Supported Metal Nanoparticle Catalysts Research Articles

Oxidant‐free Dehydrogenation of Glycerol to Lactic Acid by Heterogeneous Platinum Catalysts

AbstractAmong various supported metal nanoparticle catalysts, Pt‐loaded carbon (Pt/C) catalysts, including a commercial one, showed the highest yield for selective dehydrogenation of glycerol to lactic acid under oxidant‐free, solvent‐free, and alkaline conditions. For the reaction with Pt/C, the effects of conditions (type of basic additives, the amount of water, atmosphere, reactor) on the catalytic activity and selectivity were studied. Combined with a reaction pathway in the literature and our result of control reactions, we proposed a strategy for decreasing the selectivity of byproducts. The optimized conditions gave a high turnover number of 69 000. To clarify the structural factors affecting the catalytic activity, we show the effect of electronic states of various transition metals on the activity as well as the effect of Pt particle size on the turnover frequency per surface Pt atom.

Optimised hydrogen production by aqueous phase reforming of glycerol on Pt/Al2O3

Aqueous phase reforming of glycerol was studied over a series of γ-Al2O3 supported metal nanoparticle catalysts for hydrogen production in a batch reactor. Of the metals studied, Pt/Al2O3 was found to be the most active catalyst under the conditions tested. A further systematic study on the impact of reaction parameters, including stirring speed, pressure, temperature, and substrate/metal molar ratio, was conducted and the optimum conditions for hydrogen production (and kinetic regime) were determined as 240 °C, 42 bar, 1000 rpm, and substrate/metal molar ratio ≥ 4100 for a 10 wt% glycerol feed. The glycerol conversion and hydrogen yield achieved at these conditions were 18% and 17%, respectively, with negligible CO and CH4 formation. Analysis of the spent catalyst using FTIR provides an indication that the reaction pathway includes glycerol dehydrogenation and dehydration steps in the liquid phase in addition to typical reforming and water gas shift reactions in the gas phase.

Resolving Interparticle Heterogeneities in Composition and Hydrogenation Performance between Individual Supported Silver on Silica Catalysts.

Supported metal nanoparticle catalysts are commonly obtained through deposition of metal precursors onto the support using incipient wetness impregnation. Typically, empirical relations between metal nanoparticle structure and catalytic performance are inferred from ensemble averaged data in combination with high-resolution electron microscopy. This approach clearly underestimates the importance of heterogeneities present in a supported metal catalyst batch. Here we show for the first time how incipient wetness impregnation leads to 10-fold variations in silver loading between individual submillimeter-sized silica support granules. This heterogeneity has a profound impact on the catalytic performance, with 100-fold variations in hydrogenation performance at the same level. In a straightforward fashion, optical microscopy interlinks single support particle level catalytic measurements to structural and compositional information. These detailed correlations reveal the optimal silver loading. A thorough consideration of catalyst heterogeneity and the impact thereof on the catalytic performance is indispensable in the development of catalysts.

On the metal–support synergy for selective gas-phase ethanol oxidation over MgCuCr2O4 supported metal nanoparticle catalysts

Achieving high yields in the production of bulk chemicals is an important goal for the chemical industry. We investigated the influence of the metal on the catalytic performance of M/MgCuCr2O4 (M=Cu, Ag, Pd, Pt, Au) catalysts to better understand the metal–support synergy for the aerobic oxidation of ethanol. Pt/MgCuCr2O4 and Pd/MgCuCr2O4 are more active and less selective for ethanol oxidation than the other catalysts, mainly because they can dehydrogenate and then cleave the carbon–carbon bonds in ethanol at relatively low temperature. Because of the facile oxidation of Cu0 and Ag0 under aerobic oxidation conditions, Cu/MgCuCr2O4 and Ag/MgCuCr2O4 are less active for ethanol oxidation. On contrary, Au/MgCuCr2O4 is a very active, selective and stable catalyst for sustainable production of acetaldehyde, achieving 96% selectivity at full ethanol conversion (space–time–yield up to 583galdehydegAu−1h−1) at 250°C. Low gold loading and high gold dispersion are important to enhance the Au0–Cu+ synergy and the catalytic efficiency of Au/MgCuCr2O4.

Single-atom gold catalysis in the context of developments in parahydrogen-induced polarization.

