Unequal-sphere packing model for simulation of the uniaxially compressed iodine adlayer on Au(111)

A simple unequal-sphere packing (USP) model, based on pure geometrical principles, was applied to study the centered-rectangular iodine c(px radical3)R30 degrees adlayer on the Au(111) surface, well-known from surface X-ray structure (SXS), low energy electron diffraction (LEED), and scanning tunneling microscopy (STM) experiments. To reproduce the exact patterns observed in experiments, two selective conditions-minimum average adsorbate height and minimum adlayer roughness-were imposed. As a result, a series of adlayer patterns with c(px radical3)R30 degrees symmetry (2.3 < p < 3), with precise structural details, including atomic registry and identification of the p-bisector as the most likely trajectory for the iodine adatom movement during the so-called uniaxial compression phenomenon, were identified. In addition, using the same model, the difference between the iodine adlayer arranged in hexagonal and centered-rectangular c(px radical3)R30 degrees patterns, as in the case of Pt(111) and Au(111) surfaces, was investigated. Qualitative and quantitative comparison shows that iodine adatoms in these two arrangements differ significantly in atomic registry, distance from the substrate, and the adlayer corrugation. Our findings could be of special interest in the study of the nature of the iodine adatom bonding to different substrates (i.e., Au vs Pt).     

Thermodynamic considerations and computer simulations on the formation of core-shell nanoparticles under electrochemical conditions

We report on thermodynamic modeling and computer simulations on the electrochemical generation of metallic and bimetallic nanoparticles (NPs) by means of quenched molecular dynamics (QMD). The present results suggest that the spontaneous formation of core-shell NPs depends on several factors, i.e. size and shape of the core, chemical composition of the system, and under-/oversaturation conditions. Homo- and heteroatomic prototypical systems were considered. The former systems were Au and Pt. The latter were Ag(core)/Au(shell), Pt(core)/Au(shell), Au(core)/Ag(shell) and Au(core)/Pt(shell).     

A density functional theory approach to mushroom-like platinum clusters on palladium-shell over Au core nanoparticles for high electrocatalytic activity

Recently, it was found that Pt clusters deposited on Pd shell over Au core nanoparticles (Au@Pd@Pt NPs) exhibit unusually high electrocatalytic activity for the electro-oxidation of formic acid (P. P. Fang, S. Duan, et al., Chem. Sci., 2011, 2, 531-539). In an attempt to offer an explanation, we used here carbon monoxide (CO) as probed molecules, and applied density functional theory (DFT) to simulate the surface Raman spectra of CO at this core-shell-cluster NPs with a two monolayer thickness of Pd shell and various Pt cluster coverage. Our DFT results show that the calculated Pt coverage dependent spectra fit the experimental ones well only if the Pt clusters adopt a mushroom-like structure, while currently the island-like structure is the widely accepted model, which follows the Volmer-Weber growth mode. This result infers that there should be a new growth mode, i.e., the mushroom growth mode as proposed in the present work, for Au@Pd@Pt NPs. We suggest that such a mushroom-like structure may offer novel active sites, which accounts for the observed high electrocatalytic activity of Au@Pd@Pt NPs.     

Au Nanoparticles Modified with Pt,Ru and SnO2 as Electrocatalysts for Ethanol Oxidation Reaction in Acids

The anodic reaction in direct ethanol fuel cells (DEFCs), ethanol oxidation reaction (EOR) faces challenges, such as incomplete electrooxidation of ethanol and high cost of the most efficient electrocatalyst, Pt in acidic media at low temperature. In this study, core‐shell electrocatalysts with an Au core and Pt‐based shell (Au@Pt) are developed. The Au core size and Pt shell thickness play an important role in the EOR activity. The Au size of 2.8 nm and one layer of Pt provide the most optimized performance, having 6 times higher peak current density in contrast to commercial Pt/C. SnO₂ as a support also enhances the EOR activity of Au@Pt by 1.73 times. Further modifying the Pt shell with Ru atoms achieve the highest EOR current density that is 15 and 2.5 times of Pt/C and Au@Pt. Our results suggest the importance of surface modification in rational design of advanced electrocatalysts.     

