Pt/MWNTs催化剂的制备及其性能

以多壁碳纳米管为载体，用液相还原法制备了Pt／MWNTs催化剂，通过XRD、TEM等技术对催化剂进行了表征，并将所制催化剂组装成燃料电池，以H2、O2为反应气，测试了催化剂的性能，结果显示Pt／MWNTs催化剂具有优良的电催化活性。     

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.     

SnNi nanoneedles assembled 3D radial nanostructure loaded with SnNiPt nanoparticles: Towards enhanced electrocatalysis performance for methanol oxidation

A desirable methanol oxidation electrocatalyst was fabricated by metal atom diffusion to form an alloy of an assembled three-dimensional (3D) radial nanostructure of SnNi nanoneedles loaded with SnNiPt nanoparticles (NPs).Herein,metal atom diffusion occurred between the SnNi support and loaded Pt NPs to form a SnNiPt ternary alloy on the catalyst surface.The as-obtained catalyst combines the excellent catalytic performance of the alloy and advantages of the 3D nanostructure;the SnNiPt NPs,which fused on the surface of the SnNi nanoneedle support,can dramatically improve the availability of Pt during electrocatalysis,and thus elevate the catalytic activity.In addition,the efficient mass transfer of the 3D nanostructure reduced the onset potential.Furthermore,the catalyst achieved a favorable CO poisoning resistance and enhanced stability.After atomic interdiffusion,the catalytic activity drastically increased by 45％,and the other performances substantially improved.These results demonstrate the significant advantage and enormous potential of the atomic interdiffusion treatment in catalytic applications.     

核壳型铂基燃料电池催化剂制备方法与微结构控制综述

目前催化剂是制约燃料电池走向市场的关键,限制了燃料电池发展及大规模商业应用,寻求能够同时降低催化剂成本和提高催化剂性能的有效方法十分迫切。具有核壳结构的Pt-M催化剂不仅可以降低贵金属铂的用量,而且能显著提高催化活性。本文总结了近20年来核壳型Pt-M催化剂的主要制备方法,包括晶种法、去合金法、电化学沉积法等;重点分析非贵金属-铂核壳结构(M@Pt,M=Ni、Co、Cu、Fe等)的制备途径,总结了每种方法的特点。另外,还讨论了核壳结构在纳米层次上的精细控制和设计方案,这有助于理解核壳结构对电化学催化动力学的作用规律,更好地设计开发新型催化剂。     

Electrodeposition of gold thin films with controlled morphologies and their applications in electrocatalysis and SERS

Here, an easy and effective electrochemical route towards the synthesis of gold thin films with well-controlled roughness, morphology and crystallographic orientation is reported. To control these different factors, the applied potential during deposition played a major role. A tentative nucleation and growth mechanism is demonstrated by means of electrochemical characterizations and a formation mechanism is proposed. Interestingly, the differences in geometry and orientation of the different gold deposits have shown a clear correlation with the electrocatalytical activity in the case of oxygen sensing. In addition, not only the electrocatalytical activity but also the surface-enhanced Raman scattering of the gold deposits have been found to depend both on the roughness and on the size of the surface nanostructures, allowing a fine tuning by controlling these two parameters during deposition.     

Facile synthesis of highly branched jacks-like ZnO nanorods and their applications in dye-sensitized solar cells

Highly branched, jacks-like ZnO nanorods architecture were explored as a photoanode in dye-sensitized solar cells, and their photovoltaic performance was compared with that of branch-free ZnO nanorods photoanodes. The highly branched network and large pores of the jacks-like ZnO nanorods electrodes enhances the charge transport, and electrolyte penetration. Thus, the jacks-like ZnO nanorods DSSCs render a higher conversion efficiency of η = 1.82% (V_oc = 0.59 V, J_sc = 5.52 mA cm⁻²) than that of the branch-free ZnO nanorods electrodes (η = 1.08%, V_oc = 0.49 V, J_sc = 4.02 mA cm⁻²). The incident photon-to-current conversion efficiency measurements reveal that the jacks-like ZnO nanorods DSSCs exhibit higher internal quantum efficiency (∼59.1%) than do the branch-free ZnO nanorods DSSC (∼52.5%). The charge transfer resistances at the ZnO/dye/electrolyte interfaces investigated using electrochemical impedance spectroscopy showed that the jacks-like ZnO nanorods DSSC had high charge transfer resistance and a slightly longer electron lifetime, thus improving the solar-cell performance.     

