Electrocatalytic performance of bimetallic platinum–ruthenium nanoclusters supported on graphite nanofibers

In this work, graphite nanofibers (GNFs) as a catalysts supports were impregnated with Pt and Ru precursor compounds to investigate the effect of various Pt–Ru compositions on the catalytic activity of direct methanol fuel cells (DMFCs). The particle sizes and morphological structures of the catalysts were analyzed by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The electrochemical oxidation of the prepared catalysts was investigated by cyclic voltammetry (CV) measurement. Inductive coupled plasma-mass spectrometer (ICP-MS) analysis showed that the metallic ratio in the catalysts was very near to expectations. Cyclic voltammetry showed that the catalysts were electro catalytically active in the methanol oxidation. Among the prepared catalysts, the Pt₅₀Ru₅₀ catalysts exhibited the best electrocatalytic performance. It was concluded that catalytic activity is dependent on the alloy compositions of the catalysts, and that Ru metal has a positive effect on CO poisoning of Pt metal for methanol oxidation.     

Superconductivity of the platinum doped 122 iron arsenide SrFe2−xPtxAs2

Pt doped 122 iron arsenide SrFe_1?xPt_xAs₂ (0 ? x ? 0.4) was successfully synthesized. The tetragonal unit-cell volume and the lattice constant a increase with increasing the Pt content, while c decreases, suggesting that the Fe ions are indeed replaced by Pt ions. By the Pt doping, the magnetic order of the parent phase is suppressed, and superconductivity emerges at approximately x = 0.15. T_c reaches the maximum of 16 K at x = 0.2. The compounds series can be a suitable subject to investigate role of the doped 5d state in the superconducting 3d Fe–As layer.     

X-ray photoelectron spectra of platinum compounds excited with monochromatic AgLα irradiation

Non-monochromatic MgK_α and monochromatic AgL_α irradiations were used to measure Pt4f and Pt3d_5/2 X-ray photoelectron spectra from platinum black and from several platinum compounds with different Pt oxidation states. The Pt3d_5/2 core level binding energies from platinum compounds were measured for the first time. Potential of these data to XPS study of Pt/Al₂O₃ catalysts is demonstrated.     

Muon Knight shift in platinum and in β-PdHx (x=0.70, 0.75)

The ⁺ Knight shift in platinum has been measured between 20 K and 785 K. It shows a strong temperature dependence and scales with the magnetic bulk susceptibility. A temperature independent contribution of +40 to +60 ppm and a d-electron induced hyperfine field per unpaired d-electron per atom ofB _hf,d =–5.03 kG (±8.5%) are obtained. The ⁺ Knight shift in PdH_0.70 and PdH_0.75 shows no dependence on temperature between 20 K andRT and increases fromK ppm forx=0.70 toK ppm forx=0.75, in good agreement with proton Knight shift measurements.     

Muon knight shift in platinum and in β-PdHx (x=0.70, 0.75, 0.86)

The ⁺ Knight shift in Platinum has been measured between 20 K and 785 K. It shows a strong temperature dependence and scales with the magnetic bulk susceptibility. A temperature independent contribution of +53±15 ppm and a d-electron induced hyperfine field per unpaired d-electron per atom of B _hfd ^a =–5.03 kG(±8.5%) are obtained. The ⁺ Knight shift in PdH_0.70, PdH_0.75 and PdH_0.86 shows no dependence on temperature between 20 K and RT and increases from K=–(8±3) ppm for x=0.70 to K =+(6.5±3) ppm K=+(6.5±3) ppm for x=0.86, in good agreement with proton Knight shift measurements.     

Making precious metals cheap: A sonoelectrochemical – Hydrodynamic cavitation method to recycle platinum group metals from spent automotive catalysts

Platinum group metals, such as Pd and Pt, found in three-way catalyst converters were recycled in a two-step method: hydrodynamic cavitation followed by sonoelectrochemical dissolution. High shear forces were obtained by using a convergent nozzle with a throat diameter of 0.2 mm, feeded by a plunger pump at a pressure of 60 MPa. Cavitating submerged jets acted locally on the water dispersed waste catalyst. As-obtained samples were analyzed by scanning electron microscopy and transmission electron microscopy. Electron microscopy on the initial sample showed that round shaped Pd and Pt nanoparticles were randomly distributed on the Al₂O₃ matrix. Cavitated samples show two zones in which Pt and Pd were partially and completely separated from the cordierite. The hydrodynamic cavitation separates the Pd and Pt from the cordierite leading to an apparent increase in Pd and Pt concentrations of 9% and 34% respectively. Conventional electrochemistry showed a dissolution of 20% in 1 h. To further accelerate the dissolution, a sonotrode operating at 20 kHz and 75 W was placed inside an electrochemical cell in order to increase the mass transport and obtain high dissolution rates. Indeed, the results showed that 40% of the available Pd and Pt can be recycled in just 1 h. In the absence of hydrodynamic cavitation and using conventional electrochemistry less than 10% of the available Pt and Pd is recovered in 1 h. The cost analysis showed that Pd and Pt can be recovered at less than 10 EUR per g which is 5 times smaller than their current market price.     

