Promotional effect of gold added to palladium supported on a new mesoporous TiO2 for total oxidation of volatile organic compounds

Gold and palladium were supported on a mesoporous TiO₂ for total oxidation of volatile organic compounds (VOCs). Mesoporous high surface area titania support was synthesised using of Ti(OC₂H₅)₂ in the presence of CTMABr surfactant. After removing the surfactant molecules, 0.5 or 1.5 wt% of palladium and 1 wt% of gold were precipitated on the support by, respectively, wet impregnation and deposition–precipitation methods. The activity for toluene and propene total oxidation of the prereduced samples follows the same order: 0.5%Pd-1%Au/TiO₂ > 1.5%Pd/TiO₂ > 0.5%Pd/TiO₂ > 1%Au-0.5%Pd/TiO₂ > 1%Au/TiO₂ > TiO₂. Moreover, a catalytic comparison with samples based on a conventional TiO₂, shows the catalytic advantage of the mesoporous TiO₂ support. The promotional effect of gold added to palladium could be partly explained by small metallic particles (TEM), but meanly by metallic particles made up of Au-rich core with a Pd-rich shell. Moreover, the hydrogen TPR profile of 0.5%Pd-1%Au/TiO₂ shows only the signal attributed to small PdO particles. Gold also implies a protecting effect of the support under reduction atmosphere. Operando diffuse reflectance infrared fourier transform (DRIFT) spectroscopy was carried on and allowed to follow the VOCs oxidation and the formation of coke molecules, but also a metallic electrodonor effect to the adsorbed molecule which increases in the same order as the activity for oxidation reaction. The presence of coke after test was also shown by DTA–TGA by exothermic signals between 300 and 500 °C and by EPR (g = 2.003).     

Bimetallic gold/palladium catalysts for the selective liquid phase oxidation of glycerol

A new methodology for the preparation of single phase bimetallic Au–Pd on activated carbon (AC) has been recently developed and now used for preparing Au/Pd catalysts at different atomic ratio. The bimetallic catalysts have been tested in the liquid phase oxidation on glycerol in water using oxygen as the oxidant and compared with monometallic Au and Pd catalysts. We observed that strong synergistic effect is present in a large range of Au/Pd ratio, being maximized for Au₉₀–Pd₁₀ composition. Gold-rich composition showed an increased durability compared to palladium-rich alloy.     

Combustion of methane over palladium/zirconia: effect of Pd-particle size and role of lattice oxygen

The catalytic combustion of methane over palladium/zirconia catalyst prepared by oxidation and subsequent reduction of Pd/Zr glassy metals has been investigated with special emphasis on the influence of the catalyst structure (particle size and specific surface area) on the catalytic performance and the impact of a redox mechanism on the product formation. The reaction of 1% methane and 4% oxygen (balance of He) in a fixed-bed microreactor was found to be strongly dependent on the particle size of palladium, which was controlled by appropriate reduction before catalytic testing. Pre-reduction of PdO resulted in an enhanced activity compared to the unreduced catalysts. The structural changes induced upon reduction were accompanied by altered physico-chemical properties, evidenced by different behaviors in the decomposition of PdO and the reduction of PdO by methane. The correlation established between catalytic performance and the rate of reduction of PdO by methane led to the postulation of a redox mechanism, involving the reaction of methane with the active palladium oxide phase and subsequent reoxidation of metallic Pd by oxygen, which was independently confirmed by the use of ¹⁸O labeled catalysts and pulse methods.     

Research on unsupported nanoporous gold catalyst for CO oxidation

Nanoporous gold (NPG), a novel unsupported gold catalyst prepared by dealloying, exhibits exceptional catalytic activity for CO oxidation. Systematic studies were carried out on this new catalytic system, including the active sites of catalysts, the reaction kinetics, and activity dependence as functions of space velocity and temperature. Our results show strong evidence that metallic gold atoms on NPG are the intrinsic active sites at which the reaction of CO with O₂ occurs. The kinetic study found that the reaction rate of CO oxidation on unsupported NPG depends significantly on CO concentration but only slightly on O₂ concentration. We suggest that CO adsorption plays a decisive role in CO oxidation on NPG as the rate-limiting step. By completely ruling out the support influence, our findings provide considerable insight into the role of gold catalysts.     

