Synthesis and electronic property of platinum nanowire and nanoparticle in mesoporous silica template

Platinum nanowires and nanoparticles were selectively synthesized in mesoporous silicas FSM-16 and HMM-1. The nanowires are 3 nm in diameter and several hundred nm to μm in length with high crystallinity. Pt nanowires and nanoparticles can be isolated by dissolving silica matrix with HF. The Pt wires extracted from organosilica HMM-1 have a nanonecklace structure, while the wires from siliceous FSM-16 have a nanorod structure. The extracted Pt nanoparticles (3 nm in size) on HOPG show the Coulomb staircase phenomena in STM/STS analysis. The mechanism for formation of the Pt nanowires is based on the migration of Pt ions in the mesoporous channels.     

Nanoscale fabrication of metal particles and wires using mesoporous silica templates: Electronic properties and catalytic performances in PROX reaction

Pt nanowires and nanoparticles were selectively synthesized in mesoporous silica templates FSM-16 and HMM. The wires and particles were characterized by physicochemical methods. Extracted Pt nanoparticles on HOPG show Coulomb blockade phenomena in STM/STS measurements. Pt nanowires and -particles in FSM-16 shows high catalytic activity and selectivity in preferential oxidation (PROX) of CO in H₂.     

Preparation,XAFS Characterization,and Catalysis of Platinum Nanowires and Nanoparticles in Mesoporous Silica FSM-16

Pt nanowires are prepared in mesoporous FSM-16 by photoreduction of H₂PtCl₆, while H₂-reduction of H₂PtCl₆/FSM-16 at 673 K gives Pt nanoparticles in FSM-16. The Pt nanowires and nanoparticles are characterized by physicochemical methods such as XAFS, TEM, XRD, and XPS. The formation mechanism of the Pt nanowires and the catalytic performance in the water–gas-shift reaction are also investigated.     

Pore-Size Dependence of the Acidic Property of Mesoporous Silica FSM-16

The pore-size dependence of the acidic properties of mesoporous silica FSM-16 in the range from 1.8 to 3.8 nm was investigated with the catalysis of 2-butanol dehydration and using FTIR spectra of adsorbed pyridine. The activity was the highest for FSM-16 with a minimum pore diameter, and decreased with increasing pore size. Differences in the acid amounts of siliceous FSM-16 and the strength dependent on the pore diameter were not confirmed by FTIR characterization using pyridine as a probe molecule.     

Enhancement of electrodes modified by electrodeposited PEDOT‐nanowires with dispersed Pt nanoparticles for formic acid electro‐oxidation

Preparation of electrodes modified with poly(3,4‐ethylenedioxythiophene) nanowires, PEDOT‐nw, was optimized using nanoparticles of dispersed Pt, Pt‐np, to be tested for HCOOH electro‐oxidation. The PEDOT‐nw is electrosynthesized directly on the working electrode, using mesoporous silica as template, by cyclic voltammetry from a 0.01 mol L^?1 monomer + 0.1 mol L^?1 tetrabutylammonium hexafluorophosphate solution in acetonitrile, on the Pt|PEDOT|mesoporous silica template previously modified electrodes. Using SEM, the presence of PEDOT nanowires with 20 to 25 nm in diameter was verified. In addition, its p ‐doping response is about 500 times larger than that obtained on the bulk polymer, maintaining full reversibility of the process. The subsequent electrochemical insertion of Pt‐np and formation of Pt‐np with average diameter of about 20 nm, checked by TEM, demonstrated that the catalytic activity of this nanostructured electrode remarkably enhanced HCOOH electro‐oxidation. The obtained current is up to 2 orders of magnitude higher than previously reported in similar studies, using a much smaller amount of Pt and with a potential decrease greater than 100 mV. Thus, we have at our disposal a simple, inexpensive, and highly reproducible way to prepare in situ nanostructured electrodes using just electrochemical techniques, which can be useful on all the applications of these devices. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44723.     

Ca-Containing Mesoporous Silica as a Solid Base Catalyst for the Knoevenagel Condensation Reaction

Abstract  

We synthesized Ca-containing FSM-16 (Ca-FSM-16) for use as a solid base catalyst for the Knoevenagel condensation reaction. Extended X-ray absorption fine structure (EXAFS) results indicated that Ca species were introduced as a calcium silicate-like phase with distorted tetrahedral coordination into the pore walls of FSM-16. Compared with conventional aminopropyl-functionalized mesoporous silica, Ca-FSM-16 showed higher activity as a solid-base catalyst for the Knoevenagel condensation reaction.     

