Synthesis of carbon supported palladium nanoparticles catalyst using a facile homogeneous precipitation-reduction reaction method for formic acid electrooxidation

A highly dispersed and ultrafine carbon supported Pd nanoparticles (Pd/C) catalyst is synthesized by a facile homogeneous precipitation-reduction reaction method. Under the appropriate pH conditions, [PdCl₄]²⁻ species in PdCl₂ solution are slowly transformed into the insoluble palladium oxide hydrate (PdO·H₂O) precipitation by heat treatment due to a slow hydrolysis reaction, which results in the generation of carbon supported PdO·H₂O nanoparticles (PdO·H₂O/C) sample with the high dispersion and small particle size. Consequently, a highly dispersed and ultrafine Pd/C catalyst can be synthesized by PdO·H₂O → Pd⁰ in situ reduction reaction path in the presence of NaBH₄. As a result, the resulting Pd/C catalyst possesses a significantly electrocatalytic performance for formic acid electrooxidation, which is attributed to the uniformly sized and highly dispersed nanostructure.     

Deactivation of carbon supported palladium catalyst in direct formic acid fuel cell

A new carbon black supported palladium catalyst for direct formic acid fuel cell applications has been prepared and characterized by X-ray diffraction. Bi-modal distribution of Pd crystallite sizes was observed. The average Pd size for crystallites in small size and large size ranges were about 2.7 nm and 11.2 nm, respectively. The initial activity of the catalyst in the oxidation of formic acid tested in a fuel cell was similar to a commercial well dispersed 20 wt.% Pd/Vulcan. The rates of the fuel cell power decay were measured for formic acid of two purities for various current loadings. The results showed that various mechanisms contribute to the decrease of cell power with time. In direct formic acid fuel cell (DFAFC) fed with a very pure HCOOH accumulation of CO₂ gas bubbles in anode catalyst layer is responsible for observed power decay. In DFAFC fed with a pure for analysis (p.a.) grade formic acid the formation of CO_ads poison from the formic acid impurities is the main deactivation reason.     

Promotion of partial oxidation of methanol over thin Pt and Pd film catalysts by resonance oscillation of acoustic waves

The thickness extension mode resonance oscillation (TERO) of bulk acoustic waves generated on z-cut LiNbO₃ by rf electric power was employed to the catalytic oxidation of methanol over thin Pt and Pd film catalysts deposited. Both the catalysts produced formaldehyde, methyl formate, and carbon dioxide as carbon-containing products in the gas phase. The TERO considerably increased the selectivity for formaldehyde production on Pt at a moderate rf power, indicating the ability of promoting the partial oxidation of methanol, whereas a small and monotonous decrease in the selectivity of the reaction on Pd occurred with power. The different TERO effects on the selectivity are discussed.     

Progress in Developments of Inorganic Nanocatalysts for Application in Direct Methanol Fuel Cells

Significant progress has been made in the last few years toward synthesizing highly dispersible inorganic catalysts for application in the electrodes of direct methanol fuel cells. In addition, research toward achieving an efficient catalyst supporting matrix has also attracted much attention in recent years. Carbon black- (Vulcan XC-72) supported Platinum and Platinum-Ruthenium catalysts have for long served as the conventional choice as the cathode and the anode catalyst materials, respectively. Oxygen reduction reaction at the cathode and methanol oxidation reaction at the anode occur simultaneously during the operation of a direct methanol fuel cell. However, inefficiencies in these reactions result in a generation of mixed potential. This, in turn, gives rise to reduced cell voltage, increased oxygen stoichiometric ratio, and generation of additional water that is responsible for water flooding in the cathode chamber. In addition, the lack of long-term stability of Pt-Ru anode catalyst, coupled with the tendency of Ru to cross through the polymer electrolyte membrane and eventually get deposited on the cathode, is also a serious drawback. Another source of potential concern is the fact that the natural resource of Pt and the rare earth metal Ru is very limited, and has been predicted to become exhausted very soon. To overcome these problems, new catalyst systems with high methanol tolerance and higher catalytic activity than Pt need to be developed. In addition, the catalyst-supporting matrix is also witnessing a change from traditionally used carbon powder to transition metal carbides and other high-performance materials. This article surveys the recent literature based on the advancements made in the field of highly dispersible inorganic catalysts for application in direct methanol fuel cells, as well as the progress made in the area of catalyst-supporting matrices.     

