Showing papers on "Platinum published in 2011"

Single-atom catalysis of CO oxidation using Pt1/FeOx

Abstract: Platinum-based heterogeneous catalysts are critical to many important commercial chemical processes, but their efficiency is extremely low on a per metal atom basis, because only the surface active-site atoms are used. Catalysts with single-atom dispersions are thus highly desirable to maximize atom efficiency, but making them is challenging. Here we report the synthesis of a single-atom catalyst that consists of only isolated single Pt atoms anchored to the surfaces of iron oxide nanocrystallites. This single-atom catalyst has extremely high atom efficiency and shows excellent stability and high activity for both CO oxidation and preferential oxidation of CO in H-2. Density functional theory calculations show that the high catalytic activity correlates with the partially vacant 5d orbitals of the positively charged, high-valent Pt atoms, which help to reduce both the CO adsorption energy and the activation barriers for CO oxidation.

High-Performance Electrocatalysts for Oxygen Reduction Derived from Polyaniline, Iron, and Cobalt

Abstract: The prohibitive cost of platinum for catalyzing the cathodic oxygen reduction reaction (ORR) has hampered the widespread use of polymer electrolyte fuel cells. We describe a family of non-precious metal catalysts that approach the performance of platinum-based systems at a cost sustainable for high-power fuel cell applications, possibly including automotive power. The approach uses polyaniline as a precursor to a carbon-nitrogen template for high-temperature synthesis of catalysts incorporating iron and cobalt. The most active materials in the group catalyze the ORR at potentials within ~60 millivolts of that delivered by state-of-the-art carbon-supported platinum, combining their high activity with remarkable performance stability for non-precious metal catalysts (700 hours at a fuel cell voltage of 0.4 volts) as well as excellent four-electron selectivity (hydrogen peroxide yield <1.0%).

Enhancing Hydrogen Evolution Activity in Water Splitting by Tailoring Li+-Ni(OH)2-Pt Interfaces

Abstract: Improving the sluggish kinetics for the electrochemical reduction of water to molecular hydrogen in alkaline environments is one key to reducing the high overpotentials and associated energy losses in water-alkali and chlor-alkali electrolyzers. We found that a controlled arrangement of nanometer-scale Ni(OH)(2) clusters on platinum electrode surfaces manifests a factor of 8 activity increase in catalyzing the hydrogen evolution reaction relative to state-of-the-art metal and metal-oxide catalysts. In a bifunctional effect, the edges of the Ni(OH)(2) clusters promoted the dissociation of water and the production of hydrogen intermediates that then adsorbed on the nearby Pt surfaces and recombined into molecular hydrogen. The generation of these hydrogen intermediates could be further enhanced via Li(+)-induced destabilization of the HO-H bond, resulting in a factor of 10 total increase in activity.

A Synthetic Nickel Electrocatalyst with a Turnover Frequency Above 100,000 s−1 for H2 Production

Abstract: Reduction of acids to molecular hydrogen as a means of storing energy is catalyzed by platinum, but its low abundance and high cost are problematic. Precisely controlled delivery of protons is critical in hydrogenase enzymes in nature that catalyze hydrogen (H(2)) production using earth-abundant metals (iron and nickel). Here, we report that a synthetic nickel complex, [Ni(P(Ph)(2)N(Ph))(2)](BF(4))(2), (P(Ph)(2)N(Ph) = 1,3,6-triphenyl-1-aza-3,6-diphosphacycloheptane), catalyzes the production of H(2) using protonated dimethylformamide as the proton source, with turnover frequencies of 33,000 per second (s(-1)) in dry acetonitrile and 106,000 s(-1) in the presence of 1.2 M of water, at a potential of -1.13 volt (versus the ferrocenium/ferrocene couple). The mechanistic implications of these remarkably fast catalysts point to a key role of pendant amines that function as proton relays.

Low-platinum and platinum-free catalysts for the oxygen reduction reaction at fuel cell cathodes

Abstract: Fuel cell reactions invariably involve an oxygen reduction reaction (ORR) at the cathode, which is one of the main rate-decreasing steps on platinum (Pt)-catalysts in the water formation reaction and energy conversion efficiency in polymer electrolyte membrane fuel cells (PEMFCs). The Pt scarcity and cost have led to the development of alternative catalyst materials for fuel cell applications. This paper reviews ORR catalysts with regard to their classification, mechanism, activity and performances. From conventional Pt-based catalysts to non-noble metal or bio-inspired catalysts, we show how significant progresses were made in ORR catalysis.

