Probing platinum degradation in polymer electrolyte membrane fuel cells by synchrotron X-ray microscopy

Synchrotron-based scanning transmission X-ray spectromicroscopy (STXM) was used to characterize the local chemical environment at and around the platinum particles in the membrane (PTIM) which form in operationally tested (end-of-life, EOL) catalyst coated membranes (CCMs) of polymer electrolyte membrane fuel cells (PEM-FC). The band of metallic Pt particles in operationally tested CCM membranes was imaged using transmission electron microscopy (TEM). The cathode catalyst layer in the beginning-of-life (BOL) CCMs was fabricated using commercially available catalysts created from Pt precursors with and without nitrogen containing ligands. The surface composition of these catalyst powders was measured by X-ray Photoelectron Spectroscopy (XPS). The local chemical environment of the PTIM in EOL CCMs was found to be directly related to the Pt precursor used in CCM fabrication. STXM chemical mapping at the N 1s edge revealed a characteristic spectrum at and around the dendritic Pt particles in CCMs fabricated with nitrogen containing Pt-precursors. This N 1s spectrum was identical to that of the cathode and different from the membrane. For CCM samples fabricated without nitrogen containing Pt-precursors the N 1s spectrum at the Pt particles was indistinguishable from that of the adjacent membrane. We interpret these observations to indicate that nitrogenous ligands in the nitrogen containing precursors, or decomposition product(s) from that source, are transported together with the dissolved Pt from the cathode into the membrane as a result of the catalyst degradation process. This places constraints on possible mechanisms for the PTIM band formation process.     

AFM characterization of dendrimer-stabilized platinum nanoparticles

This work describes the use of atomic force microscopy (AFM) to measure the size of dendrimer-stabilized Pt nanoparticles (Pt DNs) deposited from aqueous solutions onto mica surfaces. Despite considerable previous work in this area, we do not fully understand the mechanisms by which PAMAM dendrimers template the formation of Pt DNs. In particular, Pt DN sizes measured by high-resolution transmission electron microscopy (HRTEM) are reported to be larger than expected if one assumes that each PAMAM molecule templates one spherical Pt nanoparticle. AFM provides a vertical height measurement that complements the lateral dimension measurement from HRTEM. We show that AFM height measurements can distinguish between "empty" PAMAM and Pt DNs. If the complexation of Pt precursor with PAMAM is prematurely terminated, AFM images and feature height distributions show evidence of arrested precipitation of Pt colloids. In contrast, sufficient Pt-PAMAM complexation time leads to AFM images and height distributions that have relatively narrow, normal distributions with mean values that increase with the nominal Pt:PAMAM ratio. The surface density of features in AFM images suggest that these Pt DNs reside on the mica surface as two-dimensional surface aggregates. These observations are consistent with an intradendrimer templating mechanism for Pt DNs. However, we cannot determine if the mechanism obeys a fixed loading law because we do not have definitive information about Pt DN shape. A second peak in the Pt DN height distribution appears when the Pt loading exceeds about 66% of PAMAM's theoretical capacity for Pt. Excluding these secondary particles, the dependence of mean feature height on the Pt:PAMAM ratio follows a power-law relationship. Also considering the magnitudes of the measured mean height values, the data suggest that Pt DNs exist as ramified, noncompact aggregates of Pt atoms interspersed within the PAMAM framework.     

