Synthesis and characterization of PtSn/carbon and Pt3Sn/carbon nanocomposites as methanol electrooxidation catalysts

Two Pt-Sn/vulcan carbon nanocomposites containing nanoclusters of PtSn (niggliite) and Pt3Sn highly dispersed on a carbon powder support have been prepared using Pt(SnPh2Cl)(PPh3)2(Ph) or [Pt3[mu-(PPh2)2CH2]3(mu 3-SnF3) (mu 3-CO)][PF6] as single-source precursors of metal alloy. PtP2 or Pt metal is also present as a secondary phase. Bimetallic Pt-Sn nanoclusters with an average diameter of 5-8 nm are formed at a total metal loading of ca. 15 wt%. Evaluation of both Pt-Sn/C nanocomposites as electrooxidation catalysts in a direct methanol fuel cell gives fuel cell performances comparable to that expected for Pt-Sn catalysts prepared by more conventional methods.     

Synthesis, characterization, and electrochemical properties of mono-, di-, and trinuclear transition Metal [60]fullerene complexes containing diphosphine cis-Ph2PCH=CHPPh2 ligand

New transition metal fullerene complexes containing cis-Ph2PCH=CHPPh2 (dppet) ligand have been investigated. The mononuclear complexes (etau2-C60)M(cis-dppet) (1, 2; M = Pd, Pt) were prepared by reaction of C60 with M(dba)2 (dba = dibenzylideneacetone) followed by treatment with cis-dppet, while the in situ prepared 1 and 2 reacted with M1(PPh3)4 to afford dinuclear complexes (eta2 : eta2-C60)M(cis-dppet)M1 (PPh3)2 (3-6; M, M1 = Pd, Pt). Similarly, trinuclear complexes (eta2 : eta2-C60) M(cis-dppet)M1 (dppr) (7-10; M, M1 = Pd, Pt; dppr = (eta5-Ph2PC5H4)2Ru) could be synthesized by reaction of the in situ prepared 3-6 with dppr. 1-10 were characterized by elemental analysis and spectroscopy. Cyclic voltammetric studies on 2 (M = Pt), 3 (M = Pd, M1 = Pd) and 9 (M = Pt, M1 = Pd) provided further evidence for the eta2-coordination of C60 to one metal fragment or two metal fragments in these complexes.     

Facet-controlled Pt–Ir nanocrystals with substantially enhanced activity and durability towards oxygen reduction

Nanocrystals made of Pt–Ir alloys are fascinating catalysts towards the oxygen reduction reaction (ORR), but the lack of control over their surface atomic structures hinders further optimization of their catalytic performance. Here we report, for the first time, a class of highly active and durable ORR catalysts based on Pd@Pt–Ir nanocrystals with well-controlled facets. With an average of 1.6 atomic layers of a Pt₄Ir alloy on the surface, the nanocrystals can be made in cubic, octahedral, and icosahedral shapes to present Pt–Ir {1 0 0}, {1 1 1}, and {1 1 1} plus twin boundaries, respectively. The Pd@Pt–Ir nanocrystals exhibit not only facet-dependent catalytic properties but also substantially enhanced ORR activity and durability relative to a commercial Pt/C and their Pd@Pt counterparts. Among them, the Pd@Pt–Ir icosahedra deliver the best performance, with a mass activity of 1.88 A·mg⁻¹_Pt at 0.9 V, which is almost 15 times that of the commercial Pt/C. Our density functional theory (DFT) calculations attribute the high activity of the Pd@Pt–Ir nanocrystals, and the facet dependence of these activities, to easier protonation of O* and OH* under relevant OH* coverages, relative to the corresponding energetics on clean Pd@Pt surfaces. The DFT calculations also indicate that incorporating Ir atoms into the Pt lattice destabilizes OH–OH interactions on the surface, thereby raising the oxidation potential of Pt and greatly improving the catalytic durability.     

Pt nanoparticles: Heat treatment-based preparation and Ru(bpy)(3)2+-mediated formation of aggregates that can form stable films on bare solid electrode surfaces for solid-state electrochemiluminescence detection

A simple thermal process for the preparation of small Pt nanoparticles is presented, carried out by heating a H2PtCl6/3-thiophenemalonic acid aqueous solution. The following treatment of such colloidal Pt solution with Ru(bpy)(3)2+ causes the assembly of Pt nanoparticles into aggregates. Most importantly, directly placing such aggregates on bare solid electrode surfaces can produce very stable films exhibiting excellent electrochemiluminescence behaviors.     