Recent progress in fluorescent and colorimetric chemosensors for detection of precious metal ions (silver, gold and platinum ions)

Abstract: Due to the wide range of applications and biological significance, the development of optical probes for silver, gold and platinum ions has been an active research area in the past few years. This tutorial review focuses on the recent contributions concerning the fluorescent or colorimetric sensors for these metal ions, and is organized according to their structural classifications (for Ag+ detection) and unique mechanisms between the sensors and metal ions (for Au3+ and Pt2+ detection).

Bioinspired molecular co-catalysts bonded to a silicon photocathode for solar hydrogen evolution

Abstract: The production of fuels from sunlight represents one of the main challenges in the development of a sustainable energy system. Hydrogen is the simplest fuel to produce and although platinum and other noble metals are efficient catalysts for photoelectrochemical hydrogen evolution, earth-abundant alternatives are needed for large-scale use. We show that bioinspired molecular clusters based on molybdenum and sulphur evolve hydrogen at rates comparable to that of platinum. The incomplete cubane-like clusters (Mo(3)S(4)) efficiently catalyse the evolution of hydrogen when coupled to a p-type Si semiconductor that harvests red photons in the solar spectrum. The current densities at the reversible potential match the requirement of a photoelectrochemical hydrogen production system with a solar-to-hydrogen efficiency in excess of 10%. The experimental observations are supported by density functional theory calculations of the Mo(3)S(4) clusters adsorbed on the hydrogen-terminated Si(100) surface, providing insights into the nature of the active site.

Catalytic activity trends of oxygen reduction reaction for nonaqueous Li-air batteries.

Abstract: We report the intrinsic oxygen reduction reaction (ORR) activity of polycrystalline palladium, platinum, ruthenium, gold, and glassy carbon surfaces in 0.1 M LiClO4 1,2-dimethoxyethane via rotating disk electrode measurements. The nonaqueous Li+-ORR activity of these surfaces primarily correlates to oxygen adsorption energy, forming a “volcano-type” trend. The activity trend found on the polycrystalline surfaces was in good agreement with the trend in the discharge voltage of Li-O2 cells catalyzed by nanoparticle catalysts. Our findings provide insights into Li+-ORR mechanisms in nonaqueous media and design of efficient air electrodes for Li-air battery applications.

Shape and composition-controlled platinum alloy nanocrystals using carbon monoxide as reducing agent.

Abstract: The shape of metal alloy nanocrystals plays an important role in catalytic performances. Many methods developed so far in controlling the morphologies of nanocrystals are however limited by the synthesis that is often material and shape specific. Here we show using a gas reducing agent in liquid solution (GRAILS) method, different Pt alloy (Pt-M, M = Co, Fe, Ni, Pd) nanocrystals with cubic and octahedral morphologies can be prepared under the same kind of reducing reaction condition. A broad range of compositions can also be obtained for these Pt alloy nanocrystals. Thus, this GRAILS method is a general approach to the preparation of uniform shape and composition-controlled Pt alloy nanocrystals. The area-specific oxygen reduction reaction (ORR) activities of Pt(3)Ni catalysts at 0.9 V are 0.85 mA/cm(2)(Pt) for the nanocubes, and 1.26 mA/cm(2)(Pt) for the nanooctahedra. The ORR mass activity of the octahedral Pt(3)Ni catalyst reaches 0.44 A/mg(Pt).

Platinum concave nanocubes with high-index facets and their enhanced activity for oxygen reduction reaction