Durable electrocatalytic-activity of Pt-Au/C cathode in PEMFCs

Longevity remains as one of the central issues in the successful commercialization of polymer electrolyte membrane fuel cells (PEMFCs) and primarily hinges on the durability of the cathode. Incorporation of gold (Au) to platinum (Pt) is known to ameliorate both the electrocatalytic activity and stability of cathode in relation to pristine Pt-cathodes that are currently being used in PEMFCs. In this study, an accelerated stress test (AST) is conducted to simulate prolonged fuel-cell operating conditions by potential cycling the carbon-supported Pt-Au (Pt-Au/C) cathode. The loss in performance of PEMFC with Pt-Au/C cathode is found to be ～10% after 7000 accelerated potential-cycles as against ～60% for Pt/C cathode under similar conditions. These data are in conformity with the electrochemical surface-area values. PEMFC with Pt-Au/C cathode can withstand >10,000 potential cycles with very little effect on its performance. X-ray diffraction and transmission electron microscopy studies on the catalyst before and after AST suggest that incorporating Au with Pt helps mitigate aggregation of Pt particles during prolonged fuel-cell operations while X-ray photoelectron spectroscopy reflects that the metallic nature of Pt is retained in the Pt-Au catalyst during AST in comparison to Pt/C that shows a major portion of Pt to be present as oxidic platinum. Field-emission scanning electron microscopy conducted on the membrane electrode assembly before and after AST suggests that incorporating Au with Pt helps mitigating deformations in the catalyst layer.     

Comparative study of nanoscale surface structures of calcite microcrystals using FE-SEM, AFM, and TEM.

The bulk morphology and surface features that developed upon precipitation on micrometer-size calcite powders and millimeter-size cleavage fragments were imaged by three different microscopic techniques: field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) of Pt-C replicas, and atomic force microscopy (AFM). Each technique can resolve some nanoscale surface features, but they offer different ranges of magnification and dimensional resolutions. Because sample preparation and imaging is not constrained by crystal orientation, FE-SEM and TEM of Pt-C replicas are best suited to image the overall morphology of microcrystals. However, owing to the decoration effect of Pt-C on the crystal faces, TEM of Pt-C replicas is superior at resolving nanoscale surface structures, including the development of new faces and the different microtopography among nonequivalent faces in microcrystals, which cannot be revealed by FE-SEM. In conjunction with SEM, Pt-C replica provides the evidence that crystals grow in diverse and face-specific modes. The TEM imaging of Pt-C replicas has nanoscale resolution comparable to AFM. AFM yielded quantitative information (e.g., crystallographic orientation and height of steps) of microtopographic features. In contrast to Pt-C replicas and SEM providing three-dimensional images of the crystals, AFM can only image one individual cleavage or flat surface at a time.     

Synthesis of single-crystalline platinum nanorods within a soft crystalline surfactant-Pt(II) complex.

Single-crystalline platinum nanorods, monodisperse in diameter, are synthesized through a simple process at room temperature, in cetyltrimethyl ammonium bromide (CTAB) solution. The complexation of the CTA+ surfactant ion with tetrachloroplatinate in the presence of hexanol leads to the formation of a precipitate with a lamellar crystalline structure. The reduction of Pt(II) metal ions to Pt(0) is carried out using gamma radiolysis. Transmission electron microscopy (TEM) observations of the nanoparticles extracted from the solution, three weeks after radiolysis, revealed single-crystalline Pt nanorods, monodisperse in diameter (3-4 nm) and 20-60 nm long. By following the shape of the nanorods at various stages of the growth, it was found that the single-crystalline nanorods grow by coalescence of spherical seeds 3-4 nm in diameter. This suggests an aggregative mechanism similar to that recently observed for silver particles in solution.     

预制铂纳米颗粒对质子交换膜燃料电池用铂纳米线阴极的结构影响

铂纳米线（Pt NWs）由于其独特的结构特点,比商业Pt/C具有更高的氧还原反应（ORR）比活性。在本工作中,我们将预先制备好的铂纳米颗粒（Pt NPs）引入到碳基体中,用于诱导生长Pt NWs,获得了均匀分布Pt NWs的阴极。通过改变Pt NP载量（0~0.015 mg·cm^-2）和Pt NP来源（不同Pt含量的Pt/C）研究了所制备阴极的结构和性能。用扫描电镜对阴极表面进行了表征,并用透射电镜和X射线衍射分析了Pt NW的形貌和晶体结构。在单电池中分别进行了极化曲线和循环伏安曲线测试。当Pt NP来源为40% Pt/C且其载量为0.005 mg·cm^-2时,制备的Pt NW阴极具有最佳的单电池性能和最大的电化学表面积（ECSA）。最后,提出了预制Pt NP影响Pt NWs分布的可能机制。     

