Functionalization of electrospun TiO2 nanofibers with Pt nanoparticles and nanowires for catalytic applications

This paper reports a simple procedure for derivatizing the surface of anatase TiO2 nanofibers with Pt nanoparticles and then Pt nanowires. The nanofibers were prepared in the form of a nonwoven mat by electrospinning with a solution containing both poly(vinyl pyrrolidone) and titanium tetraisopropoxide, followed by calcination in air at 510 degrees C. The fiber mat was then immersed in a polyol reduction bath to coat the surface of anatase fibers with Pt nanoparticles of 2-5 nm in size with controllable density of coverage. Furthermore, the coated fibers could serve as a three-dimensional scaffold upon which Pt nanowires of roughly 7 nm in diameter could be grown at a high density and with a length up to 125 nm. The fiber membranes functionalized with Pt nanoparticles and nanowires are interesting for a number of catalytic applications. It was found to show excellent catalytic activity for the hydrogenation of azo bonds in methyl red, which could be operated in a continuous mode by passing the dye solution through the membrane at a flow rate of 0.5 mL/s.     

One-step preparation of poly(vinyl alcohol)-protected Pt nanoparticles through a heat-treatment method

A heat-treatment method for the preparation of well-stable, polymer-protected Pt nanoparticles in the range of 2-7 nm in diameter is demonstrated. The formation of Pt nanoparticles occurs in a single step process, carried out by heating an aqueous solution containing a poly(vinyl alcohol) polymer and H₂PtCl₆, with the use of PVA to serve as both a reducing reagent and a protective reagent. The Pt nanoparticles were characterized by UV-vis absorption spectra, transmission electron microscopy (TEM), and X-ray photoelectron spectrum (XPS) and the Pt nanoparticle formation process was further investigated by in situ UV-vis experiment.     

Mechanism of Pt loading on multi-walled carbon nanotubes

Microwave treatment of multi-walled carbon nanotubes (MWCNTs) with nitric acid (HNO3) and 0.2 M sodium chlorate (NaClO3) can generate and enhance defects on the surfaces of MWCNTs. These defects are the important sites to load Pt nanoparticles (NPs). We investigated the defect induced Raman spectra and observed a decrease in the R-values (D-band/G-band peak ratio) and a slight up-shift of the both peaks as the amount of loaded Pt NPs increased. Using the Brunauer-Emmett-Teller (BET) method, we observed that the pore size distribution and the pore volume changed according to the amount of Pt NPs loaded. Fewer micropores and mesopores were observed on MWCNTs loaded with Pt NPs. Based on the pore size distribution calculated from the BET results, Pt NPs loaded mainly on pores/defects with a size of 2-8 nm. Transmission electron microscopy and Raman spectroscopy results confirmed that most well-crystallized Pt NPs loaded on the surface defect sites and pores spontaneously through the exchange of electrons between Pt and C atoms.     

Microwave polyol synthesis of Pt/C catalysts with size-controlled Pt particles for methanol electrocatalytic oxidation

Pt/C catalysts with different mean size of Pt particles were prepared by a microwave-assisted polyol process and characterized by TEM and XRD. The effects of the synthesis solution pH on Pt particles size and distribution, and their activity for methanol electrooxidation were investigated. Pt nanoparticles were small and uniform with mean size of 2.7 nm under the pH of 9.5. Pt/C catalyst showed high activity for methanol electrooxidation.     

薄壳层核壳型Ni/Pt纳米粒子的制备及电催化性能

通过胶体-化学镀法制备不同厚度薄壳层核壳型Ni/Pt纳米粒子, 采用HRTEM、EDS、XPS和XRD手段对粒子的形貌、晶型和组成进行物理表征. 采用动电位、循环伏安法对其氧电还原和甲醇电氧化活性进行测试. 实验结果表明, 核壳结构Ni/Pt纳米颗粒基本为球形, 其中Ni₁-Pt_0.067平均直径为7 nm左右, 壳层厚度约1 nm. 与Pt/C相比, 核壳型Ni/Pt纳米粒子对氧电还原和甲醇电氧化的催化活性显著提高. 在所制备的不同壳层厚度催化剂中, Ni₁-Pt_0.067/C在0.5 mol/L H₂SO₄中氧电还原的最大峰电流密度可达到143.06 mA/mg, 是相同反应条件Pt/C峰电流密度的1.4倍; 而Ni₁-Pt_0.067/C在0.5 mol/L H₂SO₄+1.0 mol/L CH₃OH溶液中甲醇电氧化峰电流密度可达538.3 mA/mg, 是Pt/C峰电流密度的5.2倍. 若以1 mg贵金属Pt为基准, Ni₁-Pt_0.067/C的比质量活性相对Pt/C的提高了30倍.     

