Unusual physical and chemical properties of Cu in Ce(1-x)Cu(x)O(2) oxides

The structural and electronic properties of Ce(1-x)Cu(x)O(2) nano systems prepared by a reverse microemulsion method were characterized with synchrotron-based X-ray diffraction, X-ray absorption spectroscopy, Raman spectroscopy, and density functional calculations. The Cu atoms embedded in ceria had an oxidation state higher than those of the cations in Cu(2)O or CuO. The lattice of the Ce(1)(-x)Cu(x)O(2) systems still adopted a fluorite-type structure, but it was highly distorted with multiple cation-oxygen distances with respect to the single cation-oxygen bond distance seen in pure ceria. The doping of CeO(2) with copper introduced a large strain into the oxide lattice and favored the formation of O vacancies, leading to a Ce(1-x)Cu(x)O(2-y) stoichiometry for our materials. Cu approached the planar geometry characteristic of Cu(II) oxides, but with a strongly perturbed local order. The chemical activities of the Ce(1-x)Cu(x)O(2) nanoparticles were tested using the reactions with H(2) and O(2) as probes. During the reduction in hydrogen, an induction time was observed and became shorter after raising the reaction temperature. The fraction of copper that could be reduced in the Ce(1-x)Cu(x)O(2) oxides also depended strongly on the reaction temperature. A comparison with data for the reduction of pure copper oxides indicated that the copper embedded in ceria was much more difficult to reduce. The reduction of the Ce(1-x)Cu(x)O(2) nanoparticles was rather reversible, without the generation of a significant amount of CuO or Cu(2)O phases during reoxidation. This reversible process demonstrates the unusual structural and chemical properties of the Cu-doped ceria materials.     

A new promising Pt(Mo2C) catalyst for hydrogen evolution reaction prepared by galvanic displacement reaction

Journal of Solid State Electrochemistry - A new method for the synthesis of Pt(Mo2C) catalysts using the redox reaction between Mo2C and solution containing potassium tetracholoplatinate (II) is...     

Mechanism of electrocatalytic reduction of nitric oxide on Pt(100)

The mechanism of electrocatalytic reduction of nitric oxide on Pt(100)-(1 x 1) in acidic media has been studied using voltammetry, in-situ infrared spectroscopy, and on-line mass spectroscopy, considering the effect of surface defects, NO coverage, and the nature of the supporting electrolyte (sulfate vs perchlorate). Related mechanistic aspects of hydroxylamine (HAM) transformations on the same surface have been also examined. The adsorption of nitric oxide on Pt(100) results in the formation of an adlayer with a structure similar to that formed under ultrahigh vacuum (UHV) conditions. Ammonia was shown to be the main product of NOads reduction on Pt(100). The saturation coverage of NO adsorbate on Pt(100) was found to be around 0.5 ML, in agreement with previous UHV and electrochemical studies. Two features observed in the voltammetric profile for the electrocatalytic reduction of saturated and subsaturated NO adlayers were tentatively ascribed to reactions of NO species having different reactivity. The Tafel slope analysis of these voltammetric features gives values of ca. 60 mV decade(-1). This value was interpreted in terms of an EC mechanism, in which the first electron/proton transfer is at equilibrium, resulted in formation of HNOads intermediate, while the second reaction step is a chemical rate-determining step. This chemical step is assumed to involve the N-O bond breaking in HNOads intermediate, which most probably requires a free neighboring site. From a comparison with NOads reduction on Pt(111) and Pt(110), it follows that (i) the reaction mechanism is structure sensitive and (ii) Pt(100) is the most active surface for breaking the N-O bond, which is in agreement with the trend observed under UHV conditions. As suggested in our previous studies, the electrocatalytic reduction of HAM is likely to proceed through its partial dehydrogenation. In this study, we further develop this idea, and, based on the mechanism for NOads reduction proposed here, we suggest HNOads to be the intermediate appearing both in HAM reduction/oxidation and in NOads reduction.     