Platinum Nanoparticles Modified with Perfluorinated Alkylamines as a Model Cathode Catalyst for Fuel Cells

Platinum nanoparticles (NPs) modified with undecafluorohexylamine (UFHA) and octylamine were synthesized as a novel model cathode catalyst for fuel cells. The modified Pt NPs were well characterized by FTIR, X‐ray photoelectron spectroscopy, thermogravimetric analysis, and transmission electron microscopy. These NPs supported on carbon black were applied as electrocatalysts for the oxygen reduction reaction. The UFHA‐modified Pt NP catalyst showed high electrocatalytic activity and durability compared to a commercial catalyst. Besides suppression of undesired oxide formation on the Pt surface, the affinity between the perfluorinated alkyl chains of UFHA and Nafion^® improved the catalyst activity by creating a desirable proton conduction path. Additionally, UFHA modification improved durability by suppressing Pt dissolution and carbon corrosion because of restricted water accessibility. The β ‐oxide formation, which is responsible for Pt dissolution, was significantly attenuated by surface modification.     

Electrochemical Sensor for Oxidation of NO Based on Au-Pt Nanoparticles Self-assembly Film

Au-Pt bimetallic nanoparticles film used as an efficient electrochemical sensor was prepared by self-assembled Au-Pt bimetallic nanoparticles on a glassy carbon (GC) substrate using thioglycolic acid as a linker. Atomic force microscopy (AFM) and scanning electron microscopy (SEM) showed that the Au-Pt nanoparticles self-assembly film was dense and uniform. Electrochemical experiments revealed that Au-Pt bimetallic nanoparticles film/GC electrode showed high electrocatalytic activity to the oxidation of nitric oxide.     

Cyclability of sulfur/dehydrogenated polyacrylonitrile composite cathode in lithium–sulfur batteries

Sulfur/dehydrogenated polyacrylonitrile composite has been studied as cathode material for lithium–sulfur rechargeable batteries. Nonetheless, capacity fading has been a challenge for the commercialization of batteries. In this study, characterization techniques of scanning electron microscopy, energy dispersive X-ray spectroscopy, elemental analysis, cyclic voltammetry, and electrochemical impedance spectroscopy are used to investigate the change of cathode properties with charge–discharge cycles. Elemental analysis reveals that sulfur accumulates on the surface of the composite at the end of charge, and the sulfur formation decreases with cycle number. Scanning electron microscopy observations indicate that cathode surface morphology changes significantly after several cycles. By modeling the electrochemical impedance spectra of the cell in different discharge states, we suggest that capacity fading arises mainly from the formation and accumulation of irreversible Li₂S (and Li₂S₂) on the cathode surface.     

AFM study of conducting polymer polypyrrole nanoparticles formed by redox enzyme - glucose oxidase - initiated polymerisation

Redox enzyme – glucose oxidase E.C. 1.1.3.4 from Penecillum vitale (GOx) – initiated polypyrrole (Ppy) synthesis was applied for the formation of polypyrrole based nanoparticles. The increase in optical absorbance at λ = 460 nm was exploited for the monitoring of polypyrrole polymerisation process. The shape and size of the formed Ppy nanoparticles was also monitored by means of contact mode AFM. The highest increase in the diameter of the formed Ppy nanoparticles was detected during 15-day period. AFM imaging was performed in contact mode to investigate the shape and flexibility of particles deposited on the SiO₂ and Pt surfaces. Contact mode AFM investigations allowed us to conclude that after drying at 50 °C the formed Ppy particles are more flexibly deposited on the Pt electrode if compared to those deposited on the SiO₂ substrate. The application of well-shaped Ppy nanoparticles in biomedicine, chromatography and bioanalysis may be predicted.     