Ni-Rhodanine Complex Supported on FSM-16 as Mesoporous Silica Support: Synthesis,Characterization and Application in Synthesis of Tri and Tetrasubstituted Imidazoles and 3,4-Dihydropyrimidine-2-(1H)-Ones

A new, efficient and recoverable heterogeneous catalyst was successfully synthesized by functionalization of mesoporous silica FSM-16. The FSM-16/CPTMS-Rh-     

Volumetric distribution of Pt nanoparticles supported on mesoporous carbon substrates studied by X-ray photoelectron spectroscopy depth profiling

We present an X-ray photoelectron spectroscopy depth profiling study of the size and volumetric distributions of Pt nanoparticles supported on two mesoporous carbons. Based on the analysis of the chemical shift of the Pt4f peaks, we found the one with a mesopore diameter of ∼5 nm has a uniform distribution of crystalline Pt nanoparticles throughout the porous body. In contrast, the other with a mesopore diameter of ∼3 nm has a distinct distribution of crystalline Pt nanoparticles on the outermost surfaces of the porous material and extremely small (<1 nm) Pt nanoparticles in the interior region. The small Pt particle size in the interior represents the effect of pore entrance blockage of those mesopore channels with diameter less than 3 nm. Such blockage gives rise to the encapsulation of very small amounts of Pt precursors inside the nanospace of the porous matrix, with the result that the particles grown in the interior region of the support are less than 1 nm in size.     

Large-Scale Synthesis and CO Oxidation Study of FeCr Alloy Supported Pt Nanocatalyst by Electrical Wire Explosion Process

Abstract  

Platinum nanoparticles supported on FeCr alloy have been synthesized at a large-scale by sequential electrical explosion of FeCr alloy and Pt wires in ethanol. X-ray diffraction showed corresponding peaks of non-oxide phase Pt and FeCr alloy nanoparticles. Transmission electron microscopy showed uniform dispersion of Pt nanoparticles on the support with an average size of 2 nm and high thermal stability up to 600 °C. These Pt-FeCr alloy nanoparticles were found to be active for CO oxidation with an activation energy of 15 kcal mol⁻¹ and negligible deactivation. This work demonstrated the application of the electrical wire explosion process for synthesis of supported metal catalysts with high thermal stability and activity.     

Morphology controllable growth of Pt nanoparticles/nanowires on carbon powders and its application as novel electro-catalyst for methanol oxidation

Pt nanowires (PtNWs) have been controllably synthesized on carbon powders by the reduction of H(2)PtCl(6) with HCOOH. By adjusting the pH value of the solution, PtCl(6)(2-) can be controllable reduced into particles or nanowires. The Pt nanowires are single crystals growing along the <111> direction with a diameter of 3 nm and a length of 10 nm. The dispersion of Pt nanowires on the surface of carbon powders can be controlled by changing the loading of Pt. The PtNWs/C is evaluated as the catalyst for methanol oxidation. The PtNWs/C with 20 wt% Pt has a larger electrochemical active surface area and much higher mass activity for methanol oxidation than that of commercial Pt/C catalyst. The PtNWs/C catalyst shows significant improvement in the kinetics for methanol oxidation and mass transfer property due to the single crystal structure of the Pt nanowires. The PtNWs/C catalyst holds promising potential applications in energy converting devices and environmental protection.     

Impact of framework structure of ordered mesoporous carbons on the performance of supported Pt catalysts for oxygen reduction reaction

Ordered mesoporous carbons (OMCs) are investigated as support materials for Pt catalysts for oxygen reduction reaction (ORR). Three types of OMCs (CMK-3, CMK-3G, and CMK-5) are prepared by a nanocasting method using ordered mesoporous silica, SBA-15, as a template. These OMCs with the same hexagonal mesostructure have different carbon frameworks and graphiticity, which can affect their surface area and microporosity. Pt nanoparticles with an average size of 1 nm are uniformly supported on the three OMCs and Ketjenblack® and their electrochemical performance and durability are evaluated. Pt/CMK-3G exhibits the highest electrochemically active surface area, kinetic current density, mass activity, and half-wave potential, whereas Pt/CMK-3 shows the lowest values. Pt/CMK-3G also shows the highest ORR activity after an accelerated durability test, with a minimal shift in half-wave potential. The higher ORR activity of Pt/CMK-3G is attributed to the formation of highly crystalline Pt particles as well as its highly graphitic, crystalline carbon structure, which causes the weak adsorption of surface oxide and a strong interaction between the Pt particles and the support. Moreover, we can establish that the mass activity of the catalysts is nearly inversely proportional to the micropore volume of the carbon supports.     

