Composition-controlled synthesis of platinum and palladium nanoalloys as highly active electrocatalysts for methanol oxidation

Platinum and palladium(PtPd)alloy nanoparticles(NPs)are excellent catalysts for direct methanol fuel cells.In this study,we developed PtPd alloy NPs through the co‐reduction of K2PtCl4and Na2PdCl4in a polyol synthesis environment.During the reaction,the feed molar ratio of the two precursors was carried over to the final products,which have a narrow size distribution with a mean size of approximately4nm.The catalytic activity for methanol oxidation reactions possible depends closely on the composition of as‐prepared PtPd alloy NPs,and the NPs with a Pt atomic percentage of approximately75%result in higher activity and stability with a mass specific activity that is7times greater than that of commercial Pt/C catalysts.The results indicate that through composition control,PtPd alloy NPs can improve the effectiveness of catalytic performance.

Extraction of gold, palladium, and platinum from acidic media with cyclic sulfoxide derivative

The extraction of gold （Ⅲ）, palladium （Ⅱ）, and platinum （Ⅳ） from the acidic media with the cyclic sulfoxide derivative of α-dodecyl-tetrahydrothiophene 1-oxide （dtmso） was investigated. Gold （Ⅲ）, palladium （Ⅱ）, and platinum （Ⅳ） could be separated from the acidic media with suitable sulfoxide concentration and acidity. The extraction reaction of gold （Ⅲ）, palladium （Ⅱ） or platinum （Ⅳ） is exothermic when dtmso is used as an extracting reagent. The coordination number was studied by the slope method. The results indicate that, in high acidity, the dtmso coordination number for extracting gold （Ⅲ） or palladium （Ⅱ） is 3, and that for platinum （Ⅳ） is 2. UV and FT-IR spectra were used to analyze the structure of the complex. Gold （Ⅲ） is coordinated with the oxygen atom in S=O group in dtmso, and palladium （Ⅱ） or platinum （Ⅳ） is coordinated with the sulfur atom in S=O group in dtmso.

SYNTHESIS AND CATALYTIC HYDROSILYLATION PROPERTY OF POLYSILOXANE-SUPPORTED MERCAPTOSELENAETHER PLATINUM OR RHODIUM COMPLEX

Silica-bound mercaptoselenaether-containing silsesquioxane and its platinum or rhodium complex were synthesized from gamma-(2,3-epithiopropyl) propyltrimethoxysilane via ring-opening reaction with bis(2-hydroxyethyl) selenide, followed by hydrolysis and immobilization on fumed silica, and then reacting with potassium chloroplatinite or rhodium chloride in acetone under nitrogen atmosphere. It was found that two noble metal complexes can catalyze the hydrosilylation of olefins with triethoxysilane effectively. The influences of temperature, the amount of complex used, the nature of olefin on catalytic activity were investigated.

Studies on Dual-beam Spectrometric Simultaneous Determination of Platinum and Rhodium with Water-Insoluble Porphine T(3-M-4HP)P

The optimal conditions for the complexation reaction of meso- tetra(3-methoxy-4-hy-droxyphenyl) porphine T(3-M-4HP)P with platinum and rhodium are presented. Beer' s Law is obeyed when the concentration of rhodium is in the range of 0. 45-1.15 μg/25mL. The molar absorptivity of rhodium was found to be 1.99×106 L·mol-1·cm-1 at 460 nm. The value of εPt was found to be 6. 28×105 L·mol-1·cm-1 by linear regression method. The K coefficient method and compensating coefficient were used to determine platinum and rhodium simultaneouly without removal or masking of the interferents in the sample. The results for the determination of platinum and rhodium in the mixed solution of platinum and rhodium are satisfactory.

Liquid Etherification of Alkoxybenzyl Alcohols, Cinnamyl Alcohols and Fluorinated Phenylalkenols with Platinum on Carbon (Pt/C) and Palladium on Carbon (Pd/C)

In the presence of either Pd/C or Pt/C, 4-alkoxybenzyl alcohols, 4-alkoxy-phenylalkyl alcohols and cinnamyl alcohols undergo liquid etherification to bis(4-alkoxybenzyl) ethers, bis[(4-alkoxybenzyl)alkyl] ethers and bis(cin-namyl) ethers at temperatures of 100°C - 135°C. In a number of cases, Pt/C and Pd/C as catalysts, also when they are doped with Ru, show distinct differences when the reactions run in air, with an oxidative dehydrogenation of the alcohols as side-reaction, yielding the corresponding ketones and aldehydes as by-products. Also, the reactivity of fluorinated phenylalkenols under these conditions has been investigated. Furthermore, the immobilization of alkyl aryl ethers on silica within a column with passage of hexane as solvent was found to lead to the formation and elution of styrenes from the column in fair yield.