Abstract: Platinum nanoparticles are widely used as the primary catalysts in a myriad of industrial processes such as CO/NOx oxidation in catalytic converters, nitric acid production, petroleum cracking, as well as hydrogen (or alcohol) oxidation and oxygen reduction reactions in fuel-cell technology. For most catalytic reactions, it has been shown that high-index planes, which are associated with large numbers of atomic steps, edges, and kinks hold the key to the enhancement of catalytic performance in terms of activity and/or selectivity. A number of protocols have been demonstrated for generating Pt nanoparticles enclosed by high-index facets, including those based on electrochemical reduction and heat treatment. For example, Sun and co-workers have reported the synthesis of tetrahexahedral (THH) Pt nanocrystals with high-index facets, such as {730}, {210}, and {520}, by applying a square-wave potential to polycrystalline Pt microspheres supported on a glassy carbon electrode. Although these Pt nanocrystals have been shown to have high catalytic activity, their sizes are still relatively too large and the method of preparation is rather limited in terms of production volume. It still remains a challenge to produce Pt nanocrystals with high-index facets by using a simple, scalable route based on wet chemical reduction. Over the past several years, kinetic control has been demonstrated as a simple and versatile approach to the shapecontrolled synthesis of noble-metal nanocrystals in the solution phase. In general, kinetic control can be achieved by: 1) substantially slowing down the formation rate of atoms, 2) using a weak reducing agent, 3) introducing an oxidation process, and 4) taking advantage of Ostwald ripening. When the concentration of metal atoms in the solution is low, the atoms tend to add to the edges and corners of a seed rather than the entire surface, thus leading to the formation of nanocrystals with thermodynamically unfavorable morphologies, including rods, plates, multipods, and dendritic structures. In recent years, nanocrystals with concave rather than flat faces have attracted attention because of their high-index facets. To this end, Zheng and co-workers have demonstrated the synthesis of concave Pd polyhedral nanocrystals with high electrocatalytic activity for formic acid oxidation. Mirkin and co-workers have also reported the synthesis of concave cubic Au nanocrystals, and demonstrated higher chemical activity compared to octahedra enclosed by lowindex {111} facets. Herein we report the first synthesis of Pt concave nanocubes enclosed by high-index facets including {510}, {720}, and {830} by slowly adding an aqueous NaBH4 solution and a mixture containing K2PtCl4, KBr, and Na2H2P2O7 into deionized water by using two syringe pumps. In this synthesis, the formation of a Pt pyrophosphato complex (that is formed by mixing K2PtCl4 and Na2H2P2O7) and the slow addition of this precursor by a syringe pump are believed to play a key role in the formation of Pt concave nanocubes. In this case, the seeds selectively overgrow from corners and edges, and the Br ion serves as a capping agent to block the growth of the h100i axis. The Pt concave nanocubes exhibited substantially enhanced specific activity (per unit surface area) relative to those of Pt nanocubes, cuboctahedra, and commercial Pt/C catalysts that are bounded by low-index facets such as {100} and {111} toward the oxygen reduction reaction (ORR), which is the ratedetermining step in a proton-exchangemembrane (PCM) fuel cell. In a typical synthesis, an aqueous NaBH4 solution and a mixture containing K2PtCl4, KBr, and Na2H2P2O7 were prepared separately and then injected simultaneously at an injection rate of 67 mLmin 1 by using two syringe pumps into deionized water maintained at 95 8C. The color of the solution immediately turned from light pink to black upon the addition of the reactant solutions, thus indicating rapid reduction of PtCl4 2 into elemental Pt by NaBH4. Figure 1a shows a typical transmission electron microscopy (TEM) image of the product that contains Pt nanocubes with a concave structure. [*] Dr. T. Yu, D. Y. Kim, Prof. H. Zhang, Prof. Y. Xia Department of Biomedical Engineering Washington University Saint Louis, MO 63130 (USA) E-mail: xia@biomed.wustl.edu D. Y. Kim Department of Chemical and Biomolecular Engineering (BK21 graduate program) Korea Advanced Institute of Science and Technology (KAIST) 335 Gwahangro, Yuseong-gu, Daejeon 305-701 (Korea)

A Highly Durable Platinum Nanocatalyst for Proton Exchange Membrane Fuel Cells: Multiarmed Starlike Nanowire Single Crystal