Effect of Particle Size on Monometallic and Bimetallic (Au,Pd)/C on the Liquid Phase Oxidation of Glycerol

The influence of metal particle size of monometallic and bimetallic supported catalysts (Au, Pd, Au–Pd)/C was studied using as a model reaction the liquid phase oxidation of glycerol. By tuning the metal particle size from 2 to 16 nm a progressive decrease of activity and simultaneously an increase in the selectivity to sodium glycerate was observed. Moreover, the influence of the temperature was studied and it was found that by increasing the temperature, only with a large particle size the formed glycerate was retained and not over-oxidized to tartronate.     

Use of renewables for the production of chemicals: Glycerol oxidation over carbon supported gold catalysts

As a renewable feedstock and due to its high functionality glycerol is an attractive reactant for the production of a large number of valuable compounds. We report on an environmentally friendly alternative to produce chemicals from the glycerol oxidation, which are currently produced either by stoichiometric oxidation processes or by enzymatic routes. We investigate the heterogeneously catalyzed liquid-phase oxidation of glycerol with carbon supported gold catalysts. The prepared nanosized gold catalysts are highly active, so that the reaction could be performed under atmospheric pressure. The influence of the preparation method of the catalysts has been investigated. Moreover, the support effect on the catalytic process has been studied and discussed in terms of pore structure of the investigated carbon materials. The promotor effect of platinum on Au/C catalysts was examined and it could be shown that the presence of Pt increases not only the catalyst activity but also the selectivity. By promoting the gold catalysts with platinum the selectivity to dihydroxyacetone could be increased from 26% (Au/C) to 36% (Au–Pt/C).     

The role of carbon deposition on precious metal catalyst activity during dry reforming of biogas

Gold and palladium were supported on a mesoporous TiO₂ for total oxidation of volatile organic compounds (VOCs). Mesoporous high surface area titania support was synthesised using of Ti(OC₂H₅)₂ in the presence of CTMABr surfactant. After removing the surfactant molecules, 0.5 or 1.5 wt% of palladium and 1 wt% of gold were precipitated on the support by, respectively, wet impregnation and deposition–precipitation methods. The activity for toluene and propene total oxidation of the prereduced samples follows the same order: 0.5%Pd-1%Au/TiO₂ > 1.5%Pd/TiO₂ > 0.5%Pd/TiO₂ > 1%Au-0.5%Pd/TiO₂ > 1%Au/TiO₂ > TiO₂. Moreover, a catalytic comparison with samples based on a conventional TiO₂, shows the catalytic advantage of the mesoporous TiO₂ support. The promotional effect of gold added to palladium could be partly explained by small metallic particles (TEM), but meanly by metallic particles made up of Au-rich core with a Pd-rich shell. Moreover, the hydrogen TPR profile of 0.5%Pd-1%Au/TiO₂ shows only the signal attributed to small PdO particles. Gold also implies a protecting effect of the support under reduction atmosphere. Operando diffuse reflectance infrared fourier transform (DRIFT) spectroscopy was carried on and allowed to follow the VOCs oxidation and the formation of coke molecules, but also a metallic electrodonor effect to the adsorbed molecule which increases in the same order as the activity for oxidation reaction. The presence of coke after test was also shown by DTA–TGA by exothermic signals between 300 and 500 °C and by EPR (g = 2.003).     