Self-assembly of mixed Pt and Au nanoparticles on PDDA-functionalized graphene as effective electrocatalysts for formic acid oxidation of fuel cells

Pt and Au nanoparticles with controlled Pt?:?Au molar ratios and PtAu nanoparticle loadings were successfully self-assembled onto poly(diallyldimethylammonium chloride) (PDDA)-functionalized graphene (PDDA-G) as highly effective electrocatalysts for formic acid oxidation in direct formic acid fuel cells (DFAFCs). The simultaneously assembled Pt and Au nanoparticles on PDDA-G showed superb electrocatalytic activity for HCOOH oxidation, and the current density associated with the preferred dehydrogenation pathway for the direct formation of CO(2) through HCOOH oxidation on a Pt(1)Au(8)/PDDA-G (i.e., a Pt?:?Au ratio of 1?:?8) is 32 times higher than on monometallic Pt/PDDA-G. The main function of the Au in the mixed Pt and Au nanoparticles on PDDA-G is to facilitate the first electron transfer from HCOOH to HCOO(ads) and the effective spillover of HCOO(ads) from Au to Pt nanoparticles, where HCOO(ads) is further oxidized to CO(2). The Pt?:?Au molar ratio and PtAu nanoparticle loading on PDDA-G supports are the two critical factors to achieve excellent electrocatalytic activity of PtAu/PDDA-G catalysts for the HCOOH oxidation reactions.     

Study of nucleation and growth mechanism of the metallic nanodumbbells

We propose a general nucleation and growth model that can explain the mechanism of the formation of CoPt(3)/Au, FePt/Au, and Pt/Au nanodumbbells. Thus, we found that the nucleation event occurs as a result of reduction of Au(+) ions by partially oxidized surface Pt atoms. In cases when Au(3+) is used as a gold precursor, the surface of seeds should be terminated by ions (e.g., Co(2+), Pb(2+)) that can reduce Au(3+) to Au(+) ions, which can further participate in the nucleation of gold domain. Further growth of gold domain is a result of reduction of both Au(3+) and Au(+) by HDA at the surface of gold nuclei. We explain the different ability of CoPt(3), Pt, and FePt seeds to serve as a nucleation center for the reduction of gold and further growth of dumbbells. We report that the efficiency and reproducibility of the formation of CoPt(3)/Au, FePt/Au, and Pt/Au dumbbells can be optimized by the concentration and oxidation states of the surface ions on metallic nanocrystals used as seeds as well as by the type of the gold precursor.     

Quasi-relativistic density functional study of aurophilic interactions

Fifteen molecules containing the Au(I) species have been calculated by ab initio HF and MP2 methods and by five different density functional approaches. The aurophilic Au(d10)-Au(d10) bonding mechanism has been investigated. Both, one-electron interactions (i.e., electrostatic, polarization, charge transfer, and orbital interference) and two-electron effects (i.e., correlation, dispersion) contribute significantly to the so-called 'secondary' or metallophilic bonds representing the Au-Au interaction. Second, the applicability of density functional approaches to this type of bonding has been tested. It is well-known that present day density functionals are not yet designed to simulate the long-range London dispersion forces between nonoverlapping systems, whereas they approximately reproduce the short range dynamical electron correlations of strongly overlapping chemically bonded nondegenerate species. It is found here empirically for the investigated groups of gold(I) cluster compounds that simple local density functionals (LDF) of the Slater (or Slater plus Vosko) type yield rather reasonable estimates for the equilibrium distances, and (on the average) also for the aurophilic interaction energies, though with rather large standard deviations. Still LDF are useful for survey investigations of Au cluster compounds. Common gradient corrected DF are not recommended here, nor are the large core pseudopotentials for Au.     

Adsorption of cyclohexene and its dehydrogenation intermediates on nAu/Pt(100)(n＝0,1,2) surfaces:A DFT study

Adsorption of cyclohexene and its dehydrogenation intermediates on the nAu/Pt(100) (n = 0, 1, 2 means clean Pt, one monolayer and two layers of Au covered Pt surfaces, respectively.) has been investigated by self-consistent (GGA-PW91) density functional theory combined with periodic slab model. It is found that on the clean platinum, there are two kinds of favorable adsorption sites, i.e., hollow sites and bridge sites, and the adsorption energy at the hollow site is larger than that at the bridge site. However, on the Au/Pt and 2Au/Pt surfaces, there are three kinds of adsorption sites, and the adsorption energies are alike at both the bridge site and the top site. The magnitude order of the adsorption energies is as follows: clean Pt > Au/Pt > 2Au/Pt. The configurations of cyclohexene molecule have been distorted a little during the geometry optimizations. The lengths of C–M (M = Pt or Au, on the top layer of the slab) bonds are closely related to the corresponding adsorption energies.     