Abstract: Despite significant recent advances, the long-term durability of Pt catalyst at the cathode is still being recognized as one of the key challenges that must be addressed before the commercialization of proton exchange membrane fuel cells (PEMFCs). 2] The loss of Pt electrochemical surface area (ECSA) over time, because of corrosion of the carbon support and Pt dissolution/aggregation/Oswald ripening, is considered one of the major contributors to the degradation of fuel cell performance. Up to now, highly dispersed Pt nanoparticles (NPs, 2–5 nm) on carbon supports are still being widely used as the state-of-the-art commercial catalysts, and most reported studies are focused on nanoparticles of Pt. However, Pt with nanosized particle morphologies has high surface energies, thereby inducing severe Oswald ripening and/or grain growth during fuel cell operation. One-dimensional (1D) nanostructures of Pt, such as nanowires (NWs) and nanotubes (NTs), have been demonstrated to overcome the drawbacks of NPs in fuel cells, owning to their unique 1D morphologies. Yan et al. reported that unsupported Pt nanotubes exhibit much enhanced catalytic activity and durability as fuel cell cathode catalyst. Sun et al. and Zhou et al. reported the improved oxygen reduction reaction (ORR) activities of Pt NWs at the cathode under fuel cell operating conditions. However, up to now, the durability of Pt NW-based electrocatalysts has never been reported in the literature. Here we describe a new approach to address, for the first time, both the activity and durability issues by using carbonsupported multiarmed starlike Pt nanowires (starlike PtNW/ C) as electrocatalysts. Interestingly, the durability can be further improved by eliminating the carbon support, that is, using unsupported Pt nanowires as the cathode catalyst. As a result of their unique 1D morphology, the starlike Pt nanowire electrocatalyst can provide various advantages. First, the interconnected network consists of multiarmed, star-shaped 1D NWs with arm lengths of tens of nanometers which makes the Pt less vulnerable to dissolution, Ostwald ripening, and aggregation during fuel cell operation compared to Pt nanoparticles. Second, this network structure reduces the number of embedded electrocatalyst sites in the micropores of the carbon supports relative to those in nanogrannular Pt. Third, the mass transfer within the electrode can be effectively facilitated by networking the anisotropic morphology. Carbon-supported multiarmed starlike platinum nanowires were synthesized by the chemical reduction of a Pt precursor with formic acid in aqueous solution at room temperature and under ambient atmosphere. No surfactant, which is usually harmful for catalytic activities, was used in the experiments. Figure 1A and B show the representative scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images, respectively, of carbon-supported Pt nanowires at 40 wt % loading of Pt. It can be seen that the assynthesized Pt is nanostar-shaped, being composed of several short arms of Pt nanowires. The number of arms of each nanostar is found to vary ranging from several to over ten. Occasionally, single-armed nanowires standing on the carbon surface can also be observed. Diameter and length of the arms of starlike Pt nanowires are about 4 nm and 15 nm, respectively. More interestingly, from the connected atomic arrangement shown in the high-resolution TEM (HRTEM) images (see Figure S1 in the Supporting Information and the inset in Figure 1B), the nanostar is found to be a single crystal. The fast Fourier transform (FFT; see inset in Figure S1) of the original HRTEM image shows a dotted pattern, further proving that the nanostar is a single crystal. This indicates that the formation mechanism of the nanostar involves seeded growth rather than an aggregation of seeded particles or an assembly process of the nanowires. The X-ray diffraction (XRD) pattern (Figure S2) confirms that the carbon-supported Pt nanowires are crystallized in a face-centered-cubic (fcc) structure similar to bulk Pt, which is consistent with the HRTEM investigations. We believe that the growth of the multiarmed starlike PtNWs on carbon black supports follows a similar process to that for Pt NWs on other supports. Typically, Pt nuclei are first formed in solution through the reduction of H2PtCl6 by HCOOH, and they deposit on the surface of carbon spheres. The freshly formed nuclei act as the sites for further nucleation through the continual absorption and reduction of Pt(IV) ions leading to the formation of particle seeds. For fcc structures, the sequence of surface energies is g{111} < g{100} [*] Dr. S. Sun, Dr. G. Zhang, Dr. D. Geng, Y. Chen, R. Li, Prof. X. Sun Department of Mechanical and Materials Engineering The University of Western Ontario London, Ontario N6A 5B9 (Canada) Fax: (+ 1)519-661-3020 E-mail: xsun@eng.uwo.ca

Metal–Support Interactions between Nanosized Pt and Metal Oxides (WO3 and TiO2) Studied Using X-ray Photoelectron Spectroscopy

Abstract: Platinum nanoparticles have been selectively deposited on composites of titanium oxide-carbon and tungsten oxide-carbon. Selectivity of the deposition made it possible to investigate changes in electronic properties of both platinum and oxide support, induced by the so-called strong metal–support interactions (SMSI). X-ray photoelectron spectroscopy (XPS) was used, and changes in binding energy of Pt 4f, Ti 2p, and W 4f core-levels and Pt 4f peak asymmetry were determined. These parameters allowed us to state the changes in local electron density, when Pt is deposited on oxide support. In all cases the binding energy of the Pt 4f signal for platinum deposited on an oxide support was significantly lower in comparison to samples where Pt was solely supported onto carbon. The increase in Pt 4f XPS signal asymmetry was observed. This suggests an increased electron density on Pt. No electron donor could be identified from the analysis of the oxide supports. To explain the observed data, at least two effects mu...