Shape and composition-controlled platinum alloy nanocrystals using carbon monoxide as reducing agent

The shape of metal alloy nanocrystals plays an important role in catalytic performances. Many methods developed so far in controlling the morphologies of nanocrystals are however limited by the synthesis that is often material and shape specific. Here we show using a gas reducing agent in liquid solution (GRAILS) method, different Pt alloy (Pt-M, M = Co, Fe, Ni, Pd) nanocrystals with cubic and octahedral morphologies can be prepared under the same kind of reducing reaction condition. A broad range of compositions can also be obtained for these Pt alloy nanocrystals. Thus, this GRAILS method is a general approach to the preparation of uniform shape and composition-controlled Pt alloy nanocrystals. The area-specific oxygen reduction reaction (ORR) activities of Pt(3)Ni catalysts at 0.9 V are 0.85 mA/cm(2)(Pt) for the nanocubes, and 1.26 mA/cm(2)(Pt) for the nanooctahedra. The ORR mass activity of the octahedral Pt(3)Ni catalyst reaches 0.44 A/mg(Pt).     

Facile synthesis of highly faceted multioctahedral Pt nanocrystals through controlled overgrowth

Highly faceted Pt nanocrystals with a large number of interconnected arms in a quasi-octahedral shape were synthesized simply by reducing H2PtCl6 precursor with poly(vinyl pyrrolidone) in aqueous solutions containing a trace amount of FeCl3. The iron species (Fe(3+) or Fe(2+)) play a key role in inducing the formation of the multioctahedral structure by decreasing the concentration of Pt atoms and keeping a low concentration for the Pt seeds during the reaction. This condition favors the overgrowth of Pt seeds along their corners and thus the formation of multiarmed nanocrystals. Electron microscopy studies revealed that the multioctahedral Pt nanocrystals exhibit a large number of edge, corner, and surface step atoms. The size of the multioctahedral Pt nanocrystals can be controlled by varying the concentration of FeCl3 added to the reaction and/or the reaction temperature. These multioctahedral Pt nanocrystals were tested as electrocatalysts for the oxygen reduction reaction in a proton exchange membrane fuel cell and exhibited improved specific activity and durability compared to commercial Pt/C catalyst.     

Synthesis of FePt nanorods and nanowires by a facile method

FePt nanorods and nanowires have been synthesized by the reduction of Pt(acac)(2) and the thermal decomposition of Fe(CO)(5) in the presence of solvents/surfactants by simply controlling the sequence of addition of surfactants. The as-synthesized FePt nanorods and nanowires have a face centered cubic structure with average diameter of 3?nm. Length of nanorods and nanowires can be adjusted in the range of 15-150?nm by varying reaction parameters. Nanocrystalline L1(0) FePt phase with coercivity up to 24?kOe was obtained after heat treatments.     

原位表面掺杂增强PtNiCoRh纳米晶对C1燃料电氧化的催化性能

异质原子掺杂的铂基纳米晶在多相催化领域具有广阔的应用前景,然而基于原位表面掺杂策略来优化表面原子构型仍颇具挑战.本研究通过原位表面掺杂的化学方法制备出多枝状PtNiCoRh四元金属纳米晶.抗坏血酸和铑离子的配位作用实现了铑离子的延迟还原,从而可控地将铑原子锚定在催化剂表面层.电催化研究表明原位表面掺杂的Pt₆₇Ni₁₆Co₁₆Rh₁纳米晶针对甲醇、甲醛和甲酸电氧化都具有优异的催化活性、稳定性及抗CO中毒特性.原位电化学红外光谱结果表明抗腐蚀性强的铑原子的表面掺杂能有效调控催化剂表面Pt位点,其中CO中毒中间体以更容易氧化消除的桥位态吸附在Rh–Pt异质位点.本研究提出的原位表面掺杂策略将有助于设计高原子利用率的高效多相催化剂.     