Ni 1-x Pt x (x = 0-0.12) hollow spheres as catalysts for hydrogen generation from ammonia borane

In this paper, nest-like Ni1-xPtx (x = 0, 0.03, 0.06, 0.09, and 0.12) hollow spheres of submicrometer sizes have been prepared through a template-replacement route and investigated as catalysts for generating hydrogen from ammonia borane (NH3BH3). Experimental investigations have demonstrated that the obtained Ni1-xPtx alloy hollow spheres exhibit favorable catalytic activities for both the hydrolysis and the thermolysis of NH3BH3. It was found that, in the presence of the Ni0.88Pt0.12 catalyst, the hydrolysis of NH3BH3 causes a quick release of H2, while the thermal decomposition of NH3BH3 occurs at lowered temperatures with increased mass loss. The present results indicate that NH3BH3 along with Ni1-xPtx alloy hollow spheres may find some applications for small-scale on-board hydrogen storage and supply.     

A general and high-yield galvanic displacement approach to Au-M (M = Au, Pd, and Pt) core-shell nanostructures with porous shells and enhanced electrocatalytic performances

In this work, we utilize the galvanic displacement synthesis and make it a general and efficient method for the preparation of Au-M (M = Au, Pd, and Pt) core-shell nanostructures with porous shells, which consist of multilayer nanoparticles. The method is generally applicable to the preparation of Au-Au, Au-Pd, and Au-Pt core-shell nanostructures with typical porous shells. Moreover, the Au-Au isomeric core-shell nanostructure is reported for the first time. The lower oxidation states of Au(I), Pd(II), and Pt(II) are supposed to contribute to the formation of porous core-shell nanostructures instead of yolk-shell nanostructures. The electrocatalytic ethanol oxidation and oxygen reduction reaction (ORR) performance of porous Au-Pd core-shell nanostructures are assessed as a typical example for the investigation of the advantages of the obtained core-shell nanostructures. As expected, the Au-Pd core-shell nanostructure indeed exhibits a significantly reduced overpotential (the peak potential is shifted in the positive direction by 44?mV and 32?mV), a much improved CO tolerance (I(f)/I(b) is 3.6 and 1.63 times higher), and an enhanced catalytic stability in comparison with Pd nanoparticles and Pt/C catalysts. Thus, porous Au-M (M = Au, Pd, and Pt) core-shell nanostructures may provide many opportunities in the fields of organic catalysis, direct alcohol fuel cells, surface-enhanced Raman scattering, and so forth.     

DFT characterization of adsorbed NH(x) species on Pt(100) and Pt(111) surfaces

Periodic density functional theory (DFT) calculations using plane waves have been performed to systematically investigate the adsorption and relative stability of ammonia and its dehydrogenated species on Pt(111) and Pt(100) surfaces. Different adsorption geometries and positions have been studied, and in each case, the equilibrium configuration has been determined by relaxation of the system. The vibrational spectra of the various ammonia fragments have been computed, and band assignments have been compared in detail with available experimental data. The adsorption of NH3 (on top) and NH2 (bridge) is more favorable on Pt(100) than on Pt(111), while similar adsorption energies were computed for NH (hollow) and N (hollow) on both surfaces. The remarkably lower adsorption energy of NH2 over Pt(111) as compared with Pt(100) (the difference being approximately 0.7 eV) can be related to different geometric and electronic factors associated with this particular intermediate. Accordingly, the type of platinum surface determines the most stable NH(x) fragment: Pt(100) has more affinity for NH2 species, whereas NH species are preferred over Pt(111).     