Platinum-based electrocatalysts with core-shell nanostructures.

Abstract: The development of low-temperature hydrogen fuel cells for automotive applications has witnessed tremendous progress over the past several years, and the total distance driven by fuel-cell-operated vehicles exceeded the million-mile mark in 2009. New cell modules continue to reduce the cost, volume, and weight of fuel cells at a rapid pace. One driving force for this fast development lies in the great progress made in making active cathode catalysts for proton exchange membrane fuel cells (PEMFCs). Improvement of the activity and durability of electrocatalysts for the oxygen reduction reaction (ORR) remains a key research area for the creation of future generations of PEMFCs for automotive applications. As there is still no viable alternative to the replacement of catalysts made of Pt group metals (PGMs), the need of low cost, highly active, and durable fuel-cell electrodes heightens the design criteria. In this regard, multicomponent nanostructures can play important roles in the design of ORR catalysts with high activity and durability. 2] Core–shell or core–shell-like nanostructures are a convenient way to build multifunctionality into the electrocatalysts of metallic nanoparticles, which have a typical average diameter between 2 and 5 nm. With the increasing complexity of core–shell nanoparticles, the study of structure–property relationships becomes even more important and essential than before in the design of new catalysts. Sun and co-workers recently reported a synthesis of multimetallic core–shell nanoparticles, which is the latest of several recent investigations into the synthesis and electrocatalytic properties of multimetallic core–shell nanoparticles. Spherical Pd/Au and Pd/Au/FePt core–shell nanoparticles were synthesized in octadecene using oleylamine and oleic acid as the capping agents. The structures were characterized by high-resolution transmission electron microscopy (TEM) and aberrationcorrected high-angle annular dark-field scanning TEM (HAADF-STEM). The core–shell nanoparticles were fairly monodisperse in size and had overall diameters of about 7 nm for Pd/Au bimetallic core–shell nanoparticles. Furthermore, 11 nm Pd/Au/FePt multimetallic core–shell nanoparticles were also readily produced by using a similar solution-phase synthesis. The size of these bimetallic or multimetallic core– shell nanoparticles can also be easily tuned within a certain range by changing the reaction conditions. To date, reports on the synthesis of well-defined multimetallic core–shell nanoparticles with sizes below about 10 nm are still relatively uncommon. In principle, the synthesis of multimetallic core–shell nanoparticles or core–shelllike heterogeneous nanostructures including dendrite, particle-on-particle, raspberry, or flower, however, is usually thermodynamically favored. The synthesis is possible as the heterogeneous nucleation of second metal component on the existing nanoparticle seed or core has a lower critical energy barrier, that is, the overall excess free energy, than the homogenous nucleation. Depending on the overall excess energy, which is largely related to the surface and interfacial energy terms, and the strain energy because of lattice mismatch at the interface, three different major types of nanostructures form, namely, layer-by-layer, island-on-wetting layer, and island growth modes (Figure 1). When the interfacial structures are not known or cannot be well defined, or the shape of the nanostructure is important, a generic description based on the morphology, such as raspberry, nanoflower, dendrite, particle-on-particle, or core–shell nanoparticle, is often used. In the solution-phase synthesis and with the use of capping ligands, metallic cores can exist in ordered or disordered forms, and can be formed from metal alloys (Figure 1). Heterogeneous deposition of a metal or metal alloy on the core occurs through one of the three growth modes to form core–shell or core–shell-like nanostructures. So why have relatively few multimetallic core–shell nanoparticles with sizes less than 10 nm been reported? Besides the intrinsic challenges in the synthesis, one important reason perhaps lies in the difficulty of characterizing multimetallic core–shell nanoparticles in detail. Yang and coworkers have previously reported shape-controlled Pt/Pd core–shell nanoparticles. Pt/Pd core–shell nanocubes, cuboctahedra, and octahedra could be made by using Pt cube seed crystals. High-resolution TEM (HRTEM) images revealed [*] Prof. Dr. H. Yang Department of Chemical Engineering University of Rochester Gavett Hall 206, Rochester, NY 14627 (USA) Fax: (+ 1)585-273-1348 E-mail: hongyang@che.rochester.edu Homepage: http://www.che.rochester.edu/~hongyang/

Switching on luminescence by the self-assembly of a platinum(II) complex into gelating nanofibers and electroluminescent films.