低温静电自组装法制备贵金属修饰TiO_2纳米结构薄膜及其增强的光催化性能(英文)

以碱-水热法在金属Ti片上原位生长了TiO2纳米结构(纳米花和纳米线)薄膜,并采用低温静电自组装方法将超细贵金属(金、铂、钯)纳米颗粒均匀沉积于多孔TiO2薄膜上.负载于Ti片上的贵金属/TiO2纳米结构薄膜具有一体化结构、多孔架构和高光催化活性.超高分辨率场发射扫描电子显微镜(FESEM)直接观察表明贵金属纳米颗粒在TiO2表面分布均匀,且颗粒之间相互分离,金、铂、钯纳米颗粒的平均粒径分别约为4.0、2.0和10.0nm.俄歇电子能谱(AES)纵深成分分析表明贵金属不仅沉积于薄膜表面,且大量分布于TiO2纳米结构薄膜内部,其深度超过580 nm.X射线光电子能谱(XPS)分析表明,经300°C下在空气中热处理后,纳米金仍保持金属态,纳米铂部分被氧化成PtOabs,而钯粒子则完全被氧化成氧化钯(PdO).以低温静电自组装法沉积贵金属,贵金属负载量可通过调节组装时间与溶胶pH值来控制.光催化降解甲基橙的结果表明,沉积的纳米金和铂能显著增加TiO2纳米结构薄膜的光催化活性,说明金和铂粒子可促进光生载流子的分离;但负载的PdO对TiO2薄膜的光催化性能增强几乎无作用.     

Electrochemistry of conductive polymers 39. Contacts between conducting polymers and noble metal nanoparticles studied by current-sensing atomic force microscopy

Electrical properties of contacts formed between conducting polymers and noble metal nanoparticles have been examined using current-sensing atomic force microscopy (CS-AFM). Contacts formed between electrochemically prepared pi-conjugated polymer films such as polypyrrole (PPy), poly(3-methylthiophene) (P3MeT), as well as poly(3,4-ethylenedioxythiophene) (PEDOT) and noble metal nanoparticles including platinum (Pt), gold (Au), and silver (Ag) have been examined. The Pt nanoparticles were electrochemically deposited on a pre-coated PPy film surface by reducing a platinum precursor (PtCl62-) at a constant potential. Both current and scanning electron microscopic images of the film showed the presence of Pt islands. The Au and Ag nanoparticles were dispersed on the P3MeT and PEDOT film surfaces simply by dipping the polymer films into colloid solutions containing Au or Ag particles for specified periods (5 to approximately 10 min). The deposition of Au or Ag particles resulted from either their physical adsorption or chemical bonding between particles and the polymer surface depending on the polymer. When compared with PPy, P3MeT and PEDOT showed a stronger binding to Au or Ag nanoparticles when dipped in their colloidal solutions for the same period. This indicates that Au and Ag particles are predominantly linked with the sulfur atoms via chemical bonding. Of the two, PEDOT was more conductive at the sites where the particles are connected to the polymer. It appears that PEDOT has better aligned sulfur atoms on the surface and is strongly bonded to Au and Ag nanoparticles due to their strong affinity to gold and silver. The current-voltage curves obtained at the metal islands demonstrate that the contacts between these metal islands and polymers are ohmic.     

Well-controlled synthesis of Au@Pt nanostructures by gold-nanorod-seeded growth

Pt nanodots were formed on Au nanorods (NRs) by using a simple seed-mediated growth. Their density and distribution on the Au NR can be finely tuned by varying the reaction parameters. At lower Pt/Au ratios, the Pt nanodots mainly appear at endcaps and side edges of the Au rod. At higher Pt/Au ratios, they distribute homogeneously over the whole Au rod. The obtained Pt nanostructure is a single crystal owing to the epitaxial growth of Pt on the Au rod. Due to the unique surface plasmon resonance (SPR) features of the Au NRs, the Au core/Pt shell (Au@Pt) nanostructures also exhibit well-defined and red-shifted longitudinal SPR bands in the visible and near-infrared region. The position and intensity can be regulated by the thickness and amount of the Pt shell. At a thinner Pt thickness, the Au@Pt NRs show higher dielectric sensitivity than the corresponding Au NRs. It thus opens up the potential of Pt nanostructures for SPR-based sensing.     