Nanoparticles of Palladium, Platinum and Silver:Incoporation into Perfluoro-Sulfonated Membrane MF-4SK and Ionic Nafion

The purpose of the investigation is the study of the physico-chemical properties and electro-catalytic characteristics of the Nafion and MF-4SK membranes with the author’s nanoparticles (A. Revina, 2008) incorporated into the perfluoro- sulphonated cationic membranes. An important advance in the creation of new nano-composite materials with poly-functional activity is the inclusion of nanoparticles of various metals (Pd, Pt, Ag) in these membranes. Polymer ion exchange membranes represent widely applicable materials in various areas of modern nanotechnologies. The obtained nanocomposites on the base of included nanoparticles have the perspective properties and polyfunctional activity for the applications.

Platinum and Palladium Abundances in Floodplain Sediments and Their Geochemical Provinces

Results obtained from the wide spaced floodplain sediments indicate that the abundances of Pt and Pd in floodplain sediments are 0.46 ng/g and 0.40 ng/g, respectively. Three geochemical provinces, Yunnan Guizhou, Xinjiang Gansu and Tibet of Pt and Pd with a content of 0.8 ng/g, were delineated.

Simultaneous Spectrophotometric Determination of Trace Palladium and Rhodium with2，4－TADAT

ＳｉｍｕｌｔａｎｅｏｕｓＳｐｅｃｔｒｏｐｈｏｔｏｍｅｔｒｉｃＤｅｔｅｒｍｉｎａｔｉｏｎｏｆＴｒａｃｅＰａｌｌａｄｉｕｍａｎｄＲｈｏｄｉｕｍｗｉｔｈ２，４－ＴＡＤＡＴＺＨＡＮＧＸｉａｏ－ｌｉｎｇ；ａｎｄＺＨＡＮＧＧｕａｎｇ（ＤｅｐａｒｔｍｅｎｔｏｆＣｈ...

Palladium,Platinum and Gold Concentrations in Fengshan Porphyry Cu-Mo Deposit,Hubei Province,China

The Fengshan porphyry-skarn copper-molybdenum （Cu-Mo） deposit is located in the south-eastern Hubei Province in east China. Cu-Mo mineralization is hosted in the Fengshan granodiorite porphyry stock that intruded the Triassic Daye Formation carbonate rocks in the early Cretaceous （-140 Ma）, as well as the contact zone between granodiorite porphyry stock and carbonate rocks, forming the porphyry-type and skaru-type association. The Fengshan granodiorite stock and the immediate country rocks are strongly fractured and intensely altered by hydrothermal fluids. In addition to intense skarn alteration, the prominent alteration types are potassic, phyllic, and propylitic, whereas argiilation is less common. Mineralization occurs as veins, stock works, and disseminations, and the main ore minerals are chalcopyrite, pyrite, molybdenite, bornite, and magnetite. The contents of palladium, platinum and gold （Pd, Pt and Au） are determined in nine samples from fresh and mineralized granodiorite and different types of altered rocks. The results show that the Pd content is systematically higher than Pt, which is typical for porphyry ore deposits worldwide. The Pt content ranges from 0.037 tol.765 ppb, and the Pd content ranges between 0.165 and 17.979 ppb. Pd and Pt are more concentrated in porphyry mineralization than skarn mineralization, and have negative correlations with Au. The reconnaissance study presented here confirms the existence of Pd and Pt in the Fengshan porphyry-skarn Cu-Mo deposit. When compared with intracontinent and island arc geotectonic settings, the Pd, Pt, and Au contents in the Fengshan porphyry Cu-Mo deposit in the intracontinent is lower than the continental margin types and island are types. A combination of available data indicates that Pd and Pt were derived from oxidized alkaline magmas generated by the partial melting of an enriched mantle source.