钯/活性炭催化剂中贵金属钯的回收

研究了废钯/活性炭催化剂中金属钯的回收。将废钯/活性炭催化剂用高温焙烧的方法除去其中大部分炭,钯渣用甲酸还原后用王水浸出。考察了焙烧、还原及浸出条件对钯回收率的影响,得到的氯化钯回收率95%,纯度99%。     

Solvent-free oxidation of benzyl alcohol using titania-supported gold–palladium catalysts: Effect of Au–Pd ratio on catalytic performance

The oxidation of benzyl alcohol with molecular oxygen under solvent-free conditions has been investigated using a range of titania-supported Au–Pd alloy catalysts to examine the effect of the Au–Pd ratio on the conversion and selectivity. The catalysts have been compared at high reaction temperature (160 °C) as well as at 100 °C, to determine the effect on selectivity since at lower reaction temperature the range of by-products that are formed are limited. Under these conditions the 2.5 wt.% Au–2.5 wt.% Pd/TiO₂ was found to be the most active catalyst, whereas the Au/TiO₂ catalyst demonstrated the highest selectivity to benzaldehyde. Toluene, formed via either a hydrogen transfer process or an oxygen transfer process, was observed as a major by-product under these forcing conditions.     

New approaches to designing selective oxidation catalysts: Au/C a versatile catalyst

Selective oxidation is of key importance in the synthesis of chemical intermediates. For many years a number of oxides and supported metal catalysts have been used. The key questions involved in the design of selective oxidation catalysts are discussed in the initial part of this paper. One of the most exciting recent developments in the field of selective oxidation has been the discovery that supported gold catalysts are active. The second part of the paper discusses Au/C catalysts, which are shown to be particularly versatile for oxidation reactions. Four examples of selective oxidation are described using molecular oxygen as oxidant: (a) selective oxidation of glycerol to glycerate in the presence of base; (b) the oxidation of cyclohexane to cyclohexanol and cyclohexanane in the presence of a radical initiator; (c) the oxidation of hydrogen to hydrogen peroxide, and (d) the oxidation of benzyl alcohol to benzaldehyde under solvent free conditions. In contrast, the Au/C catalysts are not active for oxidation of carbon monoxide at ambient temperature. These examples demonstrate that there exists a rich potential for Au/C as a selective oxidation catalyst and that research efforts should now be focussed on selective oxidation using supported gold catalysts.     

Minitab软件确定电镀镍钯金引线框架银胶扩散因素

电镀镍钯金引线框架工艺流程繁琐,所用的导电银胶在其每一个工艺步骤都有可能使引线发生银胶扩散现象,导致产品报废.为了减少实验盲目性和不必要的经济损失,采用Minitab软件中的Plackett-Burman设计方法,对可能影响电镀镍钯金引线框架银胶扩散的20个工艺因素进行筛选,得出钯厚度、镍厚度、镀金占空比、钯比重、镀镍...     

The influence of solution pH on rates of an electrocatalytic reaction: Formic acid electrooxidation on platinum and palladium

We found for the first time that solution pH makes a significant difference in the rate of a prototypical electrocatalytic reaction, formic acid electrooxidation, under conditions where H⁺ and OH⁻ do not adsorb strongly on the surface, and we demonstrate that the results can be explained using the Marcus model. We changed the pH of formic acid solutions and found enhanced oxidation on Pd and Pt black catalysts with increased pH. The interpolated current density for the oxidation of 1 M HCOOH in 0.1 M perchlorate electrolyte after 2 min at 0.22 V vs. SHE on Pt increased 30-fold from 0.005 to 0.17 mA cm⁻² as the pH was increased from 1 to 5, while for Pd there was a 4-fold increase from 0.12 to 0.53 mA cm⁻². The data was also interpolated at a current density of 0.1 mA cm⁻², and the potential required to reach this current shifted negative 62 mV per pH on palladium and 56 mV per pH on platinum. A 24 h experiment compared two solution pH, in which the higher pH demonstrated remarkably stronger performance. In addition, the potential for oxidation of surface CO shifts negative on both catalysts, as much as ∼57 mV per pH on Pd.     