Platinum electrodeposits on glassy carbon: The formation mechanism, morphology, and adsorption properties

The deposition of platinum on glassy carbon (GC) is studied by chronoamperometry. Basic tendencies of the formation of aggregate platinum particles on the oxidized carbon surface are established. These include a primary instantaneous nucleation of platinum under diffusion control and the beginning of a secondary nucleation prior to filling primary active centers. The deposit morphology is examined byex situ methods of scannng electron microscopy (SEM), transmission electron microscopy (TEM), and scanning tunneling microscopy (STM). A globular structure of platinum, formed by crystallites 3–5 nm in size, is revealed. A comparison of the STM, SEM, and TEM data demonstrates a high information value and accuracy of STM in studies of disperse materials in both nanometer and submicron ranges. Various coulometry techniques intended for the determination of the true surface area of deposited platinum are compared. The most informative techniques are the voltammetry of desorption of copper adatoms and chemisorbed carbon monoxide at, respectively, low and high platinum contents. Differences in the formation kinetics and properties of aggregate particles in Pt/GC and Pt/Pt are found, specifically, smaller Pt/GC crystallites and higher degrees of their concrescence (screening)     

Effect of composition on the conductivity and morphology of poly(3-hexylthiophene)/gold nanoparticle composite Langmuir-Schaeffer films

Ultrathin Langmuir-Schaeffer (LS) films were fabricated from blends of regioregular poly(3-hexylthiophene) (P3HT) and highly monodispersed dodecanethiolate-capped gold nanoparticles (Au NPs) mixed in varying weight ratios. The morphology of the ultrathin films was investigated by UV-visible absorption spectroscopy, atomic force microscopy (AFM) and field-emission scanning electron microscopy (FE-SEM). The results of the structural investigations were correlated with the lateral conductivity of the films, with P3HT in its unintentionally doped state, probed by scanning electrochemical microscopy (SECM), which proved to be a very sensitive technique. Control over the P3HT/Au NP ratio led to remarkable changes in the morphology and lateral conductivity of the films. Inclusion of Au NPs into P3HT was found to influence the ordering of P3HT, which ultimately determined the macroscopic charge transport characteristics of the films. Composite films with ca. 33% by weight of Au NPs were found to be the most ordered and exhibited the highest conductivity, substantially higher than P3HT alone. To provide insight into the film formation process, LS composite films comprising equal quantities of P3HT and Au NPs (by weight) were transferred at several surface pressures and investigated by SECM, AFM and FE-SEM.     

Liquid crystal alignment properties on surface-reformed solution-derived lanthanum-doped zinc oxide films

Liquid crystal (LC) alignment characteristics were investigated using a solution-derived lanthanum-doped zinc oxide (La:ZnO) film that was exposed to various intensities of ion-beam (IB) irradiation. At an IB intensity of 1700 eV, uniform and homogeneous LC alignment was achieved, as revealed by cross-polarized optical microscopy and pre-tilt angle measurement. Field-emission scanning electron microscopy (FE-SEM), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS) were used to verify that the IB irradiation induced physical and chemical surface reformation of the La:ZnO film that relate to LC alignment. FE-SEM and AFM revealed that the IB irradiation reformed the existing surface structure into a new structure with an altered surface roughness. The XPS results showed that the van der Waals force with anchoring energy increased as the IB intensity increased, and this profoundly affected the state of LC alignment. The capacitance-voltage (C-V) hysteresis curve was measured as a function of IB intensity to characterize the accumulated charge as a residual DC. Nearly zero C-V hysteresis was achieved at an IB intensity of 1700 eV. Therefore, a solution-derived La:ZnO film with an IB intensity of 1700 eV has great potential for high-quality LC applications.     