Pt-Ir合金化提高PEMFC中纯铂催化剂的催化活性和稳定性

采用乙二醇为还原剂的液相还原法和后续热处理途径制备了Pt/Ir原子比1∶1的Pt-Ir合金催化剂,利用X射线衍射(XRD)、透射电子显微镜(TEM)、电感耦合等离子体质谱(ICP)、X射线光电子能谱(XPS)等方法对合金催化剂的形貌和结构进行了表征,并采用循环伏安法(CV)、线性电势扫描(LSV)等电化学方法评价了它们的电催化活性和稳定性。结果表明,经过400℃热处理的Pt-Ir/CNC-400催化剂表现出了高于商业JM催化剂的电催化性能和稳定性。其原因主要在于,Pt-Ir纳米颗粒的合金化作用使颗粒表面的电子结构和组成发生了变化,更有利于提高催化剂的催化活性。     

有序介孔纳米膜的形成机理及在电池中的应用展望

阐述目前制备有序介孔薄膜所用的模板剂(离子型和非离子型表面活性剂)制备介孔薄膜的研究进展,并且就有关现今粉体介孔材料与有序介孔纳米薄膜的形成条件、制备机理的研究方法进行总结,最后展望有序介孔结构薄膜材料在电池器件领域中潜在的应用价值.     

Covalent functionalization of metal oxide and carbon nanostructures with polyoctasilsesquioxane (POSS) and their incorporation in polymer composites

Polyoctasilsesquioxane (POSS) has been employed to covalently functionalize nanostructures of TiO₂, ZnO and Fe₂O₃ as well as carbon nanotubes, nanodiamond and graphene to enable their dispersion in polar solvents. Covalent functionalization of these nanostructures with POSS has been established by electron microscopy, EDAX analysis and infrared spectroscopy. On heating the POSS-functionalized nanostructures, silica-coated nanostructures are obtained. POSS-functionalized nanoparticles of TiO₂, Fe₂O₃ and graphite were utilized to prepare polymer-nanostructure composites based on PVA and nylon-6,6.     

Formation of size and shape tunable gold nanoparticles in solution by bio-assisted synthesis with bovine serum albumin in native and denaturated state

We have successfully controlled the size and shape of gold nanoparticles (GNPs) through a one-step bio-assisted procedure by using bovine serum albumin (BSA) protein as both reducing and stabilizing agent. We found that the growing process of GNPs can be directly manipulated by simply controlling the BSA concentration in solution and the reaction temperature. The GNPs formation was followed both experimentally by UV–vis–NIR spectroscopy and transmission electron microscopy (TEM) and theoretically by finite difference time domain (FDTD) simulations. The surface plasmon resonance of as-prepared GNPs suits the needs of many biological applications.     

Preparation of Zr-doped mesoporous TiO2 particles and their applications in the novel working electrode of a dye-sensitized solar cell

This paper presents an implementation of our recent theory on the suspension of electron-hole recombination via electronic- and micro-structure optimization to study the influence of Zr-doping on the efficiency (η) of TiO₂-based dye-sensitized solar cells (DSSCs). We developed a four-layered working electrode, in which the size of particles increased from the bottom layer of TiO₂ (P-25) through three successive layers of Zr-doped TiO₂, which were calcined at 450, 600, and 850 °C respectively. The enhancement in open-circuit photovoltage (V_oc) and short-circuit photocurrent density (J_sc) can be attributed to the electronic- and micro-structures in the working electrode. The former is related to band bending, whereas the latter is related to light-scattering within multiple layers. Simulation results (FactSage) demonstrate that Zr doping in TiO₂ can suspend or delay the formation of oxygen vacancies and thereby reduce the number of electron scattering centers, which helps to suspend electron-hole recombination by strengthening Ti-O bonds. The proposed four-layered working electrode produced an 80.2% increase in η, compared with DSSCs using a TiO₂ (P-25) electrode. This study demonstrated a novel metal doping strategy for the manipulation of electronic structure and photoelectron conversion efficiency. The proposed methodology could also be used to guide the design of photo-catalysts in general.     

Deposition of a-C:N films and evaluation of their robustness in electrochemical applications

A multilayer a-C:N film electrode deposition process has been developed using the filtered cathodic vacuum arc (FCVA) system based on the highly conductive silicon wafer with a Ti interlayer for ohmic contacts. Its robustness has been evaluated under the practical electrochemical conditions and shows that it has no pin-hole and no breaking point happened when voltages are applied on it. Extremely large errors will arise in the electrochemical characterizing a-C:N film electrodes (hydrogen and oxygen evolutions and oxygen reduction) when there is a pin-hole or a broken point in the films. And the error caused by the non-ohmic contact amplifies at a high potential range. It is expected that non-robust a-C:N film electrodes and non-ohmic contacts mislead the electrochemical characterizing on a-C:N films.     

Direct synthesis of highly conductive poly（3,4- ethylenedioxythiophene）：poly（4-styrenesulfonate） （PEDOT：PSS）/graphene composites and their applications in energy harvesting systems

We report for the first time highly conductive poly（3,4-ethylenedioxythiophene）： poly（4-styrenesulfonate） （PEDOT：PSS）/graphene composites fabricated by in situ polymerization and their applications in a thermoelectric device and a platinum （Pt）-free dye-sensitized solar cell （DSSC） as energy harvesting systems. Graphene was dispersed in a solution of poly（4-styrenesulfonate） （PSS） and polymerization was directly carried out by addition of 3,4-ethylenedioxythiophene （EDOT） monomer to the dispersion. The content of the graphene was varied and optimized to give the highest electrical conductivity. The composite solution was ready to use without any reduction process because reduced graphene oxide was used. The fabricated film had a conductivity of 637 S.cm-1, corresponding to an enhancement of 41%, after the introduction of 3 wt.% graphene without any further complicated reduction processes of graphene being required. The highly conductive composite films were employed in an organic thermoelectric device, and the device showed a power factor of 45.7 μW·m^-1K^-2 which is 93% higher than a device based on pristine PEDOT：PSS. In addition, the highly conductive composite films were used in Pt-free DSSCs, showing an energy conversion efficiency of 5.4%, which is 21% higher than that of a DSSC based on PEDOT：PSS.     

