Iron catalysts for selective anti-Markovnikov alkene hydrosilylation using tertiary silanes

Alkene hydrosilylation, the addition of a silicon hydride (Si-H) across a carbon-carbon double bond, is one of the largest-scale industrial applications of homogeneous catalysis and is used in the commercial production of numerous consumer goods. For decades, precious metals, principally compounds of platinum and rhodium, have been used as catalysts for this reaction class. Despite their widespread application, limitations such as high and volatile catalyst costs and competing side reactions have persisted. Here, we report that well-characterized molecular iron coordination compounds promote the selective anti-Markovnikov addition of sterically hindered, tertiary silanes to alkenes under mild conditions. These Earth-abundant base-metal catalysts, coordinated by optimized bis(imino)pyridine ligands, show promise for industrial application.     

Platinum catalysts for the high-yield oxidation of methane to a methanol derivative

Platinum catalysts are reported for the direct, low-temperature, oxidative conversion of methane to a methanol derivative at greater than 70 percent one-pass yield based on methane. The catalysts are platinum complexes derived from the bidiazine ligand family that are stable, active, and selective for the oxidation of a carbon-hydrogen bond of methane to produce methyl esters. Mechanistic studies show that platinum(II) is the most active oxidation state of platinum for reaction with methane, and are consistent with reaction proceeding through carbon-hydrogen bond activation of methane to generate a platinum-methyl intermediate that is oxidized to generate the methyl ester product.     

Active nonmetallic Au and Pt species on ceria-based water-gas shift catalysts

Traditional analysis of reactions catalyzed by supported metals involves the structure of the metallic particles. However, we report here that for the class of nanostructured gold- or platinum-cerium oxide catalysts, which are active for the water-gas shift reaction, metal nanoparticles do not participate in the reaction. Nonmetallic gold or platinum species strongly associated with surface cerium-oxygen groups are responsible for the activity.     

Alkali-stabilized Pt-OHx species catalyze low-temperature water-gas shift reactions

We report that alkali ions (sodium or potassium) added in small amounts activate platinum adsorbed on alumina or silica for the low-temperature water-gas shift (WGS) reaction (H(2)O + CO → H(2) + CO(2)) used for producing H(2). The alkali ion-associated surface OH groups are activated by CO at low temperatures (~100°C) in the presence of atomically dispersed platinum. Both experimental evidence and density functional theory calculations suggest that a partially oxidized Pt-alkali-O(x)(OH)(y) species is the active site for the low-temperature Pt-catalyzed WGS reaction. These findings are useful for the design of highly active and stable WGS catalysts that contain only trace amounts of a precious metal without the need for a reducible oxide support such as ceria.     

Production of syngas by direct catalytic oxidation of methane

The reaction between methane and oxygen over platinum and rhodium surfaces in metalcoated ceramic monoliths can be made to produce mostly hydrogen and carbon monoxide (greater than 90% selectivity for both) with almost complete conversion of methane and oxygen at reaction times as short as 10(-3) seconds. This process has great promise for conversion of abundant natural gas into liquid products such as methanol and hydrocarbons, which can be easily transported from remote locations. Rhodium was considerably superior to platinum in producing more H(2) and less H(2)O, which can be explained by the known chemistry and kinetics of reactants, intermediates, and products on these surfaces.     

Combinatorial electrochemistry: A highly parallel, optical screening method for discovery of better electrocatalysts

Combinatorial screening of electrochemical catalysts by current-voltage methods can be unwieldy for large sample sizes. By converting the ions generated in an electrochemical half-cell reaction to a fluorescence signal, the most active compositions in a large electrode array have been identified. A fluorescent acid-base indicator was used to image high concentrations of hydrogen ions, which were generated in the electrooxidation of methanol. A 645-member electrode array containing five elements (platinum, ruthenium, osmium, iridium, and rhodium), 80 binary, 280 ternary, and 280 quaternary combinations was screened to identify the most active regions of phase space. Subsequent "zoom" screens pinpointed several very active compositions, some in ternary and quaternary regions that were bounded by rather inactive binaries. The best catalyst, platinum(44)/ruthenium(41)/osmium(10)/iridium(5) (numbers in parentheses are atomic percent), was significantly more active than platinum(50)/ruthenium(50) in a direct methanol fuel cell operating at 60 degreesC, even though the latter catalyst had about twice the surface area of the former.     