Palladium,Platinum and Gold Concentrations in the Fengshan Porphyry Cu-Mo Deposit,Hubei Province,China

The Fengshan porphyry-skam copper-molybdenum deposit is located in the southeastern Hubei Province, East China.Cu-Mo mineralization is hosted in the Fengshan quartz diorite porphyry stock that intruded the Triassic Daye Formation of carbonate rocks in the early Cretaceous(ca.140 Ma),as well as in the contact zone between these two,forming

Platinum/rhodium Alloy Bushing for Drawing Glass Fibers in Centrifugal-spinneret-blow Process

In this paper,glass fibers were prepared by centrifugal-spinneret-blow(CSB) process.The molten glass got different flow rate from 390 kg/h to 270 kg/h by adjusting the electric current of platinum/10 rhodium alloy bushing.The diameter and microstructure of glass fibers have been investigated by scanning electron microscopy(SEM) and vertical optical microscope(VOM).The results indicated that the flow rate of molten glass was proportional to the diameter of glass fibers when the molten glass got main flow rate of 330 kg/h.The lower the flow rate was,the finer the average diameter was.

Improving the Quality of Thermocouple Wire Made of Platinum-rhodium Alloys

For the manufacture of S-type thermocouple the so-called thermocouple wire of platinum and platinum-rhodium alloy is used.One of the main technical requirements for the quality of the wire,according to State Standard of Russia(GOST 10821),is the uniformity of its largest thermoelectric force(Thermo-emf) in the length different sections.It was found that a determining impact on the uniformity of the wire thermo-emf is the distribution of rhodium along the length of the wire.The impact of platinum-rhodium melt crystallization conditions on the inhomogeneity of wire manufactured from it.It was suggested that the chemical inhomogeneity of the wire is related to the liquation phase of platinum-rhodium alloy.

New insight into the adsorption of ruthenium,rhodium,and palladium from nitric acid solution by a silica-polymer adsorbent

A porous silica-polymer-based adsorbent,isoBuBTP/Si O2-P,was prepared by a vacuum impregnation method and used for the recovery of ruthenium,rhodium,and palladium from nitric acid solution.The experimental results revealed that iso Bu-BTP/SiO2-P exhibited unique adsorption properties such as high saturation adsorption capacity(Ru:0.35 mmol g^-1,Rh:0.32 mmol g^-1,Pd:1.05 mmol g^-1)and excellent selectivity over other metal ions,such as lanthanides(SF(PGM/M)>40)in 1 M HNO3 solution.The adsorption process conformed to the pseudosecond-order model and Langmuir model.From the UV,FTIR,and XPS analyses,it can be concluded that the strong affinity between functional groups(C–N=C)and metal ions as well as NO3-played a role in coordination during the adsorption process.Furthermore,the desorption behavior was studied,and it was found that the adsorbed Pd,Rh,and Ru could be eluted with a 0.01 M nitric acid–0.1M thiocarbamide solution,5M hydrochloric acid,and sodium hypochlorite(CP)solution,respectively.Finally,based on those findings,a simple process for the separation and recovery of Pd,Rh,and Ru from high-level liquid waste using iso Bu-BTP/SiO2-P was designed and proposed.

Synthesis of palladium-rhodium bimetallic nanoparticles for formic acid dehydrogenation

Herein,we report for the first time the synthesis of preformed bimetallic Pd-Rh nanoparticles with different Pd:Rh ratios(nominal molar ratio:80-20,60-40,40-60,20-80) and the corresponding Pd and Rh monometallic ones by sol immobilization using polyvinyl alcohol(PVA) as protecting agent and NaBH4 as reducing agent,using carbon nanofibers with high graphitization degree(HHT) as the desired support.The synthesized catalysts were characterized by means of Transmission Electron Microscopy(TEM) and inductively coupled plasma optical emission spectroscopy(ICP-OES).TEM shows that the average particle size of the Pd-Rh nanoparticles is the range of 3-4 nm,with the presence of few large agglomerated nanoparticles.For bimetallic catalysts,EDX-STEM analysis of individual nanoparticles demonstrated the presence of random-alloyed nanoparticles even in all cases Rh content is lower than the nominal one(calculated Pd:Rh molar ratio:90-10,69-31,49-51,40-60).The catalytic performance of the Pd-Rh catalysts was evaluated in the liquid phase dehydrogenation of formic acid to H2.It was found that Pd-Rh molar ratio strongly influences the catalytic performance.Pd-rich catalysts were more active than Rh-rich ones,with the highest activity observed for Pd90:Rh10(1792 h^(-1)),whereas Pd69:Rh31(921 h^(-1)) resulted the most stable during recycling tests.Finally,Pd90:Rh10 was chosen as a representative sample for the liquid-phase hydrogenation of muconic acid using formic acid as hydrogen donor,showing good yield to adipic acid.