Electrochemical Designing of Au/Pt Core Shell Nanoparticles as Nanostructured Catalyst with Tunable Activity for Oxygen Reduction

Au/Pt core shell nanoparticles (NPs) have been prepared via a layer‐by‐layer growth of Pt layers on Au NPs using underpotential deposition (UPD) redox replacement technique. A single UPD Cu monolayer replacement with Pt(II) yielded a uniform Pt film on Au NPs, and the shell thickness can be tuned by controlling the number of UPD redox replacement cycles. Oxygen reduction reaction (ORR) in air‐saturated 0.1 M H₂SO₄ was used to investigate the electrocatalytic behavior of the as‐prepared core shell NPs. Cyclic voltammograms of ORR show that the peak potentials shift positively from 0.32 V to 0.48 V with the number of Pt layers increasing from one to five, suggesting the electrocatalytic activity increases with increasing the thickness of Pt shell. The increase in electrocatalytic activity may originate mostly from the large decrease of electronic influence of Au cores on surface Pt atoms. Rotating ring‐disk electrode voltammetry and rotating disk electrode voltammetry demonstrate that ORR is mainly a four‐electron reduction on the as‐prepared modified electrode with 5 Pt layers and first charge transfer is the rate‐determining step.     

Cinchonidine adsorption on gold and gold-containing bimetallic platinum metal surfaces: an attenuated total reflection infrared and density functional theory study

Adsorption of cinchonidine on monometallic Au and bimetallic Pt-Au and Pd-Au thin model films prepared by physical vapor deposition has been investigated with attenuated total reflection infrared (ATR-IR) spectroscopy. On Au the alkaloid forms an adsorbed layer that shows higher stability against desorption than the corresponding adsorption on Pt. In this adsorption layer the intermolecular interactions dominate over metal-adsorbate interactions as indicated by the absence of the spectroscopic features attributed to strongly flat adsorbed species. This behavior is further supported by Density Functional Theory (DFT) calculations indicating that flat and tilted orientations of the quinoline ring have comparable adsorption energy on Au but lower (7-10 kcal/mol) compared to adsorption on Pt (ca. 40 kcal/mol). As a consequence, the creation of a metal surface with isolated chiral sites is prevented by formation of an adsorbed structure formed by intermolecularly bound cinchonidine molecules on Au. While the binding to Pt is due to the formation of sigma-bonds to surface atoms, such aggregates are bound to Au mainly by van der Waals forces. Given this different nature of bonding of cinchonidine to Au and Pt, addition of Au to Pt and Pd films could be used to probe the changes of fractional coverage of the different adsorbed species of cinchonidine on the platinum metals. It is demonstrated that the lowering of the domain size of the platinum group metal by Au can simulate the effect of particle size on the distribution of the surface conformations of the alkaloid on a metal surface.     

Surface-enhanced Raman spectroscopy using gold-core platinum-shell nanoparticle film electrodes: toward a versatile vibrational strategy for electrochemical interfaces

The aim of this work is to further improve the molecular generality and substrate generality of SERS (i.e., to fully optimize the SERS activity of transition-metal electrodes). We utilized a strategy of borrowing high SERS activity from the Au core based on Au-core Pt-shell (Au@Pt) nanoparticle film electrodes, which can be simply and routinely prepared. The shell thickness from about one to five monolayers of Pt atoms can be well controlled by adjusting the ratio of the number of Au seeds to Pt(IV) ions in the solution. The SERS experimental results of carbon monoxide adsorption indicate that the enhancement factor for the Au@Pt nanoparticle film electrodes is more than 2 orders of magnitude larger than that of electrochemically roughened Pt electrodes. The practical virtues of the present film electrodes for obtaining rich and high-quality vibrational information for diverse adsorbates on transition metals are pointed out and briefly illustrated with systems of CO, hydrogen, and benzene adsorbed on Pt. We believe that the electrochemical applications of SERS will be broadened with this strategy, in particular, for extracting detailed vibrational information for adsorbates at transition-metal electrode interfaces.     