In‐Situ Confined Growth of Monodisperse Pt Nanoparticle@Graphene Nanobox Composites as Electrocatalytic Nanoreactors

Monodisperse Pt nanoparticles (NPs) studded in a three‐dimensional (3D) graphene nanobox are successfully synthesized through a simple in‐situ confined growth route for the first time. The nano‐zeolite A was used as a 3D substrate for in‐situ growth of tri‐layered graphenes on the crystal‐surfaces, meanwhile, the inner micropores of which can also be utilized for the confined growth of Pt nanoparticles. The graphene sheets are curved on the edges to form a 3D hollow box morphology, where the monodisperse Pt nanoparticles are homogeneously studded on the inner surfaces. Moreover, the Pt content can be regulated from ～8 to 50 wt%, and the particle size can be tuned from 2–5 nm by varying the pristine Pt‐ion loading amount and CVD temperature. The Pt NP@graphene nanoboxes possess not only large pore volumes to effectively accommodate large amounts of oxygen, but also supply excellent electrical conductivity for the fast transfer of electrons (～3.96 e^‐), resulting in a high efficiency (175 mA/mg Pt) and long‐term stability (above 1000 cycles) for the oxygen reduction reaction.     

New method for synthesis of Pt nanoparticles embedded in a carbon matrix

Platinum (Pt) nanoparticles embedded in a carbon matrix were synthesized for the first time in benzene by an electric plasma discharge generated in the cavitation field of benzene due to an ultrasonic horn. Transmission electron microscopy (TEM) and X-ray diffraction (XRD) were used to study the particle size, structure and morphology of the synthesized nanoparticles. The Pt nanoparticles have FCC bulk Pt crystal structure. On the average Pt nanoparticle diameter ranged from 8 nm to 40 nm when synthesized at 4.1 kV and from 5 nm to 25 nm when synthesized at 3.4 kV. X-ray photoelectron Spectroscopy (XPS) and Energy dispersive X-ray Spectroscopy (EDX) were used to study the chemical composition of the synthesized nanoparticles. A cost effective new method for carbon supported Pt nanoparticles will be of potential interest in fuel cell and catalysis applications.     

Synthesis and characteristics of Ag/Pt bimetallic nanocomposites by arc-discharge solution plasma processing

Arc discharge in solution, generated by applying a high voltage of unipolar pulsed dc to electrodes of Ag and Pt, was used as a method to form Ag/Pt bimetallic nanocomposites via electrode erosion by the effects of the electric arc at the cathode (Ag rod) and the sputtering at the anode (Pt rod). Ag/Pt bimetallic nanocomposites were formed as colloidal particles dispersed in solution via the reduction of hydrogen radicals generated during discharge without the addition of chemical precursor or reducing agent. At a discharge time of 30?s, the fine bimetallic nanoparticles with a mean particle size of approximately 5?nm were observed by transmission electron microscopy (TEM). With increasing discharge time, the bimetallic nanoparticle size tended to increase by forming an agglomeration. The presence of the relatively small amount of Pt dispersed in the Ag matrix could be observed by the analytical mapping mode of energy-dispersive x-ray spectroscopy and high-resolution TEM. This demonstrated that the synthesized particle was in the form of a nanocomposite. No contamination of other chemical substances was detected by x-ray photoelectron spectroscopy. Hence, solution plasma could be a clean and simple process to effectively synthesize Ag/Pt bimetallic nanocomposites and it is expected to be widely applicable in the preparation of several types of nanoparticle.     

A simple microwave-based route for size-controlled preparation of colloidal Pt nanoparticles

A simple route for the preparation of colloidal Pt nanoparticles is demonstrated. The formation of such colloids occurs in a single-step process, involving the direct microwave-based heat-treatment of an aqueous solution containing H₂PtCl₆ and 3-thiophenemalonic acid. In the synthesis, the particle size can be controlled by the molar ratio of the reactant agents.     

