin species, two equivalents of H 2 were used to generate the single 3,7-dimethyl octanol compound [30]. Interestingly, when the aldehyde-containing molecule 3-phenyl-2-propenal was used, a multitude of products were formed from reduction of either the olefin or the aldehyde after consumption of two H 2 equivalents. The TOF values from the conversion of methyl-9-octadecenoate and 2-methyl-2-pentenal were deter- mined to be 8163 and 8030 mol product (mol Pdh) 1 , respectively [30]. The TOF values of Pd/CNT composites are almost four times those of traditional Pd on C catalysts [30]. This effect is likely to be because of the large active surface area of the Pd nanoparticles on the CNT surface that is used to drive the reaction, which was extensively characterized, as discussed above, to confirm this capability. Although the Pd/CNT materials show high reactivity, they were not selective for the hydrogenated moiety using the described conditions. Another important characteristic of the Pd/CNT materials is that they are also recoverable by centrifugation after the reaction and can be recycled for further use. Similar TOF values were observed for some substrates even after seven catalytic cycles; however, some substrates did have dimin- ished TOF values [30]. Although it is unclear which sub- strates maintained their TOFs after multiple use, or the extent to which the TOF value decreased, this ability is quite useful for catalyst use in multiple reactions over time. This suggests that the reaction mechanism minimally alters the catalytic surface for future use; however, complicated in-situ reaction- characterization studies are required to confirm this possibil- ity. Also, the ability to simply separate the Pd/CNT materials by centrifugation ensures minimal loss of the precious metal structures after the reaction. In a separate method, Ye et al. deposited Pd nano- particles on the surface of CNTs by using an organometallic precursor [70]. In this method, the CNTs were acid washed to functionalize the surface with COOH groups, which are used for metal nanoparticle deposition. The organometallic complexes were then reduced in a high-pressure system, using H 2 , to form the Pd nanoparticles on the CNT surface. Initial characterization of the materials by TEM analysis revealed Pd nanoparticles on the exterior surface of the CNTs. Employing the organometallic starting materials, nanoparticles between 5 nm and 10 nm were generated on the solid support of the CNT. Energy-dispersive spectro- scopic (EDS) analysis of the composite materials indicated that the particles were indeed composed of Pd metal, and a selected area electron diffraction (SAED) pattern of a single nanoparticle indicated that the materials were crystalline. These results were further corroborated by XPS studies of the materials that confirmed that the structures were composed of zero valent Pd. Further time-based XPS studies of the nanocomposites indicated that the Pd Fig. 8 TEM images of the production of Pd nanoparticles on the surface of CNTs. (a) CNTs before the reaction. (b) The free, unattached Pd nanoparticles. (c) The CNTs with Pd nanoparticles on the surface. (Reprinted with permission from Ref. [30]; copyright 2008 American Chemical Society) Employing high-resolution materials characterization to understand the effects of Pd nanoparticle structure 1149 components were stable to oxidation over time, thus suggesting that the CNT-based platform may be a unique method to achieve active catalysts [70]. Unfortunately, it remains unclear what is present/interacting on the metallic surface, which is an important characteristic when consid- ering the catalytic reactivity of the materials. For catalytic analysis of the CNT-based structures, the hydrogenation of trans-stilbene in liquid CO 2 was studied [70]. These conditions were employed to enhance the green chemistry attributes of the materials, an important goal for future nanocatalytic studies. Under the reaction conditions, which occurred at a pressure of 10 7 Pa, product conversion of 80% and 96% were observed at 5 min and 10 min reaction times, respectively, employing a 10% Pd by loading at a temperature of 23 C. These yields are significantly enhanced compared with those for commercially available Pd on C, for which the yield was 10% for a time >20 min [70]. This effect is likely to be because of the high metallic surface area presented to the reaction solution on the CNT surface, and which is maximized by the nanocomposite structure. Tessonnier and coworkers tested the hydrogenation selectivity of Pd/CNT composites in which the Pd was embedded within the CNTs [71]. These materials were prepared by dispersing the CNTs in a Pd-ion containing solution, which was dried and calcined to form PdO [71]. The PdO was then thermally reduced using H 2 and the final embedded structures were confirmed by TEM. From this method, based upon high-resolution, analytical