The use of galvanic displacement in synthesizing Pt(Cu) catalysts with the core-shell structure

The formation of a Pt(Cu) bimetallic catalyst on the carbon support by galvanic displacement of copper electrodeposits with platinum (PtCl ₆ ^2? as the displacing agent) is systematically studied. Composition, structure, and electrocatalytic properties of samples corresponding to different stages of copper displacement are analyzed. For substantially long displacement times, the formation of stable Pt(Cu)_st particles with the atomic ratio Pt: Cu ≈ 7: 3 is observed. The Pt(Cu)_st/C electrodes are shown to be close to the Pt/C electrode as regards the adsorption of hydrogen and copper atoms and the specific activity in methanol oxidation (with 0.5 M H₂SO₄ as the supporting electrolyte). Such electrocatalytic behavior of Pt(Cu)_st particles makes it possible to infer the formation of the “core(Pt, Cu)-shell(Pt)” structure, as confirmed by the XPS data.     

Self-assembly of a Rh(I) complex on Au(111) surfaces and its electrocatalytic activity toward the hydrogen evolution reaction

The self-assembly of a Wilkinson type of catalyst molecule, trans-RhCl(CO)(PPh3)2, on Au(111) surfaces and its electrocatalytic properties toward the hydrogen evolution reaction (HER) are investigated by employing scanning tunneling microscopy (STM), cyclic voltammetry (CV), and X-ray photoelectron spectroscopy (XPS). The self-assembled monolayers of RhCl(CO)(PPh3)2 are prepared from either dichloromethane or aqueous solutions, but the ordered structures are observed only in atmospheric conditions after solvents evaporate. In the electrolyte solutions, disordered yet uniformly sized spherical clusters of individual molecules are observed as a result of the conformational change of the molecule by the solvation effect of water. The immobilized Rh(I) molecular clusters are electrochemically stable in a wide potential window and exhibit remarkable electrocatalytic activity toward HER in perchloric acid solutions. Several comparative experiments involving similar types of immobilized complexes containing Ru(I) and Ir(I) centers and solution species of RhCl(CO)(PPh3)2 are performed. However, none of them are found to be electroactive to HER. The Tafel slope of HER on the Rh(I) complex modified Au(111) electrode in 0.1 M HClO4 is determined to be -0.061 V, which is almost in the middle of those on bare Au(111) (-0.093 V) and Rh covered (thetaRh approximately 0.3) Au(111) (-0.034 V) electrodes. XPS measurements reveal a valence change of Rh(I) to Rh(0), and an oxidative addition and reductive elimination mechanism is suggested for the enhancement of HER.     

Pt(x)Ru(1-x)/Ru(0001) surface alloys-formation and atom distribution

The formation of PtRu surface alloys by deposition of submonolayer Pt films on a Ru(0001) substrate and subsequent annealing to about 1350 K and the distribution of the Pt atoms in the surface layer were investigated by scanning tunneling microscopy. Quantitative statistical analysis reveals (i) negligible losses of Pt into subsurface regions up to coverages close below 1 monolayer, (ii) a homogeneous distribution of the Pt atoms over the surface, and (iii) the absence of a distinct long-range or short-range order in the surface layer. In addition, the density of specific adsorption ensembles is analyzed as a function of Pt surface content. Possible conclusions on the process for surface alloy formation are discussed. The results are compared with the properties of PtRu bulk alloys and the findings in previous adsorption studies on similar surface alloys (H. Rauscher, T. Hager, T. Diemant, H. Hoster, F. Bautier de Mongeot and R. J. Behm, Surf. Sci., 2007, 601, 4608; T. Diemant, H Rauscher and R. J. Behm, J. Phys. Chem. C, in press).     

Cu UPD at Pt(100) and stepped faces Pt(610), Pt(410) of platinum single crystal electrodes

The processes of adsorption/desorption of copper adatoms on the basal Pt(100) face and stepped Pt(610), Pt(410) surfaces have been studied in perchloric acid solution by cyclic voltammetry. It has been shown that the positions of the Cu stripping peaks are determined by perfection of the adlayer. The “island” model is suggested to describe electrochemical behavior of the Pt(hkl)+Cu_ad system. Obtained results are important for target modification of shape-controlled nanoparticles that are used in electrocatalysis.     