Fabrication of single-wall carbon nanotubes within the channels of a mesoporous material by catalyst-supported chemical vapor deposition

Diameter-controlled single-wall carbon nanotubes (SWCNTs) have been synthesized using Co, Fe/Co and Rh/Pd alloy nanoparticles trapped within the one-dimensional channels of a mesoporous materials (Folded Sheets Mesoporous material: FSM-16) by catalyst-supported chemical vapor deposition (CCVD) using ethanol as carbon source at 973-1173 K. The SWCNTs synthesized are characterized by transmission electron microscopy, Raman spectroscopy and photoluminescence spectroscopy. The yield, diameter distribution and quality of the SWCNTs strongly depend on the reaction temperature during CCVD. The product synthesized at 1173 K contains only SWCNTs, in marked contrast to those synthesized at lower temperatures. As the reaction temperature decreases, the relative abundance of multi-wall carbon nanotubes against SWCNTs significantly increases, whereas the mean diameter of SWCNTs increases as reaction temperature increases. The results show that a careful control of the reaction temperature is crucial to fabricate diameter-controlled SWCNTs from the channels of FSM-16.     

Pt nanowires prepared via a polymer template method: Its promise toward high Pt-loaded electrocatalysts for methanol oxidation

Platinum nanowires were prepared via a template-synthesis method by electrodeposition of platinum within pores of a track-etched polycarbonate (PCTE) membrane, followed by chemical etching to separate the Pt nanowires from the polymer. The structure and morphology of the Pt nanowires were characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), and transmission electron microscopy (TEM), revealing a polycrystalline phase with nanowire dimension up to 6 μm long and ca. 47 ± 9.8 nm of diameter. The unsupported Pt nanowires showed the better electrochemical mass activities over the methanol electro-oxidation than supported or unsupported Pt nanoparticles under the high Pt content-loaded conditions that is typically required for direct methanol fuel cells. This enhancement could be rationalized by its unique physicochemical and electrical properties arising from the inherent anisotropic one-dimensional (1D) nanostructure, such as charge transfer facilitation by reducing number of particle interfaces and more efficient use of Pt by alleviating fraction of embedded catalysts.     

Solid‐State Sintering of Glasses with Optical Nonlinearity from Mesoporous Powders

Silica glasses dispersed with Pt nanoparticles and Ag nanoparticles are derived from solid‐state sintering of mesoporous silica SBA‐15 encapsulated with Pt nanoparticles and Ag nanoparticles, respectively. Using mesoporous powders for sintering is a facile method to lower synthesis temperature for glass making and to efficiently disperse noble metal nanoparticles in silica glass matrix. The included nanoparticles still play their functional roles in impacting on optical properties of the glass products prepared by this novel method. The glass dispersed with Pt nanoparticles exhibits brown color due to the interband electron transition of Pt nanoparticles. The coloring effect of surface plasmon resonance absorption from Ag nanoparticles colors the glass dispersed with Ag nanoparticles with yellow. Open‐aperture and closed‐aperture Z‐scan methods are applied to measure third‐order nonlinear absorption and refraction coefficient of the composite glasses, respectively, under femtosecond laser radiation at 880 nm wavelength. The glass dispersed with Pt nanoparticles behaves intense nonlinear absorption comparing with nonlinear refraction in magnitude, which could be attributed to interband electron transition by monophoton absorption of Pt nanoparticles. The glass dispersed with Ag nanoparticles shows stronger nonlinear refraction than saturated absorption. The dominant contribution to third‐order optical nonlinearity of silica glass dispersed with Ag nanoparticles is intraband transition of free electrons near the Fermi surface of Ag nanoparticles. This method may have potential applications for fabricating silica glasses dispersed with ultrafine functional particles, which are potentially applicative in the fields of photonics.     

CTAB assisted microwave synthesis of ordered mesoporous carbon supported Pt nanoparticles for hydrogen electro-oxidation

Mesoporous carbon with ordered hexagonal structure derived from the co-assembly of triblock copolymer F127 and resol was employed as the carbon support of Pt catalysts for hydrogen electro-oxidation. Structural characterizations revealed that the mesoporous carbon exhibited large surface area and uniform mesopores. The Pt nanoparticles supported on the novel mesoporous carbon were fabricated by a facile CTAB assisted microwave synthesis process, wherein CTAB was expected to improve the wettability of carbon support as well as the dispersion of Pt nanoparticles. X-ray diffraction and transmission electron microscopy were applied to characterize the Pt catalysts. It was found that the Pt nanoparticles were uniform in size and highly dispersed on the mesoporous carbon supports. The cyclic voltammograms in sulfuric acid demonstrated that the electrochemical active surface area of Pt catalysts prepared with CTAB was two times than that without CTAB.     