TEM studies of the materials, Pd nanoparticles of diameters between 4 nm and 8 nm were clearly evident on the interior surface of the materials. Images of the outer surface revealed a lack of modification; however, it was evident that the Pd nanoparticles were interacting with the interior walls of the CNTs to generate the composite materials [71]. Unfortunately, it is unclear what remains bound to the displayed nanoparticle surface, but it is evident that the structures are catalytically active in the hydrogenation of cinnamaldehyde, which contains C=C and C=O function- alities [71]. Possible products of this hydrogenation reaction, as shown in Fig. 9, include hydrocinnamaldehyde, which arises from the hydrogenation of the C=C moiety, cinnamyl alcohol from the hydrogenation of C=O bond, and phenylpropanol from the hydrogenation of both functional groups. The catalytic results demonstrate selec- tive hydrogenation of the olefin over the aldehyde to produce hydrocinnamaldehyde as the lone product. When a commercially available charcoal-supported Pd catalyst was used for comparison, this species produced a mixture of both hydrocinnamaldehyde and phenylpropanol [71]. The authors attribute the high selectivity of the embedded Pd/CNT catalysts to electron transfer between the metal and the carbon nanotube, which is possible based upon the observed structure, thus increasing the charge density on the metal surface. Also, the absence of microporosity in the nanoparticles is likely to change the adsorption properties toward the reactants, which may give rise to the selectivity. Many catalytic reactions, including hydrogenation, occur in organic solvents; however, changing to more environmen- tally friendly conditions is desirable. Chun et al. have designed a system which uses ionic liquids, which may prove to be important for green chemistry, to solubilize Pd/CNT materials for the hydrogenation reaction [68]. In this sense, the CNTs are functionalized with imidazolium bromide, which makes the Pd/CNT composites soluble in both water and ionic liquids. Pd nanoparticles of 100.5 nm diameter are produced on the functionalized CNTs, as determined by high-resolution TEM, and their catalytic potential for hydrogenation was tested using trans-stilbene in methanol [68]. The TOF values show very high efficiency of 2820 mol product (mol Pdh) 1 [68]. The ease of separation of the Pd- CNTs from the reaction mixture enables the recycling of the catalyst, which can be used at least ten times without any loss of catalytic reactivity. Bimetallic nanoparticles for olefin hydrogenation Beyond synthetic strategies to optimize the ligand surface of monometallic nanoparticles, the incorporation of a second metal into the inorganic component has resulted in further enhancement of the catalytic properties of the system [15, 23, 35, 37, 72, 73]. These enhancements mainly arise from two key factors: 1. geometric arrangement of the metal atoms for specific interactions with the substrate, and 2. changes to the electronic character of the metallic system. In the first case, the metal atoms are specifically arranged within the structure to incorporate multiple Fig. 9 Catalytic pathways for the hydrogenation of cinnamaldehyde 1150 M.R. Knecht, D.B. Pacardo binding/interaction points with the reagents in solution to facilitate the reaction, which can increase the rate of product formation. In the second case, changes to the electronic make- up of the system can occur on the basis of the electro- negativities of the two metals. In this event, the more electronegative atoms pull electron density from the second component, making the second materials more electropositive and thus more reactive in the catalytic reaction. This second case is likely to directly affect the hydrogenation reaction. For this to occur, the additional metal should be more electroneg- ative than Pd, which would impart a slight positive character- istic to the catalytic moieties; this is believed to increase their interactions with the H 2 and olefin substrate to enhance the reaction TOF. Typical examples of secondary metals include Au and Pt, forming the PdAu [15, 23, 26, 67, 74] and PdPt [37] systems, respectively. Both bimetallic modes of action, however, result in substantial complexity in full confirmation of the structures of the materials. From their nature, bimetallic nanoparticles can be placed into three types of categories: alloys, coreshell, or phase segregated. Because the orientation of the atoms is important to overall activity, it is critical to determine their individual arrangement within the metallic nanoparticle to confirm the structural effects of the reaction. To achieve such a level of information, atomically-resolved and quantitative data concerning the system must be acquired, which can be rather difficult to achieve. To address these objectives, different spectroscopic and catalytic methods have