A highly isolated monoatomic gold catalyst, with single gold atoms dispersed on multiwalled carbon nanotubes (MWCNTs), has been synthesized, characterized, and tested in heterogeneous hydrogenation of 1,3-butadiene and 1-butyne with parahydrogen to maximize the polarization level and the contribution of the pairwise hydrogen addition route. The Au/MWCNTs catalyst was found to be active and efficient in pairwise hydrogen addition and the estimated contributions from the pairwise hydrogen addition route are at least an order of magnitude higher than those for supported metal nanoparticle catalysts. Therefore, the use of the highly isolated monoatomic catalysts is very promising for production of hyperpolarized fluids that can be used for the significant enhancement of NMR signals. A mechanism of 1,3-butadiene hydrogenation with parahydrogen over the highly isolated monoatomic Au/MWCNTs catalyst is also proposed.

One-pot synthesized hierarchical zeolite supported metal nanoparticles for highly efficient biomass conversion.

Hierarchically porous zeolite supported metal nanoparticles are successfully prepared through a base-assisted chemoselective interaction between the silicon species on the zeolite crystal surface and metal salts, in which in situ construction of mesopores and high dispersion of metal species are realized simultaneously.

金属ナノ粒子と無機金属酸化物との協奏的触媒機能に基づいた環境調和型分子変換システムの開発

Inorganic metal oxides-supported metal nanoparticle catalysts are designed for green molecular transformation system. The supported metal nanoparticle catalysts such as hydrotalcite-supported gold and silver nanoparticles show unique and excellent catalytic activities for versatile organic reactions such as aerobic oxidations, oxidative carbonylations, and chemoselective reductions of epoxides to alkenes and nitrostyrenes to aminostyrenes using alcohols and CO/H2O as reducing reagents. These high catalytic performances are derived from the cooperative effect between metal nanoparticles and supports. Furthermore, as a new strategy for increasing the metal-support interaction, core-shell nanoparticles consisting of active metal nanoparticles in the core with metal oxide supports in the shell are designed to maximize their metal nanoparticle-support interface areas. These core-shell nanocomposite catalysts exhibit excellent chemoselective hydrogenation of nitrostyrenes to aminostyrenes, unsaturated aldehydes to allyl alcohols, and alkynes to alkenes. Moreover, these solid catalysts developed are easily recovered from the reaction mixture by simple filtration and reusable with retaining their high catalytic activities.

Alkylation of 2-methylquinoline with alcohols under additive-free conditions by Al2O3-supported Pt catalyst

Supported metal nanoparticle catalysts are studied for alkylation of 2-methylquinoline with benzyl alcohol under additive-free conditions in N2 atmosphere. Among various metal-loaded Al2O3 catalysts and supported Pt catalysts, Pt metal nanocluster loaded-Al2O3 pre-reduced in H2 at 500°C shows highest yield (82%) of the product (2-phenethyl-quinoline). The catalyst is reusable, shows higher turnover number than a previous homogeneous catalyst, and shows good to moderate yield for alkylation of 2-methylquinoline with various alcohols. The reaction is driven by the borrowing-hydrogen pathway, in which aldehyde formed by dehydrogenation of alcohol undergoes aldol condensation with 2-methylquinoline to give the alkene intermediate which is finally hydrogenated by Pt-H species.

The Energetics of Supported Metal Nanoparticles: Relationships to Sintering Rates and Catalytic Activity

Transition metal nanoparticles on the surfaces of oxide and carbon support materials form the basis for most solid catalysts and electrocatalysts, and have important industrial applications such as fuel production, fuels, and pollution prevention. In this Account, I review my laboratory group's research toward the basic understanding of the effects of particle size and support material on catalytic properties. I focus on studies of well-defined model metal nanoparticle catalysts supported on single-crystalline oxide surfaces. My group structurally characterized such catalysts using a variety of ultrahigh vacuum surface science techniques. We then measured the energies of metal atoms in these supported nanoparticles, using adsorption calorimetry tools that we developed. These metal adsorption energies increase with increasing size of the nanoparticles, until their diameter exceeds about 6 nm. Below 6 nm, the nature of the oxide support surface reaches also greatly affects the metal adsorption energies. Using both adsorption calorimetry and temperature programmed desorption (TPD), we measured the energy of adsorbed catalytic intermediates on metal nanoparticles supported on single crystal oxide surfaces, as a function of particle size. The studies reveal correlations between a number of characteristics. These include the size- and support-dependent energies of metal surface atoms in supported metal nanoparticles, their rates of sintering, how strongly they bind small adsorbates, and their catalytic activity. The data are consistent with the following model: the more weakly the surface metal atom is attached to the nanomaterial, the more strongly it binds small adsorbates. Its strength of attachment to the nanomaterial is dominated by the number of metal-metal bonds which bind it there, but also by the strength of metal/oxide interfacial bonding. This same combination of bond strengths controls sintering rates as well: the less stable a surface metal atom is in the nanomaterial, the greater is the thermodynamic driving force for it to sinter, and the faster is its sintering rate. These correlations provide key insights into how and why specific structural properties of catalyst nanomaterials dictate their catalytic properties. For example, they explain why supported Au catalysts must contain Au nanoparticles smaller than about 6 nm to have high activity for combustion and selective oxidation reactions. Only below about 6 nm are the Au atoms so weakly attached to the catalyst that they bind oxygen sufficiently strongly to enable the activation of O₂. By characterizing this interplay between industrially important rates (of net catalytic reactions, of elementary steps in the catalytic mechanism, and of sintering) and their thermodynamic driving forces, we can achieve a deeper fundamental understanding of supported metal nanoparticle catalysts. This understanding may facilitate development of better catalytic nanomaterials for clean, sustainable energy technologies.