Nanostructured Bi(2-x)Cu(x)S3 bulk materials with enhanced thermoelectric performance

Nanostructured Bi(2-x)Cu(x)S(3) (x = 0, 0.002, 0.005, 0.007, 0.01, 0.03) thermoelectric polycrystals were fabricated by combining mechanical alloying (MA) and spark plasma sintering (SPS) methods. The effect of Cu content on the microstructure and thermoelectric property of Bi(2-x)Cu(x)S(3) bulk samples was investigated. It was found that the subtle tailoring of Cu content could reduce both the electrical resistivity and the thermal conductivity at the same time, and consequently enhancing the thermoelectric property. A low electrical resistivity of 1.34 × 10(-4)Ω m(-1) and a low thermal conductivity of 0.52 W m(-1) K(-1) were obtained for the Bi(1.995)Cu(0.005)S(3) sample at 573 K. The low thermal conductivity is supposed to be due to the nanoscopic Cu-rich regions embedded in the host matrix. A peak ZT value of 0.34 at 573 K was achieved for the Bi(1.995)Cu(0.005)S(3) composition, which is the highest value in the Bi(2)S(3) system reported so far.     

Syntheses and structural analyses of variable-stoichiometric Au-Pt-Ni carbonyl/phosphine clusters, Pt3(Pt(1-x)Ni(x))(AuPPh3)2(mu2-CO)4(CO)(PPh3)3 and Pt2(Pt(2-y)Ni(y))(AuPPh3)2(mu2-CO)4(CO)2(PPh3)2, with ligation-induced site-specific Pt/Ni substitutional disorder within butterfly-based Pt3(Pt(1-x)Ni(x))Au2 and Pt2(Pt(2-y)Ni(y))Au2 core-geometries

In ongoing attempts of directed synthesis of high-nuclearity Au-Pt carbonyl/phosphine clusters with [Ni6(CO)12]2- used as reducing agent and CO source, we have isolated and characterized two new closely related variable-stoichiometric trimetallic clusters, Pt3(Pt(1-x)Ni(x))(AuPPh3)2(mu2-CO)4(CO)(PPh3)3 (1) and Pt2(Pt(2-y)Ni(y))(AuPPh3)2(mu2-CO)4(CO)2(PPh3)2 (2). Their M4Au2 cores may be envisioned as substitutional disordered butterfly-based M4Au2 frameworks (M = Pt/Ni) formed by connections of the two basal M(B) atoms with both (Au-Au)-linked Au(PPh3) moieties. Based upon low-temperature CCD X-ray diffraction studies of eight crystals obtained from different samples, ligation-induced site-specific Pt/Ni substitutional disorder (involving formal insertion of Ni in place of Pt) in a given crystal was found to occur only at the one OC-attached basal M(B) site in 1 or at both OC-attached basal M(B) sites in 2 corresponding to a crystal composite of the Pt3(Pt(1-x)Ni(x))Au2 core in 1 or of the Pt2(Pt(2-y)Ni(y))Au2 core in 2; the Ph3P-attached M(B) site (M(B) = Pt) in 1 and two wingtip M(w) sites (M(w) = Pt) in 1 and 2 were not substitutionally disordered. The resulting variable stoichiometry of the M4Au2 core in 1 may be viewed as a crystal composite of two superimposed individual stereoisomers, Pt4(AuPPh3)2(mu2-CO)4(CO)(PPh3)3 (1a) and Pt3Ni(AuPPh3)2(mu2-CO)4(CO)(PPh3)3 (1b), in the averaged unit cell of a given crystal. Likewise, 2 represents the crystal-averaged composite of three individual stereoisomers, Pt4(AuPPh3)2(mu2-CO)4(CO)2(PPh3)2 (2a), Pt3Ni(AuPPh3)2(mu2-CO)4(CO)2(PPh3)2 (2b), and Pt2Ni2(AuPPh3)2(mu2-CO)4(CO)2(PPh3)2 (2c). Formal Ni substitution for Pt at only the basal M(B) site(s) in the four crystal composites each of 1 and 2 was found to vary widely from 17% to 79% Ni in 1 and from 21% to 95% Ni in 2. Nevertheless, reasonably close Pt/Ni occupancy factors were found within each of the four pairs of composite crystals selected from samples obtained from duplicate syntheses. Both 1 and 2 may be formally derived from the electronically equivalent classic butterfly Pt4(mu2-CO)5(PPh3)4 cluster by replacement of its bridging mu2-CO ligand spanning the basal M(B)-M(B) edge with two one-electron donating (Au-Au)-linked AuPPh3 moieties along with the substitution of a terminal CO in place of one or both M(B)-attached PPh3 ligands in 1 and 2, respectively; site-specific Pt/Ni substitutional disorder occurs only at the CO-attached M(B) sites. The variable-stoichiometric 1 and 2 re also electronically equivalent and geometrically related to the crystal-ordered butterfly-based Pt4(mu2-CO)4(PR3)4(mu3-HgX)2 clusters (R3 = Ph3, MePh2; X = CF3, Br, I).     