been used to probe the structure of the materials, as discussed below. Bimetallic nanoparticles are typically fabricated in two different structural motifs in which the two metals are alloyed together or arranged in a coreshell pattern, as shown in Fig. 10. These structures are obtained via the synthetic procedure used to prepare the materials. To achieve bimetallic alloys, co-reduction of two different metal salts, in the presence of an appropriate surface passivant, can be used. This causes the nucleation and growth of nanoparticles wherein a mixture of the two metals is generated [15, 23, 67, 74, 75]. For the coreshell arrangement, denoted by X@Y to describe these structures, where X represents the core metal and Y represents the shell metal, sequential reduction of the two metals is normally used [19, 23, 26, 74]. For this method, production of a monometallic nanoparticle is processed, from which these materials can be used as a subsequent catalytic seed to deposit the secondary metal atoms along the nanoparticle surface. This process results in the formation of the coreshell structure with a high degree of control over the resulting materials because of the step-wise-based procedure. Both methods have been extensively used for production of alloyed and coreshelled materials for hydrogenation applica- tions in which one of the metals was Pd. By combining the synthetic strategy of bimetallic nano- particles with the PAMAM dendrimer templates, bimetallic PdAu alloy and coreshell nanoparticles have been readily prepared [15, 19, 23]. This provides the unique modulation of the electronic character of the system, with the open metallic surface for reactivity. Using the co-reduction method, PdAu alloy nanoparticles were prepared with diameters <2 nm; where the metallic composition can be directly modulated by the stoichiometric ratio of the two metal ions used in synthesis [23]. EXAFS analysis of these materials confirmed a quasi random alloy; however, the core and shell of the structure was slightly enriched with Au and Pd, respectively [15]. Furthermore, no interactions with the dendrimer were noted, suggesting that the surface is highly exposed to drive the reaction. When used as catalysts for olefin hydrogenation, the bimetallic alloy DENs were significantly more reactive than physical mixtures of Pd and Au DENs, shown in Fig. 11 [23]. For this analysis, both the number of particles and the Pd:Au Fig. 10 Synthetic schemes for production of bimetallic nanoparticles. The top route, co-reduction, results in the production of alloyed materials whereas the bottom route, sequential reduction, results in the fabrication of coreshell structures Fig. 11 Bimetallic effects on the hydrogenation catalytic reactivity of PdAu alloy DENs as a function of the mole % Pd within the nanoparticle structure. For comparison, the catalytic TOF values for a physical mixture of monometallic Pd DENs and Au DENs are presented (Reprinted with permission from Ref. [23]; copyright 2004 American Chemical Society) Employing high-resolution materials characterization to understand the effects of Pd nanoparticle structure 1151 ratio in the reaction solution were maintained; however, in the alloyed particles, the Pd and Au atoms were chemically combined whereas in the physical mixture no interactions between the two metals is expected. The data were subsequently plotted on the basis of the mole % of Pd in the reaction, which was further confirmed by EXAFS and EDS analysis [15, 23], which demonstrated the alloyed particles had enhanced reactivity compared with the physical mixture at all points within the system [23]. The maximum activity was observed from the alloyed DENs that contained 25% Au atoms within the structure, which nearly doubled the observed TOF value as compared with analysis of the physical mixture. Using the dendrimer system, Au@Pd materials were also prepared using the sequential reduction method. For this, monometallic Au DENs were prepared that contained on average 55 atoms; these materials were subsequently used as seeds to deposit Pd on to the metallic surface [19, 23]. TEM analysis confirmed the increase in the particle diameter upon shell generation and the particle sizes corresponded quite well with the theoretical size as determined by the stoichiometry employed in the materials fabrication [23]. More recent EXAFS analysis verified the synthetic method and the final structure of the Au@Pd arrangement [19]. Using these materials, enhancement in the TOF values compared with monometallic Pd materials of nearly the same size was observed. A two-atom-thick shell layer of Pd on the Au core was required to increase the reaction rate 1.25 times [23]. The enhancement of the reaction was less than that observed for the alloyed materials, which may be because of the different metallic structures; more intimate contact is likely to occur in the alloyed materials to optimize the