Size-, and shape-selective synthesis of platinum nanoparticles from Pt(beta-diketonate)2 complexes in organic media

Preparation of platinum nanoparticles from two beta-diketonate complexes of platinum, Pt(hfac)2 and Pt(acac)2 (hfac: hexafluoroacetylacetonate, acac: acetylacetonate) in organic media will be presented in the contribution. Nearly spherical, well-dispersed platinum nanoparticles were fabricated by thermally-induced reduction of Pt(hfac)2 in the presence of teraalkylammonium salts as the stabilizing agents in several organic solvents. Particle sizes ranging from 9 to 15 nm can be controlled by variation of the surfactant, the concentrations of precursor and surfactant, as well as reaction temperature. Heating the solution of Pt(acac)2 complex in 1-octanol at appropriate temperatures provided the platinum nanocubes and the influence of reaction temperature on the particle shape was investigated.     

Synthesis of WO3 in nanoscale with the usage of sucrose ester microemulsion and CTAB micelle solution

WO₃ nanoparticles were successfully prepared using first the low temperature hydrolysis method and second the chemical reaction method in water-in-oil sucrose ester microemulsion consisting of S1570, 1-butanol, tetradecane and aqueous phase. In this study WO₃ nanoparticles also were prepared using the CTAB micelle solution. The resultant WO₃ nanoparticles have been investigated with X-ray diffraction (XRD), transmission electron microscopy (TEM), variable pressure scanning electron microscope (SEM) equipped with energy dispersive X-ray analysis (EDX) and X-ray photoelectron spectroscopy (XPS). The shape and particles size of the resultant WO₃ nanoparticles from both methods in sucrose ester microemulsion show similar spherical shape and size range between 10 and 50 nm. The WO₃ nanoparticles prepared with the CTAB micelle solution show spherical shape with the size range average of 25-50 nm.     

Simple approach to synthesis Pt/NiO flower microspheres and their electrocatalytic properties

A kind of novel Pt/NiO flower microsphere structure has been successfully fabricated through a two step chemical process. Firstly NiO flower microspheres could be prepared by a hydrothermal method with the assistance of biomolecule (l-glutamic acid). Secondly the Pt/NiO microsphere composition could be synthesized by the reduction of H₂PtCl₆ solution by use of glucose, and the as-deposited Pt nanoparticles with less than 40 nm in size were embedded into the gaps of the adjacent petals. The sample was characterized by XRD, SEM, TEM, EDS et al. This new kind of structure shows excellent electrocatalytic properties compared with that of Pt nanoparticles, which might provide an efficient way to improve the electrocatalytic property of nanomaterials and other applications.     

载体炭与Pt催化剂之间的相互作用及其引起的尺寸效应(英文)

通过乙二醇还原,在VulcanXC-72炭黑上负载了三种具有不同平均粒径(1.7nm,3.0nm和5.0nm)的Pt催化剂。利用透射电子显微镜,研究了载体炭黑表面的微孔与Pt催化剂之间的几何相互作用。结果表明:尺寸较小的Pt颗粒(平均粒径为1.7nm)通常被包含在载体表面的微孔中,表现为被一薄碳层所覆盖并嵌入炭黑基体。而尺寸较大的Pt颗粒(平均粒径为3.0nm和5.0nm)则不存在这种现象,往往显示出裸露的清洁表面。这种与载体表面微孔的不同相互作用引起了Pt颗粒在电化学活性比表面上的反常尺寸效应,进而影响了其催化甲醇氧化的质量比活性。     

Pt/C催化剂制备及CO催化氧化性能研究

采用大气压介质阻挡放电辅助氢气热还原方法和氢气热还原方法制备Pt/C催化剂,考察了制备方法及Pt负载量对Pt/C催化性能的影响。采用X-射线衍射(XRD)、循环伏安法、CO催化氧化反应研究Pt/C催化剂的晶相结构、电催化性能和CO催化氧化活性。结果表明:大气压介质阻挡放电辅助氢气热还原所制备的样品具有更高的电化学活性和CO催化氧化活性。当Pt负载量在2%到10%之间变化时,Pt/C-PC催化活性随负载量增加而增加。XRD测试结果显示当Pt负载量为2%,5%和10%时,Pt粒径分别为:10.6 nm,9.1 nm和6.4 nm,说明采用等离子体辅助氢气热还原方法制备的Pt/C-PC催化剂,Pt负载量越大,Pt粒径越小,CO催化氧化活性更高。     

Dendrimer templated synthesis of one nanometer Rh and Pt particles supported on mesoporous silica: catalytic activity for ethylene and pyrrole hydrogenation