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.     

Influence of hydrogen electrosorption on surface oxidation of Pd and Pd-noble metal alloys

Electrochemical oxidation of freshly deposited Pd and its alloys with other noble metals (Au, Pt, Rh) was compared with the behavior of samples subjected to prior hydrogen absorption/desorption procedure. It was found that surface oxidation of hydrogen-treated Pd and Pd–Pt–Au deposits starts at lower potentials than on non-hydrided electrodes and is accompanied by a negative shift of surface oxide reduction peak. Pd and its alloys with Au, Pt and Rh after hydrogen treatment are also more resistant to electrochemical dissolution than freshly deposited samples.     

Temperature-dependent structuring of Au-Pt bimetallic nanoclusters on a thin film of Al2O3/NiAl(100)

Au-Pt bimetallic nanoclusters on a thin film of Al(2)O(3)/NiAl(100) undergo significant structural evolution on variation of the temperature. Au and Pt deposited sequentially from the vapor onto thin-film Al(2)O(3)/NiAl(100) at 300 K form preferentially bimetallic nanoclusters (diameter ≦ 6.0 nm and height ≦ 0.8 nm) with both Au and Pt coexisting at the cluster surface, despite the order of metal deposition. These bimetallic clusters are structurally ordered, have a fcc phase and grow with their facets either (111) or (001) parallel to the θ-Al(2)O(3)(100) surface. Upon annealing the clusters to 400-500 K, the Au atoms inside the clusters migrate toward the surface, resulting in formation of a structure with a Pt core and an Au shell. Annealing the sample to 500-650 K reorients the bimetallic clusters--all clusters have their (001) facets parallel to the oxide surface--and induces oxidation of Pt. Such annealed bimetallic clusters become encapsulated with the aluminium-oxide materials and a few Au remain on the surface.     

Using Size-Exclusion Chromatography to Evaluate Changes in the Sizes of Au and Au/Pd Core/Shell Nanoparticles Under Thermal Treatment

In this study, we used size-exclusion chromatography (SEC) to evaluate the sizes of Au and Au/Pd core/shell nanoparticles (NPs) that had been subjected to thermal treatment, with the eluted NPs monitored through diode array detection (DAD) of the surface plasmon (SP) absorption of the NPs. In the absence of an adequate stabilizer, thermal treatment resulted in longer retention times for the Au NPs and shorter retention times for the Au/Pd core/shell NPs in the SEC chromatograms. Thus, thermal treatment influenced the sizes of these Au and Au/Pd core/shell NPs, through digestive ripening and Ostwald-type growth, respectively. In addition, the trends in the SP absorption phenomena of the NPs in the eluted samples, as measured using DAD, were consistent with the trends of their size variations, as measured from their elution profiles. In the presence of 3A-amino-3A-deoxy-(2AS,3AS)-??-cyclodextrin (H₂N-??-CD) as a stabilizer, the retention times and SP absorptions of the eluted Au and Au/Pd NP samples remained constant. Thus, H₂N-??-CD is a good stabilizer against size variation duration the thermal treatment of Au and Au/Pd core/shell NPs. A good correlation existed between the sizes obtained using SEC and those provided by transmission electron microscopy. Therefore, this SEC strategy is an effective means of further searching for suitable stabilizers for NPs, especially those exposed to harsh reaction conditions (e.g., in catalytic reactions).     

Structurally heterogeneous electrode films of polyacrylamide and acrylamide/vinylpyridine copolymeric gels: Mediation of ascorbic acid oxidation

The surface chemistry, i.e. adsorption and surface phase formation, on Rh, Ir, Pt and Au single-crystal electrodes in 0.5 M H₂SO₄ has been studied in the potential range between 0 and 4 V vs. a standard hydrogen electrode by X-ray photoelectron spectroscopy and cyclic voltammetry. Both methods gave complementary results which were interpreted as potential-dependent changes from physisorption of water to adsorption of hydroxyl groups, hydroxide film formation, and eventual growth of thick adlayers of oxyhydroxide (Rh, Ir and Au) or hydroxide (Pt) with increasing applied voltage.