二维碳化钛/碳纳米管负载铂钌粒子的制备及电催化性能研究

直接甲醇燃料电池因操作方便、转化效率高、操作温度低、污染少以及液体燃料易存储易运输等优势具有良好的应用前景, 但现有阳极催化剂存在催化活性低、抗CO中毒性差等缺点, 制约了其商业化应用前景。本研究采用三步法制备得到了一系列不同Pt、Ru配比的PtRu/(Ti₃C₂T_x)_0.5-(MWCNTs)_0.5阳极催化剂材料, HF腐蚀Ti₃AlC₂得到Ti₃C₂T_x, 与酸化处理的多壁碳纳米管(MWCNTs)复合后通过溶剂热法负载Pt、Ru颗粒。通过XRD、SEM、EDS、TEM、XPS等分析铂钌的协同关系。结果表明: Ru原子与Pt原子晶格混合, 形成了粒径约3.6 nm的铂钌双金属合金。电化学分析结果表明: Pt₁Ru_0.5/(Ti₃C₂T_x)_0.5-(MWCNTs)_0.5催化剂具有最佳的电化学性能, 其电化学活性面积(Electrochemical Active Area, ECSA)为139.5 m ²/g, 正向峰电流密度为36.4 mA/cm ²。     

Growth Mechanism of Metal Clusters on a Graphene/Ru(0001) Template

Using first‐principles calculations combined with scanning tunneling microscopy experiments, we investigated the adsorption configurations, electronic structures and the corresponding growth mechanism of several transition metal (TM) atoms (Pt, Ru, Ir, Ti, Pd, Au, Ag, and Cu) on a graphene/Ru(0001) moiré template (G/Ru(0001)) at low coverage. We find that Pt, Ru, Ir, and Ti selectively adsorb on the fcc region of G/Ru(0001) and form ordered dispersed metal nanoclusters. This behavior is due to the unoccupied d orbital of the TM atoms and the strong sp³ hybridization of carbon atoms in the fcc region of G/Ru(0001). Pd, Au, Ag, and Cu form nonselective structures because of the fully occupied d orbital. This mechanism can be extended to metals on a graphene/Rh(111) template. By using Pt as an example, we provide a layer by layer growth path for Pt nanoclusters in the fcc region of the G/Ru(0001). The simulations of growth mechanism agree well with the experimental observations. Moreover, they also provide guidance for the selection of suitable metal atoms to form ordered dispersed metal nanoclusters on similar templates.     

DNA binding to fluorescent ruthenium species released from calcium phosphate/nanoporous silicon structures

This work centers on an analysis of calf thymus DNA binding to emissive Ru complexes which diffuse from biocompatible calcium phosphate/nanoporous silicon films. These nanostructures were characterized by scanning electron microscopy, atomic force microscopy, energy dispersive X-ray analysis, and infrared vibrational spectroscopy. In terms of polynucleotide binding, three different systems were analyzed: (1) an aqueous solution of Ru(phen)(3)2+ (a control); (2) surface-adsorbed Ru(phen)(3)2+ onto undoped calcium phosphate/porous Si/Si in aqueous solution; (3) as-prepared and annealed Ru(phen)3(2+)-doped calcium phosphate/porous Si structures in water. For films with fluorescent Ru originally embedded throughout the film, biphasic diffusion character is found; such behavior is attributed to DNA binding to both surface-bound Ru(phen)(3)2+ and species which originate from deeper regions of the film.     

Cyclic-Oxidation Behavior of Multilayered Pt/Ru-Modified Aluminide Coating

Multilayered Pt/Ru modified aluminide coating for thermal barrier coating(TBC) systems has been investigated.2 μm Pt+2 μm Ru+2 μm Pt was first deposited on nickel-base superalloy DZ125 by electrodeposition,and then the coating was treated by annealing and a conventional pack-cementation aluminizing process.The cyclic oxidation tests were carried out at 1423 K in air.It was found that the thermal cyclic oxidation resistance of Pt/Ru-modified aluminide coating was comparable to that of Pt-modified aluminide coating,which was much better than simply aluminized DZ125.The addition of Ru to Pt-modified aluminide coating increased the resistance to rumpling.The microstructures and phase constitutions of the coating before and after oxidation were investigated.     

Superparamagnetic bimetallic iron-palladium nanoalloy: synthesis and characterization

Iron-palladium nanoalloy in the particle size range of 15-30?nm is synthesized by the relatively low temperature thermal decomposition of coprecipitated [Fe(Bipy)(3)]Cl(2) and [Pd(Bipy)(3)]Cl(2) in an inert ambient of dry argon gas. The silvery black Fe-Pd alloy nanoparticles are air-stable and have been characterized by EDX-RF, XRD, AFM, TEM, magnetometry, (57)Fe M?ssbauer and impedance spectroscopy. This Fe-Pd nanoalloy is in single phase and contains iron sites having up to 11 nearest-neighboring atoms. It is superparamagnetic in nature with high magnetic susceptibility, low coercivity and hyperfine field.     