Monodisperse rhodium (Rh) and platinum (Pt) nanoparticles as small as approximately 1 nm were synthesized within a fourth generation polyaminoamide (PAMAM) dendrimer, a hyperbranched polymer, in aqueous solution and immobilized by depositing onto a high-surface-area SBA-15 mesoporous support. X-ray photoelectron spectroscopy indicated that the as-synthesized Rh and Pt nanoparticles were mostly oxidized. Catalytic activity of the SBA-15 supported Rh and Pt nanoparticles was studied with ethylene hydrogenation at 273 and 293 K in 10 torr of ethylene and 100 torr of H 2 after reduction (76 torr of H 2 mixed with 690 torr of He) at different temperatures. Catalysts were active without removing the dendrimer capping but reached their highest activity after hydrogen reduction at a moderate temperature (423 K). When treated at a higher temperature (473, 573, and 673 K) in hydrogen, catalytic activity decreased. By using the same treatment that led to maximum ethylene hydrogenation activity, catalytic activity was also evaluated for pyrrole hydrogenation.     

Room temperature observation of size dependent single electron tunneling in a sub-2 nm size tunable Pt nanoparticle embedded metal-oxide-semiconductor structure

In this paper we report size dependent single electron tunneling behavior at room temperature in a metal-oxide-semiconductor structure with uniformly sized Pt nanoparticles embedded in an Al(2)O(3) dielectric. The sub-2 nm size Pt nanoparticles sandwiched between the Al(2)O(3) layers are deposited by a unique tilted target sputter deposition technique which produces metal nanoparticles as small as 0.5 nm with narrow size distributions at room temperature. The charging behavior of these nanoparticles shows clear single electron tunneling peaks due to the Coulomb blockade effect. Moreover, the average single electron addition energy and height of the single electron tunneling current strongly depend on the size of the Pt nanoparticle. These controllable single electron tunneling behaviors suggest a new route for fabrication of single electron devices.     

Pt nanostructure electrodes pulse electrodeposited in PVP for electrochemical power sources

In this work, we demonstrated that Pt nanostructure electrodes could be obtained by the pulse electrodeposition method in polyvinylpyrrolidone (PVP). The nanocrystal particles were confirmed by scanning electron microscopy, transmission electron microscopy and x-ray diffraction methods. The average size of Pt nanoparticles deposited in additive PVP with low and high molecular weight is 3.4 and 2.9?nm, respectively, whereas that of Pt electrodeposited without PVP is 360?nm. This means that the size of Pt nanoparticles can be controlled by PVP, resulting in an increased electrochemical surface area. The resulting Pt nanostructure electrodes showed such an improved performance for both direct methanol fuel cells and dye-sensitized solar cells.     

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.     

Nanocomposite for methanol oxidation: synthesis and characterization of cubic Pt nanoparticles on graphene sheets

Abstract

We present our recent results on Pt nanoparticles on graphene sheets (Pt-NPs/G), a nanocomposite prepared with microwave assistance in ionic liquid 2-hydroxyethanaminiumformate. Preparation of Pt-NPs/G was achieved without the addition of extra reductant such as hydrazine or ethylene glycol. The Pt nanoparticles on graphene have a cubic-like shape (about 60 wt% Pt loading, Pt-NPs/G) and the particle size is 6 ± 3 nm from transmission electron microscopy results. Electrochemical cyclic voltammetry studies in 0.5 M aqueous H₂SO₄ were performed using Pt-NPs/G and separately, for comparison, using a commercially available electrocatalyst (60 wt% Pt loading, Pt/C). The electrochemical surface ratio of Pt-NPs/G to Pt/C is 0.745. The results of a methanol oxidation reaction (MOR) in 0.5 M aqueous H₂SO₄ + 1.0 M methanol for the two samples are presented. The MOR results show that the ratios of the current density of oxidation (I_f) to the current density of reduction (I_b) are 3.49 (Pt-NPs/G) and 1.37 (Pt/C), respectively, with a preference by 2.55 times favoring Pt-NPs/G. That is, the tolerance CO poisoning of Pt-NPs/G is better than that of commercial Pt/C.     

Memory characteristics of a self-assembled monolayer of Pt nanoparticles as a charge trapping layer

A self-assembled monolayer of Pt nanoparticles (NPs) was studied as a charge trapping layer for non-volatile memory (NVM) applications. Pt NPs with a narrow size distribution (diameter ～4?nm) were synthesized via an alcohol reduction method. The monolayer of these Pt NPs was immobilized on a SiO(2) substrate using poly(4-vinylpyridine) (P4VP) as a surface modifier. A metal-oxide-semiconductor (MOS) type memory device with Pt NPs exhibits a relatively large memory window of 5.8?V under ± 7?V for program/erase voltage. These results indicate that the self-assembled Pt NPs can be utilized for NVM devices.