Abstract: Triplet emitters based on platinum(II) complexes have gained major attention in recent times. They can form aggregates or excimers, causing shifts in the emitted wavelengths and affecting the photoluminescence quantum yields (PLQYs). Even though this effect can be exploited for the construction of white organic light emitting diodes (WOLEDs), it is disadvantageous for applications where color purity is desirable. Terpyridine ligands and their N^C^N and N^N^C analogues have been coordinated to platinum(II), leading to neutral, mono-, or doubly charged species, some of which display bright luminescence. They can form supramolecular structures, such as nanowires, nanosheets, and polymeric mesophases, with interesting optical properties. For low-molecular-weight organoor hydrogelators, the operating mechanism of gelation has been recognized as a supramolecular effect, where the constituting fibers, usually of microscale lengths and nanoscale diameters, are formed in solution predominantly by unidirectional self-assembly. The entanglement of filaments gives a network that entraps solvent molecules within the compartments. As supramolecular gels provide fibrous aggregates with long-range order, they could be of interest in the fields of optoelectronic devices and sensors. In this context, organometallic gelators can display metal–metal interactions that influence their properties. Herein we present a straightforward one-pot synthesis of neutral, soluble platinum(II) coordination compounds bearing a dianionic tridentate terpyridine-like ligand. The coordination of an alkyl pyridine ancillary moiety to the 2,6bis(tetrazolyl)pyridine complex allowed us to enhance the solubility and thus the processability. The synthetic approach involved mild reaction conditions that involved a nonnucleophilic base and an adequate inorganic platinum(II) precursor. Moistureand oxygen exclusion were not required, and the product was easily purified by repeated precipitation (Scheme 1). The emission intensity of the complex attained a

Metal nanoparticles with high catalytic activity in degradation of methyl orange: An electron relay effect

Abstract: Gold, silver and platinum nanoparticles have been synthesized following a green approach by reducing the corresponding salt using tannic acid as reducing agent at room temperature in aqueous medium. The reaction is instantaneous and the average diameter of the particles formed is around 10 nm in all the three cases as measured by TEM. These nanoparticles have been used as a catalyst for the degradation of methyl orange in the presence of sodium borohydride (NaBH4). Silver nanoparticles have a drastic catalytic effect as compared to gold or platinum nanoparticles on the degradation of methyl orange in the presence of sodium borohydride. From the kinetic data it is concluded that the rate constant follows the order: kAg nanoparticles ≫ kAu nanoparticles > kPt nanoparticles ≫ kuncatalyzed reaction. The high catalytic effect of silver nanoparticles has been attributed to its low value of work function as compared to Au and Pt. The uncatalyzed reaction does not show any decrease in the absorbance value within the given experimental time due to the large kinetic barrier, i.e. high activation energy. Decrease in absorbance value for uncatalyzed reaction is observed after nearly 48 h that too at a very high concentration of reducing agent, thereby indicating that reaction is extremely slow and reduction of methyl orange is thermodynamically feasible.

Structural Changes of γ-Al2O3-Supported Catalysts in Hot Liquid Water

Abstract: The structural changes of γ-Al2O3, Ni/γ-Al2O3, and Pt/γ-Al2O3 catalysts under aqueous phase reforming conditions (liquid water at 200 °C and autogenic pressure) are examined over the course of 10 h. The changes are characterized by X-ray diffraction, NMR spectroscopy, N2 physisorption, pyridine adsorption followed by IR spectroscopy, and electron microscopy. It is demonstrated that γ-alumina is converted into a hydrated boehmite (AlOOH) phase with significantly decreased acidity and surface area. For metal-free γ-alumina, the transformation is completed within 10 h, whereas the presence of nickel and platinum particles significantly retards the formation of boehmite. In the beginning of the treatment, the surface area of γ-alumina increases, suggesting surface pitting and formation of small boehmite particles on the surface of γ-alumina. This process is followed by the formation of a compact crystalline boehmite phase. It is proposed that the metal particles affect the kinetics of this transformation by b...

Polyaniline-functionalized carbon nanotube supported platinum catalysts.

Abstract: Electrocatalytically active platinum (Pt) nanoparticles on a carbon nanotube (CNT) with enhanced nucleation and stability have been demonstrated through introduction of electron-conducting polyaniline (PANI) to bridge the Pt nanoparticles and CNT walls with the presence of platinum−nitride (Pt−N) bonding and π−π bonding. The Pt colloids were prepared through ethanol reduction under the protection of aniline, the CNT was dispersed well with the existence of aniline in the solution, and aniline was polymerized in the presence of a protonic acid (HCl) and an oxidant (NH4S2O8). The synthesized PANI is found to wrap around the CNT as a result of π−π bonding, and highly dispersed Pt nanoparticles are loaded onto the CNT with narrowly distributed particle sizes ranging from 2.0 to 4.0 nm due to the polymer stabilization and existence of Pt−N bonding. The Pt−PANI/CNT catalysts are electroactive and exhibit excellent electrochemical stability and therefore promise potential applications in proton exchange membrane...