Synthesis and self-assembly of ultrathin Ni(x)Fe(1-x)(OH)2 nanodiscs via a wet-chemistry method

Self-assembled ultrathin Ni(x)Fe(1-x)(OH)2 nanodiscs have been synthesized by using a wet-chemistry method. The uniformity and the assembly of Ni(x)Fe(1-x)(OH)2 nanostructures are sensitive to the iron ion concentration in the precursor. An optimum iron concentration of 10% results in the formation of uniform ultrathin Ni(x)Fe(1-x)(OH)2 nanodiscs with a typical side length of 50 nm and a thickness of 10 nm. They are also self-assembled by connecting their (001) facets with in-plane orientation and form a chain-like microstructure. Lattice relaxation is present within several atomic layers at the interfaces between two adjacent nanodiscs, which introduces about 6 degrees misalignment of these nanocrystals. Analytical electron microscopy analysis reveals that the iron additive atoms distribute uniformly in the nanodiscs and they are substitution atoms of Ni atoms. It has been found that the iron species is critical to the formation and assembly of the hexagonal nanodiscs.     

Determination of Dansyl Amino Acids and Oxalate by HPLC with Electrogenerated Chemiluminescence Detection Using Tris(2,2'-bipyridyl)ruthenium(II) in the Mobile Phase

A new electrogenerated chemiluminescence detection method is investigated for use in detection in reversed-phase and reversed-phase ion-pair HPLC with Ru(bpy)(3)(2+) in the mobile phase. In this method, different concentrations of Ru(bpy)(3)(2+) are dissolved in the mobile phase and the HPLC column flushed with the mobile phase for 1 h until the column is saturated with Ru(bpy)(3)(2+). The separated analytes along with Ru(bpy)(3)(2+) pass through an optical-electrochemical flow cell which has a dual platinum electrode held at a potential of 1250 mV vs a Ag/AgCl reference electrode. On the surface of the electrode, Ru(bpy)(3)(2+) is oxidized to Ru(bpy)(3)(3+) which reacts with the analytes to emit light. The retention times, retention orders, detection limits, and linearity in working curves are compared to those obtained with the conventional postcolumn Ru(bpy)(3)(2+) addition method. The retention times for dansyl amino acids with Ru(bpy)(3)(2+) in the mobile phase are longer than those obtained with the postcolumn addition approach. This may be caused by π-to-π interactions between the aromatic groups of the dansyl derivatives and the bipyridyl groups of Ru(bpy)(3)(2+) in the Ru(bpy)(3)(2+)-saturated reversed-phase column. Similarly, oxalate is separated from urine and blood plasma samples by reversed-phase ion-pair HPLC. Plasma samples are obtained using ultrafiltration to remove proteins from whole blood. Retention times for oxalate with the two detection techniques are identical, and detection limits for these techniques are compared.     

Pt-Ru双金属薄膜催化材料的合金化研究

采用离子束溅射技术制备不同Pt/Ru比PtRu合金纳米载体薄膜材料.研究了薄膜中形成PtRu合金的结构特点和组分差异.结果表明该薄膜材料在成膜过程中既有Ru渗入Pt晶格之中又有Pt渗入Ru的晶格之中,属于(Pt) (Ru)两相区的合金化过程.     

Preparation of Pt dispersed porous carbon particles from polyimide particles

We investigated the preparation of Pt and Pt/Ru bimetallic fine particles dispersed in polyimide particles by precipitation from various polyamic acid solutions containing Pt and Ru complexes, followed by the carbonization of the resulting polyimide particles. As Pt complexes, platinum(II) acetylacetonate [Pt(acac)₂], trimethylplatinum iodide [PtIMe₃], and (trimethyl) methylcyclopentadienylplatinum [Pt(MeCp)Me₃] were used. As Ru complexes, ruthenium(III) acetylacetonate [Ru(acac)₃], acenaphthylene heptacarbonyl triruthenium [(C₁₂H₈)Ru₃(CO)₇], and tetracarbonylbis(-cyclopentadienyl)diruthenium [Ru₂(CO)₄Cp₂] were used. Bow tie-like polyimide particles containing Pt or Pt/Ru bimetallic particles could be obtained from pyromellitic dianhydride /m-phenylenediamine (PMDA/MPD) polyamic acid containing Pt and Ru complexes. Sheaf-like polyimide particles were obtained by using 4,4-oxydianiline(ODA) as diamine. The morphologies of polyimide particles strongly depend on the kind and the concentration of Pt and Ru complexes. We could obtain Pt or Pt/Ru bimetallic fine particles dispersed in porous carbon particles, which morphologies are the same as the polyimide particles used as carbon precursors, by heat-treatment of the obtained polyimide particles. Pt and Pt/Ru fine particles in the range of 310 nm were contained in bow tie-like or sheaf-like carbon particles. The addition of Ru complexes to polyamic acid solutions decreased the sizes of Pt particles in carbon particles.     