C?H bond activation of ethylene by bare neutral palladium and platinum atoms: a theoretical investigation

The reactions of bare neutral palladium (Pd) and platinum (Pt) atoms with ethylene on both singlet and triplet surfaces were investigated at B3LYP and CCSD (T) levels of theory. The calculated potential energy profiles clearly show that Pt has higher reactivity than Pd toward ethylene. For both Pd and Pt, the reactions on singlet surfaces are energetically more favorable than those on triplet surfaces. However, notable barriers lie on the singlet and triplet surfaces for Pd +ethylene. This result rationalizes the experimental observation that Pd mainly forms π‐complex with ethylene. But under high‐energy condition, the reaction can proceed to yield dehydrogenation products, Pd‐CCH. and Pd (HCCH). For Pt, triplet‐singlet surface crossing was suggested to occur in the region where Pt forms π‐complex with ethylene to lead the reactions to the energetically more favorable singlet surfaces. For both the two metals, π‐complex and C? H bond insertion species are the reaction intermediates and the H.‐elimination products are the final products. Copyright © 2010 John Wiley & Sons, Ltd.     

Electronic structure and thermodynamic properties of platinum–lead oxides PbPt2O4 and Pb2PtO4 by ab initio methods

We report the electronic structure and thermodynamic properties of platinum–lead oxides PbPt₂O₄ and Pb₂PtO₄. The band structure is calculated by the full-potential, full-relativistic local orbital minimum basis (FPLO) method in the local density approximation, including the generalized gradient approximation (GGA) and GGA+U, respectively. The values of gaps in Pb₂PtO₄ were estimated as 0.47, 1.02, and 0.52 eV in GGA, GGA+U, and the full-relativistic GGA, respectively. Pb₂PtO₄ is a semiconductor, and PbPt₂O₄ is a metallic conductor with the small values of the density of states at the Fermi level. The effect of chemical disorder in Pb_2?xPt_1+xO₄ alloys is studied by the relaxation of the volume, shape, and the positions of atoms in the unit cell, using the Vienna Ab initio Simulation Package (VASP) method. The thermodynamic properties are computed in the quasi-harmonic Debye–Grüneisen model. The dependence of the thermodynamic parameters on the pressure and temperature is also presented.     

Structure and magnetic properties of iron–platinum particles with <Emphasis Type="Italic">γ</Emphasis>-ferric-oxide shell

Nanoparticles of solid solution Fe _x Pt_1?x , where 0.25≥x≥0 (?fcc lattice) with γ-Fe₂O₃ shell (lattice of the spinel type) were synthesised and characterised by high-resolution transmission electron microscopy, energy dispersive X-ray analysis, electron energy loss spectroscopy, Mössbauer spectroscopy and magnetometry. From the point of view of magnetic properties, such two-phase particles are interesting because their core is antiferromagnetic or paramagnetic (at very small values of x) whereas the shell is ferrimagnetic. The size of the particles was in the range of several nanometers. The Mössbauer measurements revealed a blocking temperature of about 100 K above which the particles are superparamagnetic. Towards lower temperatures, the magnetic characteristics of an ensemble of such particles show an increase of magnetic rigidity.     

Anomalous electrical conductivity of the potassium deficient linear chain platinum compound: K1.75Pt(CN)4·1.5H2O

Four probe single crystal dc conductivity, σ, has been measured for K_1.75Pt (CN)₄·1.5H₂O for temperature 360K > T > 30K on crystals prepared via electrochemical growth, with σ (295K)

25–50 Ω^?1cm^?1. An anomalous behavior in σ (T) is reported with σ (T) nearly constant for T > 300K and 160K > T > 80K, and rapidly decreasing σ (T) observed for 300K > T > 160K and T < 80K. The data for 200K < T < 308K are analyzed in terms of a three-dimensional second order phase transition occurring at T_c = 308K. These results contrast sharply with those of the well studied K₂Pt(CN)₄X_0.3·3H₂0 (X=Cl,Br).