Oxidation state of palladium as a factor controlling catalytic activity of Pd/SiO2–Al2O3 in propane combustion

The oxidation state of palladium on SiO₂–Al₂O₃ used for propane combustion was examined by XPS and XRD, and the correlation of the catalytic activity with the oxidation state of palladium was systematically studied. The propane conversion over 5 wt% Pd/SiO₂–Al₂O₃ was measured in the range 1.0≤S≤7.2 (S is defined as [O₂]/5[C₃H₈] based on stoichiometric ratio). The propane conversion strongly depended on the S value and reached the maximum at S=5.5. The oxidation state of palladium also changed with the S value; palladium particles were more oxidized under the reaction mixture of higher S value. On the sample used for the reaction at S=5.5, both of metallic palladium and palladium oxide were found. It is concluded that partially oxidized palladium which has optimum ratio of metallic palladium to palladium oxide shows the highest catalytic activity in propane combustion.     

Self-assembled gold nanoparticles modified ITO electrodes: The monolayer binder molecule effect

The fabrication of gold attached organosilane-coated indium tin oxide Au_NPs-MPTMS/ITO and Au_NPs-APTES/ITO electrodes [MPTMS = 3-(mercaptopropyl)-trimethoxysilane, APTES = 3-(aminopropyl)-triethoxysilane, ITO = indium tin oxide] was carried out making use of a well-known two-step procedure and the role played by the -SH and -NH₂ functional groups in the two electrodes has been examined and compared using different techniques. Information about particle coverage and inter-particle spacing has been obtained using trasmission electron microscopy (TEM), scanning electron microscopy (SEM) and atomic force microscopy (AFM) whereas, bulk surface properties have been probed with UV-vis spectroscopy, CV and electrochemical impedance spectroscopy (EIS). The catalytic activity of the two electrodes has been evaluated studying the electrooxidation of methanol in alkaline conditions. The results obtained show that the NH₂ functionality in the APTES binder molecule favours the formation of isle-like Au nanoparticle aggregates that lead to both a higher electron transfer and electrocatalytic activity.     

Reprint of: Oxidative dehydrogenation of cyclohexane and cyclohexene over supported gold, –palladium catalysts

Supported gold, palladium and gold–palladium catalysts have been used to oxidatively dehydrogenate cyclohexane and cyclohexenes to their aromatic counterpart. The supported metal nanoparticles decreased the activation temperature of the dehydrogenation reaction. We found that the order of reactivity was Pd ≥ Au–Pd > Au supported on TiO₂. Attempts were made to lower the reaction temperature whilst retaining high selectivity. The space-time yield of benzene from cyclohexane at 473 K was determined to be 53.7 mol/kg_cat/h rising to 87.3 mol/kg_cat/h at 673 K for the Pd catalyst. Increasing the temperature in this case improved conversion at a detriment to the benzene selectivity. Oxidative dehydrogenation of cyclohexene over AuPd/TiO₂ or Pd/TiO₂ catalysts was found to be very effective (conversion >99% at 423 K). These results indicate that the first step in the reaction sequence of cyclohexane to cyclohexene is the slowest step. These initial results suggest that in a fixed-bed reactor the oxidative dehydrogenation in the presence of oxygen, palladium and gold–palladium catalysts are readily able to surpass current literature examples and with further modification should yield even higher performance.     

Fabrication of palladium coated nanoporous gold film electrode via underpotential deposition and spontaneous metal replacement: A low palladium loading electrode with electrocatalytic activity

An electrochemical approach to nanoporous film-based gold catalyst design using the underpotential deposition and redox replacement technique is presented. The procedure consisted of the underpotential deposition (UPD) of copper on the gold nanoporous film, with subsequent replacement of the copper by palladium at open circuit in a palladium containing solution. The resulting electrode was studied using cyclic voltammetry and scanning electron microscopy. The electrocatalytic activity of as-prepared palladium nanoporous gold film electrodes toward the oxygen reduction reaction is presented.     