Atomic layer deposition of Ru thin film using N2/H2 plasma as a reactant

Ruthenium (Ru) thin films were grown by atomic layer deposition using IMBCHRu [(η6-1-Isopropyl-4-MethylBenzene)(η4-CycloHexa-1,3-diene)Ruthenium(0)] as a precursor and a nitrogen-hydrogen mixture (N₂/H₂) plasma as a reactant, at the substrate temperature of 270 °C. In the wide range of the ratios of N₂ and total gas flow rates (fN₂/N₂ + H₂) from 0.12 to 0.70, pure Ru films with negligible nitrogen incorporation of 0.5 at.% were obtained, with resistivities ranging from ~ 20 to ~ 30 μΩ cm. A growth rate of 0.057 nm/cycle and negligible incubation cycle for the growth on SiO₂ was observed, indicating the fast nucleation of Ru. The Ru films formed polycrystalline and columnar grain structures with a hexagonal-close-packed phase. Its resistivity was dependent on the crystallinity, which could be controlled by varying the deposition parameters such as plasma power and pulsing time. Cu was electroplated on a 10-nm-thick Ru film. Interestingly, it was found that the nitrogen could be incorporated into Ru at a higher reactant gas ratio of 0.86. The N-incorporated Ru film (~ 20 at.% of N) formed a nanocrystalline and non-columnar grain structure with the resistivity of ~ 340 μΩ cm.     

Quenching of luminescent ruthenium(II) complexes by water and polymer-based relative humidity sensors

Water quenching of luminescent [Ru(phen)(2)dppz]Cl(2), [Ru(phen)(2)dppn]Cl(2), and [Ru(4,7-Ph(2)phen)(2) dppz]Cl(2) (phen = 1,10-phenanthroline; 4,7-Ph(2)phen = 4; 4,7-diphenyl-1,10-phenanthroline; dppz = dipyrido[3,2-a:2'3'-c]phenazine; dppn = benzodipyrido(a:3,2-h:2',3'-j)phenazine) complexes was studied in acetonitrile and in polymers. The polymers contained hydrophobic and hydrophilic components to control mechanical properties and were designed to absorb water with changing humidity and, thus, affect the emission intensity and lifetime. Quenching by water in mixed solvents and in polymers was shown to arise from a combination of diffusional and static ground-state associational quenching. The factors controlling polymer properties are discussed. The systems can be tailored to give a wide range of responses or function as a binary sensor at a fixed humidity level.     

Spatial scanning spectroelectrochemistry. Study of the electrodeposition of Pd nanoparticles at the liquid/liquid interface

Spatial scanning spectroelectrochemistry is a new analytical technique that provides spectral information at different distances from an electrified liquid/liquid interface where an electrochemical process takes place. As a proof of concept, we have studied two different electrochemical processes at the electrified liquid/liquid interface: (1) Ru(bpy)(3)(2+) transfer through the water/1,2-dichloroethane interface and (2) electrodeposition of Pd nanoparticles at the water/1,2-dichloroethane interface. The instrumental setup developed consists of a movable slit for the light beam to sample at well-defined positions on both sides of the interface, providing important information about the chemical process occurring. If the slit is scanned at different distances from the interface during an electrochemical experiment, a complete picture of the reactions and equilibria in the diffusion layer can be obtained. For example, in the case of the Ru(bpy)(3)(2+), the experiments show clearly how the complex is transferred from one phase to the other. In the case of electrosynthesis of Pd nanoparticles, it is demonstrated that nanoparticles are not only deposited at the interface but diffuse to the aqueous bulk solution. These in situ observations were confirmed by ex situ experiments using transmission electron microscopy.