Characterization of Plasma-Polymerized 4-vinyl Pyridine with Silver Nanoparticles on Poly(ethylene terephthalate) Film for Anti-Microbial Properties

4-vinyl pyridine was polymerized on poly(ethylene terephthalate) (PET) film by using lower energy pulsed AC plasma under low pressure in Ar atmosphere. The plasma polymerized coating was characterized by ATR Fourier transform infrared (FT-IR), scanning electron microscopy (SEM), field emission scanning electron microscopy (FE-SEM), atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). Different thicknesses of poly(4-vinyl pyridine) coating under different plasma polymerization conditions were studied. Silver nanoparticles with diameter around 50nm deposit were precipitated on the poly(4-vinyl pyridine) coating by UV irradiation in Silver nitride water solution, in order to enhance the anti-microbial properties. Different kinds of modified PET films were tested for anti-microbial properties against yeast (Debaryomyces hansenii) by using microbiological analyser µ-4200 and direct microscopic count method.     

Formation of GeO2 under Graphene on Ge(001)/Si(001) Substrates Using Water Vapor

The problem of graphene protection of Ge surfaces against oxidation is investigated. Raman, X-Ray diffraction (XRD), atomic force microscopy (AFM) and scanning electron microscopy (SEM) measurements of graphene epitaxially grown on Ge(001)/Si(001) substrates are presented. It is shown that the penetration of water vapor through graphene defects on Gr/Ge(001)/Si(001) samples leads to the oxidation of germanium, forming GeO₂. The presence of trigonal GeO₂ under graphene was identified by Raman and XRD measurements. The oxidation of Ge leads to the formation of blisters under the graphene layer. It is suggested that oxidation of Ge is connected with the dissociation of water molecules and penetration of OH molecules or O to the Ge surface. It has also been found that the formation of blisters of GeO₂ leads to a dramatic increase in the intensity of the graphene Raman spectrum. The increase in the Raman signal intensity is most likely due to the screening of graphene by GeO₂ from the Ge(001) surface.     

Epoxy polymer coating to prevent the corrosion of aluminum nanoparticles

Aluminum nanoparticles were coated by epoxy polymer in order to prevent the corrosion reaction. The coverage of the epoxy polymer film was controlled from 0% to 100%, which changed the corrosion rate of nanoparticles quantitatively. The surface of the polymer coating was investigated by transmission electron microscopy (TEM) and atomic force microscopy (AFM), and the corrosion resistance of these nanoparticles was estimated by the wet/dry corrosion test on platinum (Pt) plate with a NaCl solution. From a TEM analysis, 10 mass% polymer‐coated Al particles in the synthesis were almost 100% covered on the surface by a polymer film of 10 nm thick. On the other hand, 3 mass% polymer‐coated Al was partially covered by a film. In the AFM–Kelvin force microscopy, the potential around the Al particles had a relatively low value by the polymer coating, which indicated that the conductivity of the Al was isolated from Pt plate by the polymer. Both the corrosion and H₂ evolution reaction rates were quantitatively reduced by the mass% of polymer coating. In the case of 10 mass% coated sample, there was very little corrosion of Al nanoparticles. This fact suggested that the electrochemical reaction was suppressed by the polymer coating. Thus, it was found that the corrosion reaction rate of Al nanoparticles could be quantitatively suppressed by the mass% of epoxy coating. Copyright © 2015 John Wiley & Sons, Ltd.     

Pickering miniemulsion polymerization using Laponite clay as a stabilizer

Solid-stabilized, or Pickering, miniemulsion polymerizations using Laponite clay discs as stabilizer are investigated. Free radical polymerizations are carried out using a variety of hydrophobic monomers (i.e., styrene, lauryl (meth)acrylate, butyl (meth)acrylate, octyl acrylate, and 2-ethyl hexyl acrylate). Armored latexes, of which the surfaces of the particles are covered with clay discs, are obtained, as confirmed by scanning electron microscopy (FE-SEM) and atomic force microscopy (AFM). Overall polymerization kinetics of the Pickering miniemulsion polymerizations of styrene were investigated via gravimetry. Comparison with the bulk polymerization analogue clearly shows compartmentalization. Moreover, retardation effects up to intermediate monomer conversions are observed; they are more prominent for the smaller particles and are ascribed to the Laponite clay. A model is presented that allows for the prediction of the average particle size of the latexes produced as a function of the amounts of monomer and Pickering stabilizers used. It shows that under specific generic conditions the number of clay discs used correlates in a linear fashion with the total surface area of the latex particles. This is a direct result of the reversibility of the Laponite clay disc adhesion process under the emulsification conditions (i.e., sonication) used.     