Effect of process conditions on dynamics and performance of PEMFC: Comparison with experiments

Three-dimensional numerical computations have been carried out to investigate the dynamics inside proton-exchange membrane fuel cell (PEMFC) and its performance using Star-CD solver, the computational fluid dynamics software. Theoretical results in polarization curves quantitatively corroborate the experimental findings previously reported in Jung et al. [2]. Also, effects of various process conditions such as relative humidity, stoichiometric ratio at anode and cathode channels, and cell configuration on the performance of fuel cell have been further scrutinized. It has been revealed that the moderately high stoichiometric ratio at cathode channel and single serpentine geometry improve the cell performance and also the humidity change at cathode makes the cell voltage variation high, comparing with the humidity change at anode.     

Recent progress in molten salt synthesis of low-dimensional perovskite oxide nanostructures,structural characterization,properties, and functional applications: A review

Molten salt synthesis (MSS) method has advantages of the simplicity in the process equipment, versatile and large-scale synthesis, and friendly environment, which provides an excellent approach to synthesize high pure oxide powders with controllable compositions and morphologies. Among these oxides, perovskite oxides with a composition of ABO3 exhibit a broad spectrum of physical properties and functions (e.g. ferroelectric, piezoelectric, magnetic, photovoltaic and photocatalytic properties). The downscaling of the spatial geometry of perovskite oxides into nanometers result in novel properties that are different from the bulk and film counterparts. Recent interest in nanoscience and nanotechnology has led to great efforts focusing on the synthesis of low-dimensional perovskite oxide nanostructures (PONs) to better understand their novel physical properties at nanoscale. Therefore, the low-dimensional PONs such as perovskite nanoparticles, nanowires, nanorods, nanotubes, nanofibers, nanobelts, and two dimensional oxide nanostructures, play an important role in developing the next generation of oxide electronics. In the past few years, much effort has been made on the synthesis of PONs by MSS method and their structural characterizations. The functional applications of PONs are also explored in the fields of storage memory, energy harvesting, and solar energy conversion. This review summarizes the recent progress in the synthesis of low-dimensional PONs by MSS method and its modified ways. Their structural characterization and physical properties are also scrutinized. The potential applications of low-dimensional PONs in different fields such as data memory and storage, energy harvesting, solar energy conversion, are highlighted. Perspectives concerning the future research trends and challenges of low-dimensional PONs are also outlined.     

Defects in woven preforms: Formation mechanisms and the effects of laminate design and layup protocol

Defects, such as in-plane waviness and out-of-plane tow wrinkles, cause significant reductions in the mechanical performance of RTM-manufactured composite parts based on woven preforms. To avoid this problem and achieve a greater acceptance rate in industrial processes, the mechanisms behind these defects must be understood. This paper presents a mechanism for the formation of these defects, which is supported through layup trials of woven preforms. Laminate design and layup protocol were found to be significant drivers behind the mechanism. Defect severity can be controlled through intelligent stacking sequence design and reducing ply bridging by manual forming actions and ply–ply adhesion during layup.     

Facile synthesis of Bi2S3 nanocrystalline-modified TiO2: Fe nanotubes hybrids and their photocatalytic activities in dye degradation

Interface-induced effects and large specific area of heteronanostructures are attracting much attention due to applications in photocatalysis. In this work, ultrafine bismuth sulfide (Bi₂S₃) nanocrystalline-modified Fe-doped TiO₂ nanotubes (NTs) were fabricated with facile methods. The effect of the ratio of Bi₂S₃ to the Fe-doped TiO₂ NTs on the microstructural, optical, and photocatalytic properties of the NTs and hybrids was studied. The NTs showed an actual Fe content of ～ 2.93 at.%. The optical bandgap of the NTs and hybrids was ～2.90 eV and ～2.46–2.88 eV, respectively, and decreased with increasing Bi₂S₃/NTs ratio. The specific surface area of the NTs was ～333 m² · g^?1; whereas the hybrids showed obviously larger specific surface area of ～ 527–689 m² · g^?1 than the NTs because of well-controlled formation process of Bi₂S₃ nanoparticles. The sunlight-excited degradation experiments of dyes in the water indicated that the photocatalytic activity of the hybrids was higher than that of the NTs and increased with increasing Bi₂S₃/NTs ratio. Moreover, the degradation rates of two dyes at different initial pH values were very different. The high photocatalytic activity of the hybrids was mainly ascribed to the narrow bandgap, large specific surface area, and effective heterojunction.