High-performance electrocatalysts for oxygen reduction derived from polyaniline, iron, and cobalt

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%).     

Electronic structure and catalytic behavior of tungsten carbide

Tungsten carbide has been shown to be an effective catalyst for a number of reactions that are readily catalyzed by platinum, but not at all by tungsten, and it was speculated that this behavior is due to changes in the electron distribution when carbon is added to tungsten. A test of this hypothesis, made by measuring the valence band x-ray photoelectron spectrum of tungsten carbide and comparing it with the spectra of tungsten and platinum, shows that, near the Fermi level, the electronic density of states of tungsten carbide more nearly resembles that of platinum than that of tungsten.     

Reactivity of the gold/water interface during selective oxidation catalysis

The selective oxidation of alcohols in aqueous phase over supported metal catalysts is facilitated by high-pH conditions. We have studied the mechanism of ethanol and glycerol oxidation to acids over various supported gold and platinum catalysts. Labeling experiments with (18)O(2) and H(2)(18)O demonstrate that oxygen atoms originating from hydroxide ions instead of molecular oxygen are incorporated into the alcohol during the oxidation reaction. Density functional theory calculations suggest that the reaction path involves both solution-mediated and metal-catalyzed elementary steps. Molecular oxygen is proposed to participate in the catalytic cycle not by dissociation to atomic oxygen but by regenerating hydroxide ions formed via the catalytic decomposition of a peroxide intermediate.     

Rare-earth oxides of manganese and cobalt rival platinum for the treatment of carbon monoxide in auto exhaust

The perovskite-like compounds RE(1-X)Pb(5)MnO(3) and RECoO(3), where RE (rare earth) is lanthanum, praseodymium, or neodymium, are active catalysts for the oxidation of carbon monoxide. Crushed single crystals of these compounds compare favorably with commercial platinum catalysts in initial activity and lifetime. Therefore, these compounds are promising substitutes for platinum in devices for the catalytic treatment of auto exhaust.     

Electrolytic univalent reduction of oxygen in aqueous solution demonstrated with superoxide dismutase

The superoxide anion, generated electrolytically at a platinum electrode in buffered aqueous solution, was detected by its ability to cause the oxidation of epinephrine to adrenochrome. The rate of electrolytic oxidation of epinephrine varied with the applied potential in a manner reminiscent of an oxygen reduction half wave. This oxidation of epinephrine was dependent upon the presence of oxygen and was completely inhibitable by superoxide dismutase. It may be concluded that superoxide radicals, generated at the electrode, diffuse into the solution to an extent which allows reaction with small molecules such as epinephrine or with enzymes such as superoxide dismutase.     

Rare-Earth manganites: surface-segregated platinum increases catalytic activity

Crushed and etched lanthanum lead manganite (La(0.7)Pb(0.3)MnO(3)) crystals containing as little as 0.005 atomic percent platinum have significantly higher catalytic activity than free platinum crystals. This higher activity is due to an almost 100-fold segregation of platinum on the surface. The surface platinum concentration found, 0.5 atomic percent, is sufficient to account for the enhanced activity provided that the platinum has the same activity as platinum supported on alumina.     

Oscillatory kinetics and spatio-temporal self-organization in reactions at solid surfaces

Chemical reactions far from equilibrium on solid surfaces may exhibit typical phenomena of nonlinear dynamics, as exemplified by the catalytic oxidation of carbon monoxide on a platinum(110) single-crystal surface. Depending on the external parameters (temperature and partial pressures of the reactants), the temporal variation of the reaction rate may become oscillatory or even chaotic. In a parallel way, the concentration distributions of the adsorbed species on the surface form spatio-temporal patterns including propagating and standing waves, rotating spirals, as well as irregular and rapidly changing structures denoted "chemical turbulence."     