Pt, Pd and Au nanoparticles supported on a DNA–MMT hybrid: efficient catalysts for highly selective oxidation of primary alcohols to aldehydes, acids and esters

Novel DNA-MMT hybrid supported metal nanoparticle catalysts, such as Pt/DNA-MMT, Pd/DNA-MMT, Au/DNA-MMT, were prepared for application in highly selective aerobic oxidation of primary alcohols to aldehydes, acids and esters, respectively. Taking advantage of the water-soluble reversibility of these catalysts, all the transformations could be performed smoothly in water and reuse of the catalysts has also been accomplished by a very simple phase separation process.

Synthesis of supported metal nanoparticle catalysts using ligand assisted methods

The synthesis and characterization methods of metal nanoparticles (NPs) have advanced greatly in the last few decades, allowing an increasing understanding of structure-property-performance relationships. However, the role played by the ligands used as stabilizers for metal NPs synthesis or for NPs immobilization on solid supports has been underestimated. Here, we highlight some recent progress in the preparation of supported metal NPs with the assistance of ligands in solution or grafted on solid supports, a modified deposition-reduction method, with special attention to the effects on NPs size, metal-support interactions and, more importantly, catalytic activities. After presenting the general strategies in metal NP synthesis assisted by ligands grafted on solid supports, we highlight some recent progress in the deposition of pre-formed colloidal NPs on functionalized solids. Another important aspect that will be reviewed is related to the separation and recovery of NPs. Finally, we will outline our personal understanding and perspectives on the use of supported metal NPs prepared through ligand-assisted methods.

Impact of Anions on Electrocatalytic Activity in Palladium Nanoparticles Supported on Ionic Liquid–Carbon Nanotube Hybrids for the Oxygen Reduction Reaction

A series of palladium nanoparticles supported on carbon nanotubes (CNTs), which were functionalized covalently with imidazolium polymer salts with different anions, Pd/polyIL(X)-CNTs (IL=ionic liquid; X=Cl, Br, I, ClO(4), BF(4), PF(6)), were prepared to investigate the influence of imidazolim salt anions on electrocatalytic activity in the oxygen reduction reaction (ORR). The anions of the imidazolium moiety significantly impacted on the ORR kinetics in a 0.1 M solution of HClO(4). The electronically active surface area results are in good agreement with the order of the ORR kinetic activity of the supported Pd/polyIL(X)-CNTs (X: Cl>ClO(4)>BF(4)>Br≈PF(6)≫I). In contrast, owing to the facile anion exchange of halide anions with hydroxide anions, anion-dependent catalytic activity has not been observed in 0.1 M NaOH. Iterative ORR experiments in acid-base solutions demonstrated anion exchange on the electrode. These results indicate that subtly varied structures of the IL moiety profoundly influence the performance of IL-CNT hybrid materials and molecular-level control of interfacial interactions between the support material, catalysts, and electrolytes is important in the design of supported metal nanoparticle catalysts for fuel cells.

Fabrication and characterization of platinum nanoparticle arrays of controlled size, shape and orientation

We present a rigorous approach for the shape design of supported metal nanoparticle catalysts, morphologically identical to each other and epitaxially grown on strontium titanate substrates using electron beam lithography. We predict the particle shapes using Wulff construction based on density functional theory calculations of surface energies. Then, according to the theoretical predictions, we are able to tweak morphologies of the already produced nanocrystals by changing annealing conditions. The ability to design, produce and characterize the catalyst nanoparticles allows us to relate microscopic morphologies with macroscopic oxygen-reduction activities in perchloric acid [Komanicky et al., J. Am. Chem. Soc. 131 (2009) 5732]. The unexpectedly high oxygen-reduction activities proportional to inactive (1 0 0) facets led us to suggest a model where the reaction intermediates can cross over to neighboring facets in nanoscale proximity.