Electrochemical templating of metal nanoparticles and nanowires on single-walled carbon nanotube networks

The use of single-walled carbon nanotube (SWNT) networks as templates for the electrodeposition of metal (Ag and Pt) nanostructures is described. Pristine SWNTs, grown on insulating SiO2 surfaces using catalyzed chemical vapor deposition, served as the working electrode. In the simplest case, electrical contact was made by depositing a gold strip on the SWNT substrate (device 1). Deposition of Ag and Pt over extensive periods (30 s) resulted in a high density of particles on the SWNTs, with almost contiguous nanowire formation from the Au/SWNT boundary moving to isolated nanoparticles at further distances from the contact. For direct electrochemical studies of Ag and Pt nucleation, the assembly was coated in a resist layer and a small window opened up to expose only the electrically connected SWNTs to solution (device 2). In this case, the electrochemical signature in voltammetric and amperometric studies of metal deposition was due solely to processes at the SWNTs. Coupled with high-resolution microscopy measurements (atomic force microscopy and field emission scanning electron microscopy), this approach provided detail on the nucleation and growth mechanisms of Ag and Pt on SWNTs under electrochemical control. In particular, Ag growth was found to be rapid and progressive with an increasing nanoparticle density with time, whereas Pt deposition was characterized by lower nucleation densities and slower growth rates with a tendency for larger particles to be produced over long times.     

纳米硫化锌的原位制备及其对多孔硅复合体系发光的调控

Zn S的带隙较宽 ,欧姆接触较差 ,并不是一种理想的半导体 .但将多种材料与硫化锌复合 ,在一定程度上可以克服这种缺陷 [1] .相关的文献报道主要集中在 Zn S∶ M( M=Mn,Cu,Ag等 ) ,Zn S∶ RE( RE=Sm,Tb,Eu等 ) ,Zn S∶ Cd S和 Zn S∶ Zn Se等复合材料上 ,同时也有关于多孔硅 ( PorousSilicon,PS)掺杂稀土 [2 ] 和有机物 [3,4 ] 以及 PS- Cd S[5～ 7] 的报道 ,但是尚未见到在多孔硅基体上原位制备硫化锌纳米材料的报道 .本文利用一种新颖、简单的化学方法 ,通过多相反应 ,在多孔硅基体的表面和纳米孔内制得纳米级的 Zn S,从而…     

Synthesis of Carbon Quantum Dots Nanoparticles by Cyclic Voltammetry and Its Application as Methanol Tolerant Oxygen Reduction Reaction Electrocatalyst

Carbon quantum dot (CQD) nanoparticles are synthesized by one‐step electrochemical method, cyclic voltammetry (CV), at different potentials using graphite rods and NaOH/EtOH as electrolyte. The electro‐chemically manufactured CQD is characterized by Transmission electron microscopy, Ultra violet absorption, X‐ray diffraction and Fourier transform infrared spectrometry. The morphology and microstructure methods confirm the formation of high quality CQD. Finally, we design a new gas diffusion electrode (GDE) based on CQD pasted on carbon paper for the oxygen reduction reaction at cathode side as methanol tolerance in direct methanol fuel cell and compared it with standard Pt‐C catalysts using cyclic voltammetry and linear sweep voltammetry. The ORR results in presence of methanol indicate that the GDE prepared from CQD exhibits methanol tolerance compared to the GDE prepared from Pt/C (Electrochem).