Shape-Controlled Synthesis of Colloidal Platinum Nanoparticles

The shapes and sizes of platinum nanoparticles were controlled by changes in the ratio of the concentration of the capping polymer material to the concentration of the platinum cations used in the reductive synthesis of colloidal particles in solution at room temperature. Tetrahedral, cubic, irregular-prismatic, icosahedral, and cubo-octahedral particle shapes were observed, whose distribution was dependent on the concentration ratio of the capping polymer material to the platinum cation. Controlling the shape of platinum nanoparticles is potentially important in the field of catalysis.     

Stabilization of platinum oxygen-reduction electrocatalysts using gold clusters

We demonstrated that platinum (Pt) oxygen-reduction fuel-cell electrocatalysts can be stabilized against dissolution under potential cycling regimes (a continuing problem in vehicle applications) by modifying Pt nanoparticles with gold (Au) clusters. This behavior was observed under the oxidizing conditions of the O2 reduction reaction and potential cycling between 0.6 and 1.1 volts in over 30,000 cycles. There were insignificant changes in the activity and surface area of Au-modified Pt over the course of cycling, in contrast to sizable losses observed with the pure Pt catalyst under the same conditions. In situ x-ray absorption near-edge spectroscopy and voltammetry data suggest that the Au clusters confer stability by raising the Pt oxidation potential.     

Controlled acceleration and inhibition of bergman cyclization by metal chlorides

The Bergman cyclization has been the subject of renewed interest with the discovery of naturally occurring enediyne-based antitumor agents that cleave DNA by means of an aromatic diradical. These natural substrates have a means to trigger this cycloaromatization process. Control of this reaction by substrate modification would allow aromatic diradicals to be generated selectively. In the studies presented here it is disclosed that the Bergman cyclization of 1,2-bis(diphenyl phosphinoethynyl) benzene was accelerated by a factor of >30,000 by the addition of palladium(II) chloride or platinum(II) chloride and was inhibited by the addition of mercury(II) chloride.     

NO3-和NO2-在有机锡修饰电极上的电化学研究

通过循环伏安法、旋转圆盘电极等方法研究了有机锡化合物在铂电极上的电化学行为，以及吸附有机锡化合物的铂电校对硝酸根和亚硝酸根的催化还原性能和pH的影响。结果表明二乙基锡在铂电极上的吸附对N03^-和N02^-的还原具有催化作用。还原时过电位减少，根据其还原过程的电化学行为，提出了可能的催化机理。同时通过催化过程动力学分析由实验得到了催化速率常数。     

Platinum-like behavior of tungsten carbide in surface catalysis

Tungsten carbide catalyzes the formation of water from hydrogen and oxygen at room temperature, the reduction of tungsten trioxide by hydrogen in the presence of water, and the isomerization of 2,2-dimethylpropane to 2-methylbutane. This catalytic behavior, which is typical of platinum, is not exhibited at all by tungsten. The surface electronic properties of the latter are therefore modified by carbon in such a way that they resemble those of platinum.     

Mixed-phase oxide catalyst based on Mn-mullite (Sm, Gd)Mn2O5 for NO oxidation in diesel exhaust

Oxidation of nitric oxide (NO) for subsequent efficient reduction in selective catalytic reduction or lean NO(x) trap devices continues to be a challenge in diesel engines because of the low efficiency and high cost of the currently used platinum (Pt)-based catalysts. We show that mixed-phase oxide materials based on Mn-mullite (Sm, Gd)Mn(2)O(5) are an efficient substitute for the current commercial Pt-based catalysts. Under laboratory-simulated diesel exhaust conditions, this mixed-phase oxide material was superior to Pt in terms of cost, thermal durability, and catalytic activity for NO oxidation. This oxide material is active at temperatures as low as 120°C with conversion maxima of ~45% higher than that achieved with Pt. Density functional theory and diffuse reflectance infrared Fourier transform spectroscopy provide insights into the NO-to-NO(2) reaction mechanism on catalytically active Mn-Mn sites via the intermediate nitrate species.