Formation and electrocatalytic properties of Pd deposits on Mo obtained by galvanic displacement

A Pd-Mo electrocatalytic system was obtained by forming palladium particles on the Mo surface that contacted a PdCl₂ solution under open-circuit conditions. The state of palladium on the electrode surface depended on the contact displacement time. Palladium particles 5–10 nm in size formed on the surface of the Pd(Mo) electrode after palladium deposition for 1 min. The specific rates of formic acid oxidation on the Pd(Mo) electrode were smaller than those on the Pd/Pt electrode. On the Pd(Mo) electrode, anode currents of methanol oxidation were recorded at a potential of 0.4 V. The difference in the effects of the Mo substrate on the activity of Pd particles in the electrooxidations of HCOOH and CH₃OH was explained by the difference in the mechanisms of these reactions.     

Effect of Cu content on structure,hydrogen storage properties and electrode performance of LaNi4.1-x Co0.6Mn0.3Cu x alloys

The effect of Cu content on structure, hydrogen storage, and electrochemical properties of LaNi_4.1-x Co_0.6Mn_0.3Cu _x alloys has been investigated. For sample, A, B, C, and D are used to represent alloys (x?=?0, 0.15, 0.3, and 0.45), respectively. The results indicate that the four alloys are all single-phase alloy with LaNi₅ phase of CaCu₅ hexagonal structure, the hydrogen storage capacities of the alloy are about 1.49 wt% (A), 1.48 wt% (B), 1.43 wt% (C), and 1.25 wt% (D) at 303 K. With the increase of Cu content (x) from A to D, hydrogen desorption plateau pressure and pressure hysteresis decrease. Alloy electrode A shows better activation property and higher capacity (334.44 mAh/g). The addition of Cu improves the cyclic stability of the alloy electrodes when x?=?0?~?0.45. However, their self-discharge properties and high-rate dischargeability (HRD) decrease with the increase of x. Further, electrochemical kinetics and electrochemical impedance spectroscopy (EIS) analysis show that the reaction of alloy electrode is controlled by charge transfer step, and the adding of Cu benefits the electrode properties in alkaline solution.     

One-pot synthesis of Cu1.94S-CdS and Cu1.94S-Zn(x)Cd(1-x)S nanodisk heterostructures

Nanodisk heterostructures consisting of monoclinic Cu(1.94)S and wurtzite CdS have been colloidally synthesized for the first time. Initially, hexagonal-shaped nanodisks of Cu(1.94)S were produced upon thermolysis of a copper complex in a solvent mixture of HDA and TOA at 250 °C. Rapid addition of Cd precursor to the reaction mixture resulted in the partial conversion of Cu(1.94)S into CdS, yielding Cu(1.94)S-CdS nanoheterostructures. The original morphology of the Cu(1.94)S nanodisks was conserved during the transformation. When Zn precursor was added together with the Cd precursor, Cu(1.94)S-Zn(x)Cd(1-x)S nanodisks were generated. These two-component nanostructures are potentially useful in the fabrication of heterojunction solar cells.     