electronic variations required for the catalytic activity compared with the Au@Pd structures. As a result, higher reaction rates may be observed with alloyed materials; however, further scientific studies are required to confirm this hypothesis. Although this method can be used to prepare Au@Pd materials, the reverse arrangement of Pd@Au could not be generated. When such a synthetic technique was employed, in which monometallic Pd cores are prepared, followed by Au shell deposition, inversion of the two metals occurs resulting in Pd on the shell with an Au core [19]. These results were quite unexpected, but were fully confirmed by EXAFS, TEM, and UVvisible analysis [19]. From the TEM results, particles of the expected sizes, based upon the molecular stoichiometries used in the reaction, were achieved; however, this information is unable to probe the metallic arrangement of the atoms within the inorganic particle. EXAFS analysis demonstrated that inversion of the two metals occurred, based upon changes to the MM CNs extracted from the X-ray absorbance data, which suggested the fabrication a Au@Pd structure over the intended Pd@Au arrangement [19]. At present, it is unclear why such an inversion process would occur; however, such events demonstrate the need to fully characterize the materials at the atomic level to ensure that a proper structural motif has been achieved that addresses the observed reactivity. PdAu alloy nanoparticles have also been used for selective hydrogenation using a heterogeneous solid sup- port for facile catalyst extraction. In the method reported by Prvulescu et al., Pd 2+ and Au 3+ ions were co-reduced in the presence of a surfactant stabilizer that produced zero valent PdAu alloy nanoparticles 3 nm in diameter, as confirmed by TEM [75]. Furthermore, the XRD patterns were consistent with the expected PdAu structure. These materials were then incorporated into a modified solgel procedure to generate SiO 2 , which encapsulated the materials within a porous metal oxide network. Based on the composite materials processing employed, the pore diameter of the SiO 2 materials ranged from 16.6 to 24.0 nm, as determined by BrunauerEmmettTeller (BET) analysis; this is sufficiently large to enable substrate molecules to penetrate the periphery and interact with the alloyed bimetallic materials [75]. The composite structures were then studied in the hydrogenation of cinnamaldehyde, which has multiple reactive chemical functionalities (Fig. 9) [75]. Using the bimetallic PdAu materials, selective generation of cinnamyl alcohol occurred, over the preferred phenylpropanol product [75]. This suggests that beyond reactivity enhancements, PdAu materials may prove to be selective for production of the desired organic materials. This is a distinct advantage when multiple reactive groups are present in a single substrate, which can significantly complicate organic synthetic designs. Similar results to those observed with the PdAu DENs have been demonstrated using other materials that employ traditional surface passivants bound to the nanoparticle surface. For instance, Mizukoshi et al. have prepared Au@Pd nanoparticles using a sonochemical-based ap- proach employing a mixed solution of Au 3+ and Pd 2+ ions [76]. UVvisible evidence indicates the Au 3+ ions are reduced first, followed by the Pd 2+ species, producing an Au@Pd coreshell motif, which results in particles of 8.0 nm in diameter, as measured via TEM analysis [76]. The diameter of the core and thickness of the shell can be controlled by modifying the Pd:Au ratio used during synthesis, adding a valuable level of synthetic control to the system. When using these materials for the catalytic hydrogenation of 4-pentenoic acid, maximum activity was observed for the coreshell materials containing 20% Au [76]. At this value, the materials are about 2.5 times more efficient than their monometallic counterparts. Furthermore, analogous Au@Pd materials with diameters of 6.32.2 nm prepared by Okitsu et al. using similar synthetic techniques 1152 M.R. Knecht, D.B. Pacardo demonstrated maximum hydrogenation activity of cyclo- hexene at 30 mol% Au [77]. Interestingly, all of these values correspond quite well to those observed with the DEN-based bimetallic materials. This suggests that a Pd:Au atomic ratio of 75:25 may be optimum for catalytic reaction efficiency. Similar to the studies that employed the biomimetic monometallic Pd particles, the cage-like protein ferritin has been used to synthesize bimetallic PdAu nanoparticles within its hollow core. The recombinant L-chain apo- ferritin from horse liver is used as a templating agent for fabrication of alloy PdAu nanoparticles using the co- reduction method and sequential-reduction methods were used to produce the coreshell structure [67]. Using this method both Au@Pd and Pd@Au materials could be prepared. In the production of PdAu alloy nanoparticles, Pd 2+ ions