An alternative route for the synthesis of silicon nanowires via porous anodic alumina masks

Amorphous Si nanowires have been directly synthesized by a thermal processing of Si substrates. This method involves the deposition of an anodic aluminum oxide mask on a crystalline Si (100) substrate. Fe, Au, and Pt thin films with thicknesses of ca. 30 nm deposited on the anodic aluminum oxide-Si substrates have been used as catalysts. During the thermal treatment of the samples, thin films of the metal catalysts are transformed in small nanoparticles incorporated within the pore structure of the anodic aluminum oxide mask, directly in contact with the Si substrate. These homogeneously distributed metal nanoparticles are responsible for the growth of Si nanowires with regular diameter by a simple heating process at 800°C in an Ar-H₂ atmosphere and without an additional Si source. The synthesized Si nanowires have been characterized by field emission scanning electron microscopy, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, and Raman.     

ZnO Nanowires Synthesized by Vapor Phase Transport Deposition on Transparent Oxide Substrates

Zinc oxide nanowires have been synthesized without using metal catalyst seed layers on fluorine-doped tin oxide (FTO) substrates by a modified vapor phase transport deposition process using a double-tube reactor. The unique reactor configuration creates a Zn-rich vapor environment that facilitates formation and growth of zinc oxide nanoparticles and wires (20–80 nm in diameter, up to 6 μm in length, density <40 nm apart) at substrate temperatures down to 300°C. Electron microscopy and other characterization techniques show nanowires with distinct morphologies when grown under different conditions. The effect of reaction parameters including reaction time, temperature, and carrier gas flow rate on the size, morphology, crystalline structure, and density of ZnO nanowires has been investigated. The nanowires grown by this method have a diameter, length, and density appropriate for use in fabricating hybrid polymer/metal oxide nanostructure solar cells. For example, it is preferable to have nanowires no more than 40 nm apart to minimize exciton recombination in polymer solar cells.     

The self-assembly of gold nanoparticles in large-pore ordered mesoporous carbons

Simple encapsulation of 3 nm gold nanoparticles in ordered mesoporous carbon with large pores of 17 nm and thick pore walls of 16 nm was achieved by a metal-ligand coordination assisted-self-assembly approach.Polystyrene-block-polyethylene-oxide (PS-b-PEO) diblock copolymer with a large molecular weight of the PS chain and mercaptopropyltrimethoxysilane were used as the template and the metal ligand,respectively.Small-angle X-ray scattering,X-ray diffraction,transmission electron microscopy,and X-ray photoelectron spectroscopy showed that monodispersed aggregation-free gold nanoparticles approximately 3 nm in size were partially embedded in the large open pore structure of the ordered mesoporous carbon.The strong coordination between the gold species and the mercapto groups and the thick porous walls increased the dispersion of the gold nanoparticles and essentially inhibited particle aggregation at 600 ℃.The gold nanoparticles in the ordered mesoporous carbon are active and stable in the reduction of nitroarenes involving bulky molecules using sodium borohydride as a reducing agent under ambient conditions (30 ℃) in water.The large interconnected pore structure facilitates the mass transfer of bulky molecules.     

Low temperature solution-phase growth of ZnSe and ZnSe/CdSe core/shell nanowires

High quality ZnSe nanowires (NWs) and complementary ZnSe/CdSe core/shell species have been synthesized using a recently developed solution-liquid-solid (SLS) growth technique. In particular, bismuth salts as opposed to pre-synthesized Bi or Au/Bi nanoparticles have been used to grow NWs at low temperatures in solution. Resulting wires are characterized using transmission electron microscopy and possess mean ensemble diameters between 15 and 28 nm with accompanying lengths ranging from 4-10 μm. Subsequent solution-based overcoating chemistry results in ZnSe wires covered with CdSe nanocrystals. By varying the shell's growth time, different thicknesses can be obtained and range from 8 to 21 nm. More interestingly, the mean constituent CdSe nanocrystal diameter can be varied and results in size-dependent shell emission spectra.     

金属改性的介孔硅材料FSM-16催化苯酚与H_2O_2合成苯二酚

研究了金属改性的介孔硅材料FSM-16在该反应中的催化性能。其中Fe和Cu改性的FSM-16表现出比较好的性能。在Fe-FSM-16的作用下,苯酚的转化率达到27.8%,对苯二酚和邻苯二酚选择性达到96.4%(邻/对=1.8)。FT-IR和XRD表征证明铜离子进入了FSM-16的骨架,并形成了Si—O—Cu键。