Mechanism of the Catalytic Oxidation of Glycerol on Polycrystalline Gold and Platinum Electrodes

Abstract: This paper addresses the oxidation mechanism of glycerol on Au and Pt electrodes under different pH conditions. Intermediates and/or reaction products were detected by using an online high-performance liquid chromatography technique (for soluble products) and online electrochemical mass spectrometry (for CO2). In alkaline media, the main product of glycerol oxidation on the Pt electrode is glyceric acid produced via glyceraldehyde. Glyceric acid is the primary oxidation product on the Au electrode, which is further oxidized to glycolic acid and formic acid at high potentials (≥0.8 V), yielding high current densities. As the pH of the solution is lowered, the glycerol oxidation becomes significantly more sluggish on both Au and Pt electrodes, which results in glyceraldehyde being the main oxidation product under neutral conditions, especially on gold. In acidic solutions, only the Pt electrode shows catalytic activity with a relatively low conversion rate, mainly to glyceraldehyde. At positive potentials corresponding to the formation of a Pt surface oxide, the PtOx surface oxide catalyzes the conversion of glyceraldehyde finally to formic acid and CO2, but only under acidic conditions. Gold catalyzes glycerol oxidation only under alkaline conditions, in contrast to a “real catalyst,” that is, platinum, which catalyzes glycerol oxidation over the entire pH range.

Catalytic Conversion of Guaiacol Catalyzed by Platinum Supported on Alumina: Reaction Network Including Hydrodeoxygenation Reactions

Abstract: The conversion of guaiacol catalyzed by Pt/γ-Al2O3 in the presence of H2 was investigated with a flow reactor at 573 K and 140 kPa. Dozens of reaction products were identified, with the most abunda...

Nitrogen-promoted self-assembly of N-doped carbon nanotubes and their intrinsic catalysis for oxygen reduction in fuel cells.

Abstract: Nitrogen atoms were found to exhibit a strong ability to promote the self-assembly of nitrogen-doped carbon nanotubes (NCNTs) from gaseous carbons, without an assistance of metal atoms. On the basis of this discovery, pure metal-free CNTs with a nitrogen-doping level as high as 20 atom % can be directly synthesized using melamine as a C/N precursor. This offers a novel pathway for carbon nanotube synthesis. Furthermore, the metal-free and intact characteristics of the NCNT samples facilitate a clear verification of the intrinsic catalytic ability of NCNTs. The results show that the NCNTs intrinsically display excellent catalytic activity for oxygen reduction in fuel cells, comparable to traditional platinum-based catalysts. More notably, they exhibit outstanding stability, selectivity, and resistance to CO poisoning, much superior to the platinum-based catalysts.

Thirty years of platinum single crystal electrochemistry

Abstract: The electrochemistry of platinum single crystals is historically reviewed. After a brief revision of historical results dating before the publication of the landmark experiment by J. Clavilier of the flame annealing in 1980, the controversy introduced by this experiment into the surface electrochemistry community is described. Questions about the structure and composition of the platinum surface after the flame annealing and their implications on the characteristic voltammetry of platinum single crystal electrodes were slowly answered in the years that followed the first introduction of this methodology. One of the last questions to be solved was that about the nature of the chemical species responsible for the charge transfer process that leads to the so-called unusual features in the voltammogram. This was solved with the charge displacement experiment. Nowadays, a great deal of knowledge has been gathered about the structure of the interphase between platinum electrodes and electrolytic solutions and also about the electrocatalytic behaviour of platinum surfaces. State-of-the-art information about platinum electrochemistry is provided, with emphasis on results from our group, especially those obtained with a thermodynamic analysis, involving either constant or variable temperatures and with the laser-induced temperature jump method.