Chemical composition of the ore and occurrence state of the elements in Jingbaoshan platinum-palladium deposit

The Jingbaoshan platinum-palladium deposit is China’s largest independent PGM (platinum-group met- als) deposit so far discovered. There are eleven kinds of useful components in the ore: Pt, Pd, Os, Ir, Ru, Rh, Au, Ag, Cu, Ni, and Co. The platinum-group elements, gold and silver occur in the form of minerals in ores. twenty-five kinds of precious metal minerals have been found, of which twenty one belong to the platinum-group minerals. The minerals are very small in grain size. Copper occurs mainly as copper sulfide with a small amount of free copper oxide, and the beneficiated copper accounts for 95.21%. Nickel occurs mainly as nickel sulfide, and some nickel silicate and nickel oxide occur in the ore. The beneficiated nickel accounts for 72.03%. Cobalt occurs mainly as co- balt sulfide, and there are some cobalt oxide and other kinds of cobalt. The beneficiated cobalt accounts for 77.58%.

Distribution of platinum group elements in road dust in the Beijing metropolitan area, China

Dust samples collected from the Beijing metropolitan area （China） were evaluated to determine the distribution and the concentration of platinum group elements （PGEs）. The dust particles that were smaller than 100 mesh size fraction （150 μm） were analyzed after aqua regia digestion. Concentrations ofPt, Rh, and Pd were found to be between 3.96 and 356.3 ng/g, 2.76 and 97.11 ng/g, and 0.1 and 124.9 ng/g, respectively, in the urban areas of Beijing, whereas for the background samples collected from the suburbs of Beijing, the concentrations of Pt, Pd, and Rh were very low and ranged from 0.1 to 0.9 ng/g, 0.5 to 1.4 ng/g, and 0.8 to 2.2 rig/g, respectively. The distributions of PGEs in road dust were an accurate reflection of the levels of pollution and were found to match with the local traffic conditions. A strong positive correlation was established among all the dements found in road dust. This suggests that emissions of abraded fragments from vehicle exhausts may be the source of the high concentration of Pt, Rh, and Pd in road dust along the main roads of Beijing.

Study on the Recovery of Rhodium from Spent Organic Rhodium Catalysts of Acetic Acid Industry Using Pyrometallurgical Process

A new process recycling rhodium from organic waste containing rhodium in acetic acid industry is developed. Use the special affinity of base metal sulfides (FeS, Ni2S3 , CuS, etc.) on platinum group metals, adopting high nickel matte trapping-aluminothermic activation method to recovery rhodium from incinerator residue of organic rhodium waste. The method is shorter process, lower equipment requirement, and the higher activity of rhodium black. In pyrometallurgy enrichment process,the recovery rate of rhodium reached 94.65%, the full flow of rhodium recovery rate was 92.04%.

Simultaneous Laser Thermal Lens Spectrometric Determination of Trace Platinum and Palladium in an Aqueous Solution

A selective and sensitive method for determination of platinum and palladium(II) in an aqueous solution simultaneously by laser thermal lens spectrometry, based on the complex reaction of 2-(3,5-dichloropyridylazo)-5-dimethylaminoamiline (3,5-diCl-PA^D~MA) with platinum and palladium, has been developed. It is shown that the palladium complex can be formed at room temperature, while the platinum complex can be only formed after being heated in a boiling water bath. By using this difference of reaction temperature and the characteristic of the complexes mentioned above, the method for simultaneous determination of platinum and palladium was established in an aqueous solution without a pre-separation. The results show that the dynamic linear ranges of determination for platinum and palladium are 0.005- 0.04 μg/mL and 0.005- 0.25 μg/mL respectively, and that the detection limits are both 0.002 μg/mL. The method has been applied to the determination of platinum and palladium simultaneously in alloy and catalyst samples with satisfactory results.

THE ^(31)P AND ^(13)C NMR STUDIES OF CYCLOPENTYL PHOSPHINE COMPLEXES OF PLATINUM (Ⅱ) AND PALLADIUM (Ⅱ)

Most of phosphine halogen complexes of transition metals, platinum and palladium, possess catalytic properties. The configurations of Pt(Ⅱ) and Pd(Ⅱ) complexes are square planar, existing as cis and trans isomers. Nuclear magnetic resonance studies of the structures of phosphine complexes of platinum and palladium were reported, but no paper appeared on cyclopentyl phosphine except the ear-

China's second largest platinumpalladium mine drawing up its curtain for exploitation

Recently,Jinbaoshan platinum-palladium mine in Midu County,Yunnan passed the expert evaluation.As a polymetallic deposit,the mine has 45 tons(metal content)platinum-palladium reserves with the grade at 1.48g/ton,making it China’s second largest platinum-palladium mine with prospected reserves and comprehen-