The conversion of polysaccharides to hydrogen gas. Part I: The palladium catalysed decomposition of formic acid/sodium formate solutions

The palladium catalysed decomposition, to H₂+CO₂, of solutions containing formic acid and sodium formate, in various proportions, has been studied in a stirred reactor in the temperature range 60–90°C. The production of hydrogen gas was at its optimum in the pH range 3.8–6.5 and the order of reaction varied with the solution composition from 0.33 (100 mol % formic acid) to 1.07 (100 mol% formate ion). Energies of activation lay in the range 20±9.5 kJ mol^?1–41.8±7 kJ mol^?1, the larger values occurring at the ends of the composition range. Electrode potential measurements were also performed and these were helpful in explaining the (i) cessation of hydrogen production at low HCOO^? ion concentrations before completion of reaction and (ii) the possible nature of catalyst poisons. In no case was the theoretical quantity of hydrogen obtained, although yields >90% can be achieved. It is proposed that reaction proceeds via a surface formate intermediate with different rate determining steps operating at high and low HCOO^? ion concentrations. A number of reversible catalyst poisons are discussed including carbon monoxide and methyl formate, which appear to be the most likely.     

In situ controlled electrochemical promotion of catalyst surfaces: Pd-catalysed ethylene oxidation

The catalytic activity of polycrystalline Pd films deposited on 8 mol% Y₂O₃-stabilized–ZrO₂ (YSZ), an O^2–-conductor, can be altered reversibly by varying the potential of the Pd catalyst film via the effect of nonfaradaic electrochemical modification of catalytic activity (NEMCA) or electrochemical promotion. The complete oxidation of ethylene was investigated as a model reaction in the temperature range 290–360 °C and atmospheric total pressure. The rate of C₂H₄ oxidation can be reversibly enhanced by up to 45% by supplying O^2– to the catalyst via positive current application. The steady-state rate change is typically 10³–10⁴ times larger than the steady-state rate I/2F of electrochemical supply or removal of promoting oxide ions. The observed behaviour is discussed on the basis of previous NEMCA studies and the mechanism of the reaction.     

Polymer-supported catalysts—selective hydrogenation of acid chlorides over palladium/polyamide

The catalytic behaviour of palladium supported on aromatic polyamides was studied in the liquid phase hydrogenation of benzoyl chloride at 1 atm total pressure and between 348 and 408 K. The specific activity of the catalysts as a function of palladium concentration was found to increase with metal loading. It is suggested that palladium in a metallic state is the active site for the acid chloride hydrogenation. A decrease in the reaction rate has been observed at the highest temperatures indicating that under these conditions the availability of hydrogen becomes the rate determining step. Results on the liquid phase hydrogenation of acyl- and aroyl-chlorides are reported. No strong influence of the nature of the substituents was observed on reaction parameters.     

Catalytic oxidation of 1,2-diols to α-hydroxy-carboxylates with stabilized gold nanocolloids combined with a membrane-based catalyst separation

Gold (Au) nanosols stabilized with poly(vinylalcohol) can be used as homogeneous oxidation catalysts, both in water and in a variety of alcoholic solvents. Under 0.5 MPa O₂ pressure, 1,2-diols with varying chain length, such as 1,2-propanediol or 1,2-octanediol, are oxidized to the corresponding α-hydroxy-carboxylates with total chemoselectivity. The activity of the sol is of the same order as previously reported for stabilized nanoparticles deposited on carbon supports. The stabilized sols retain their activity over extended periods. The Au metal colloids can efficiently be recycled by means of a nanofiltration, either from an aqueous reaction medium, or from an organic solvent. The most suitable membranes for the Au sol recuperation are cellulose acetate membranes for the aqueous filtration, and poly(dimethyl)siloxane membranes for the solvent resistant filtration. Recycling tests after nanofiltration show that catalytic activity is largely preserved in consecutive runs.