Copper Oxide Nanoparticles: Synthesis, Characterization and Their Antibacterial Activity

Abstract: Copper oxide nanoparticles were prepared by electrochemical reduction method using tetra butyl ammonium bromide (TBAB) as structure directing agent in an organic medium viz. tetra hydro furan (THF) and acetonitrile (ACN) in 4:1 ratio by optimizing current density and molar concentration of the ligand. The reduction process takes place under inert atmosphere of nitrogen over a period of 2 h. Such nanoparticles are prepared using simple electrolysis cell in which the sacrificial anode as a commercially available copper metal sheet and platinum (inert) sheet act as a cathode. The parameters such as current density, solvent polarity, distance between electrodes, and concentration of stabilizers are used to control the size of nanoparticles. The synthesized copper oxide nanoparticles were characterized by using UV–Visible, FT-IR, XRD, SEM–EDS and TEM analysis techniques. The nanoparticles were tested for antibacterial activity against human pathogens like Escherichia coli (E. coli) and Staphylococcus strains and which was proved to be excellent.

Enhancement of the performance of a platinum nanocatalyst confined within carbon nanotubes for asymmetric hydrogenation.

Abstract: Enhancement of the Performance of a Platinum Nanocatalyst Confined within Carbon Nanotubes for Asymmetric Hydrogenation

Molecular Electrocatalysts for the Oxidation of Hydrogen and the Production of Hydrogen – The Role of Pendant Amines as Proton Relays

Abstract: Electrocatalysts for efficient conversion between electricity and chemical bonds will play a vital role in future systems for storage and delivery of energy. Our research on functional models of hydrogenase enzymes uses nickel and cobalt, abundant and inexpensive metals, in contrast to platinum, a precious metal used in fuel cells. A key feature of our research is a focus on the use of pendant amines incorporated into diphosphine ligands. These pendant amines function as proton relays, lowering the barrier to proton transfers to and from the catalytically active metal site. The hydride acceptor ability of metal cations, along with the basicity of pendant amines, are key thermochemical values that determine the thermodynamics of addition of H2 to a metal complex with a pendant amine incorporated into its ligand. Nickel catalysts for oxidation of H2 have turnover frequencies up to 50 s-1 (at 1 atm H2 and room temperature). Nickel and cobalt catalysts for production of H2 by reduction of protons are studied, one of which has a turnover frequency over 1000 s-1. This material is based upon work supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the US Department of Energy, Officemore » of Science, Office of Basic Energy Sciences.« less

A new type of transparent and low cost counter-electrode based on platinum nanoparticles for dye-sensitized solar cells

Abstract: Here we report on the fabrication of a new low-cost transparent cathode based on platinum nanoparticles prepared by a bottom-up synthetic approach. Scanning Electron Microscope (SEM) images showed the platinum nanoparticles homogeneously distributed on a fluorine doped tin oxide conductive glass surface. We demonstrated that, with such a type of cathode, the solar energy conversion efficiency is the same as that obtained with a platinum sputtered counter-electrode, and is more than 50% greater than that obtained with a standard electrode, i.e. one prepared by chlorine platinum acid thermal decomposition, in similar working conditions. Using a special back-reflecting layer of silver, we improved upon the performance of a counter-electrode based on platinum sputtering, achieving an overall solar conversion efficiency of 4.75% at 100 mW cm−2 (AM 1.5) of simulated sunlight.

The Role of Bridge‐Bonded Adsorbed Formate in the Electrocatalytic Oxidation of Formic Acid on Platinum

Abstract: The oxidation of formic acid (HCOOH) on platinum electrodes has been extensively investigated as a model electrocatalytic reaction. It is generally accepted that HCOOH is oxidized to CO2 through a dual-pathway mechanism: one pathway (the main pathway) involves a fast reaction via a reactive intermediate and the second pathway includes a step in which a poisoning species is formed. This species, which is oxidized to CO2 at high potentials, has been identified as adsorbed CO, which is formed by dehydration of HCOOH. Adsorbed hydroxycarbonyl (COOHads) has long been assumed to be the reactive intermediate in the main pathway, but the spectroscopic detection of this species has not been reported to date. By using surface-enhanced infrared absorption spectroscopy in the attenuated total reflection mode (ATRSEIRAS), Miki et al. observed that formate is adsorbed in a bridge-bonded configuration on Pt electrodes during HCOOH oxidation. On the basis of systematic time-resolved ATR-SEIRAS analysis of the oxidation dynamics, Samjesk et al. suggested that adsorbed formate (HCOOads) is a reactive intermediate in the main pathway and its decomposition to CO2 is the rate-determining step (rds). The adsorbed formate is in equilibrium with HCOOH in the bulk solution and the reaction pathway (formate pathway) can be represented by Equation (1)