Tailored vapor-phase growth of Cu(x)O-TiO2 (x = 1, 2) nanomaterials decorated with Au particles

We report on the fabrication of Cu(x)O-TiO(2) (x = 1, 2) nanomaterials by an unprecedented vapor-phase approach. The adopted strategy involves the growth of porous Cu(x)O matrices by means of chemical vapor deposition (CVD), followed by the controlled dispersion of TiO(2) nanoparticles. The syntheses are performed on Si(100) substrates at temperatures of 400-550 °C under wet oxygen atmospheres, adopting Cu(hfa)(2)·TMEDA (hfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate; TMEDA = N,N,N',N'-tetramethylethylenediamine) and Ti(O-(i)Pr)(2)(dpm)(2) (O-(i)Pr = isopropoxy; dpm = 2,2,6,6-tetramethyl-3,5-heptanedionate) as copper and titanium precursors, respectively. Subsequently, finely dispersed gold nanoparticles are introduced in the as-prepared systems via radio frequency (RF)-sputtering under mild conditions. The synthesis process results in the formation of systems with chemical composition and nano-organization strongly dependent on the nature of the initial Cu(x)O matrix and on the deposited TiO(2) amount. The decoration with low-size gold clusters paves the way to the engineering of hierarchically organized nanomaterials.     

Temporal evolution of benzenethiolate SAMs on Cu(100)

The structure and thermal stability of self-assembled monolayers (SAMs) of benzenethiolate (BT) on Cu(100) have been studied by means of thermal desorption spectroscopy (TDS), scanning tunneling microscopy (STM), low-energy electron diffraction (LEED), UV photoelectron spectroscopy (UPS), X-ray photoelectron spectroscopy (XPS), and near-edge X-ray adsorption fine structure spectroscopy (NEXAFS). Vapor deposition at room temperature yields a well-ordered, densely packed c(6 × 2) saturation structure. At room temperature, this film is, however, metastable and transforms via partial decomposition by cleavage of the S-C bond into a less densely packed layer that reveals a coexisting p(2 × 2) phase. Such a transition occurs on a time scale of several days and is accompanied by a reduction of the work function change with respect to the bare Cu(100) surface from Δ? = -0.9 eV for a freshly prepared saturated layer to -0.5 eV for an aged film. TDS experiments exhibit the presence of two distinct desorption channels (dissociative and intact desorption) occurring at different temperatures that reflects a variation of the local Cu-S interaction strength of BT at differently coordinated adsorption sites. Heating to above room temperature causes a rapid degradation and continuous thinning of BT films whereas above 500 K all thiolate species have desorbed or dissociated, leaving a sulfide overlayer behind that is accompanied by a substrate reconstruction. Interestingly, the upright orientation of BT adopted in the saturated monolayer remains almost identical upon heating and demonstrates the absence of downward tilting upon thermally induced thinning of the film.     

Surface characterization of Pt electrodes using underpotential deposition of H and Cu: Part I. Pt(100)

This paper is the first in a series describing the in situ surface characterization of platinum electrodes using H and Cu deposited at underpotentials. The surface of a Pt(100) electrode pretreated by simple flame annealing and quenching in aqueous sulfuric acid is shown to contain a high concentration of defects such as vacancies and self-adsorbed Pt atoms. Adsorbed hydrogen is more strongly bound at these defects than on a uniform Pt(100) surface. Potential cycling in 1 M HCl produces a higher concentration of defects, while oxide formation and reduction in 0.5 M H₂SO₄ has the opposite effect. The nature of (100)-like sites at a polycrystalline platinum electrode is also discussed.     

Influence of the metal loading on the electrocatalytic activity of carbon-supported (100) Pt nanoparticles

Journal of Solid State Electrochemistry - The influence of the metal loading (i.e. interparticle distance) of shape-controlled Pt nanoparticles on their electrocatalytic properties is evaluated for...