are loaded into the ferritin core that has been pre- treated with Au 3+ ions [67]. Upon reduction of the metal ions using NaBH 4 , the two species randomly mix to produce the alloyed structure with an average metallic diameter of 2.2 0.2 nm. Interestingly, based upon the coordination environ- ment of the two different metal ions prior to reduction, which has been characterized using inductively coupled plasma- optical emission spectroscopy to determine the number of Au or Pd ions bound to the protein, fewer Au atoms than Pd atoms can be introduced to the ferritin-based structure. As a result, the ability to control the Pd:Au ratio in the final materials can be limited by the number of ions able to be bound by the protein. Coreshell nanoparticles, on the other hand, are synthesized by loading the Au 3+ ions into the protein; reduction then produces monometallic Au nano- particles. Pd 2+ ions are then introduced and subsequently reduced on to the Au core to produce an Au@Pd structure with an average diameter of 2.40.3 nm [67]. The inverted Pd@Au materials were produced using identical methods; however, the Pd core was prepared first, followed by Au deposition. These structural characteristics were confirmed by using high-resolution TEM and EDS methods that confirmed the composition of the materials. The catalytic activities of the PdAu alloy and the Au@Pd nanoparticles in the hydrogenation of acrylamide in water were then determined. Using these two materials, TOF values of 510, 310, and 1300 were observed for monometallic Pd nano- particles prepared in the ferritin protein, PdAu alloys, and the Au@Pd coreshell materials, respectively [67]. Such results were quite surprising, especially for the alloyed materials. The TOF value for the Au@Pd nanoparticles is 2.5-times higher than that for the Pd-monometallic species, suggesting that the catalytic activity of Pd on the surface of the nanoshell is enhanced by introduction of the Au core because of the synergistic effect of bimetallic nanoparticles; however, the TOF values for the PdAu alloys are substan- tially lower than those for both the monometallic Pd and Au@Pd materials [67]. This result is quite surprising, based upon the above described alloy results and the expected electronic configuration. In a unique peptide-based study, Slocik and Naik have demonstrated the production of PdAu nanomaterials in which small Pd nanoparticles are deposited on the surface of a larger, core, Au nanoparticle [26]. To achieve this structure, a bifunctional peptide was generated that is able to passivate the surface of Au nanoparticles while display- ing a sequence known to bind Pd nanomaterials. Upon reduction of Pd 4+ in the presence of the peptide-capped Au particles, nucleation and growth of the surface Pd materials occurs. This unique method was extensively studied using UVvisible and high-resolution TEM analysis. The main structural detail was confirmed by use of TEM, which is able to display the Pd particles attached to the Au surface. High-resolution images of the materials reveal the lattice fringes associated with both systems in intimate contact, to which electronic changes may be possible between the two materials [26]. The catalytic capabilities of this system were studied by hydrogenation of 3-buten-1-ol; this revealed a TOF value of 1016 mol H 2 (mol Pdh) 1 , significantly better than for comparable Pd nanoparticles, for which the TOF value was 501.5 mol H 2 (mol Pdh) 1 [26]. These results suggest that not all Pd atoms must be directly attached to the Au atoms, but that the structure must incorporate both species to result in the electronic shifts required to drive the increased TOFs. Conclusions In conclusion, current research has demonstrated a prom- ising future for use of nanomaterials as catalysts for olefin hydrogenation and numerous other reactions, including C- coupling and CO oxidation. A full comparison of the catalytic TOF values of the materials presented herein, compared with values for the Pd structure and substrate, is presented in the Supporting Information. As future research progresses towards understanding the catalytic reactivity of these materials, it is important to remember that the structure of the nanocatalyst is critically important to its reactivity. Complete materials characterization at the atomic level is required to fully understand the motifs responsible for driving this unique functionality, especially for the smallest of particles. Unfortunately, achieving full charac- terization of the materials to ascertain motifs that drive the reaction can be rather problematic. This is caused by the lack of sufficient analytical methods to address the nano- scale regime with a high degree of resolution. Development of new techniques is required to observe such complicated architectural changes, and these are undoubtedly being developed. 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