变压加载对直接甲醇燃料电池阳极性能的影响（英）

为评价直接甲醇燃料电池（DMFC）阳极的稳定性,利用扫描电化学显微镜和常规电化学技术,研究了变压加载过程中DMFC阳极性能的变化。结果表明,在探针扫描过程中,经不同电压加载后的DMFC阳极表面的扫描电流呈相似的锯齿状分布。当阳极加载2 h,随加载电位升高,扫描峰电流的数量减少,对应峰电流的数值则先增大再减小,表明阳极的催化活性处于不均匀分布状态且随加载时间延长和加载电位升高而逐渐降低。在不同加载电位下,随加载时间延长,循环伏安曲线上的正向和反向电流峰先负移再正移,但抗CO性能持续降低。DMFC阳极在0.6 V下分别加载16 h和72 h后,催化剂粒径由3.4 nm分别增大到3.6 nm和4.4 nm。在0.8 V下加载72 h后,Pt/Ru重量比由2.0增加到3.9。变压加载使催化活性的不均匀分布加剧催化剂粒径长大,Ru流失加快,从而导致阳极催化性能衰减。     

A rational design of bimetallic PdAu nanoflowers as efficient catalysts for methanol oxidation reaction

Methanol fuel cells have been intensively developed as clean and high-efficiency energy conversion system due to their high efficiency and low emission of pollutants. Here, we developed a simple aqueous synthetic method to prepare bimetallic Pd Au nanoflowers catalysts for methanol oxidation reaction(MOR) in alkaline environment. Their composition can be directly tuned by changing the ratio between Pd and Au precursors. Compared with commercial Pd/C catalyst, all of the Pd Au nanoflowers catalysts show the enhanced catalytic activity and durability. In particular, the Pd Au nanoflowers specific activity reached 0.72 m A/cm2, which is 14 times that of commercial Pd/C catalyst. The superior MOR activity could be attributed to the unique porous structure and the shift of the d-band center of Pd.     

Ultrasonic radiation to enable improvement of direct methanol fuel cell

To improve DMFC (direct methanol fuel cell) performance, a new method using ultrasonic radiation is proposed and a novel DMFC structure is designed and fabricated in the present paper. Three ultrasonic transducers (piezoelectric transducer, PZT) are integrated in the flow field plate to form the ultrasonic field in the liquid fuel. Ultrasonic frequency, acoustic power, and methanol concentration have been considered as variables in the experiments. With the help of ultrasonic radiation, the maximum output power and limiting current of cell can be independently increased by 30.73% and 40.54%, respectively. The best performance of DMFC is obtained at the condition of ultrasonic radiation (30 kHz and 4 W) fed with 2 M methanol solution, because both its limiting current and output power reach their maximum value simultaneously (222 mA and 33.6 mW, respectively) under this condition. These results conclude that ultrasonic can be an alternative choice for improving the cell performance, and can facilitate a guideline for the optimization of DMFC.     

Cobalt-containing oxide layers on titanium, their composition, morphology, and catalytic activity in CO oxidation

In this study possibility to form the layered compositions CoO_x + SiO₂/TiO₂/Ti by plasma electrolytic oxidation (PEO) method was shown. Compositions have been obtained by both one-stage PEO method (Method I) with addition of Co(CH₃COO)₂ into silicate electrolyte and impregnation of preliminary obtained by the PEO method SiO₂/TiO₂/Ti systems in aqueous solutions containing cobalt salts with their following annealing (Method II). XRD, XPS and SEM/EDX were used to investigate the phase and element composition, microstructure of the coatings prepared by the two various methods. Catalytic activity of the cobalt-containing composites was investigated in the CO oxidation reaction. Under experimental conditions, the structures obtained by impregnation and annealing method were more active, than those obtained by one-stage PEO method. The surface structures of cobalt-containing coatings obtained by the PEO method and by impregnation and annealing differ in both quantitative and qualitative relation. The cobalt content on the surface of impregnating coatings is three times as much as that for those formed by one-stage PEO method. It is found that coatings obtained by the Method II have a more developed surface. The surface of CoO_x + SiO₂/TiO₂/Ti compositions obtained by the PEO method contains, presumably Co(OH)₂ and Co₃O₄. The surface of the similar compositions obtained by the Method II, possibly contains CoO, either Co₂O₃, or CoOOH. The combination of these factors, perhaps, also provides a higher activity of the compositions formed by the Method II.     

High catalytic performance of Pt nanoparticles on plasma treated carbon nanotubes for electrooxidation of ethanol in a basic solution

Nanosized Pt particles deposited on plasma treated multi-walled carbon nanotubes have been used in electrocatalytic oxidation of ethanol in a basic solution. These Pt nanoparticles have very narrow size distribution and exhibit significant higher catalytic activities, higher Pt utilization efficiency (93.77%) and improved durability in comparison to the commercial available Johnson Matthey Pt/C catalyst.     

Synthesis of nitrogen-doped ZnO nanocrystallites with one-dimensional structure and their catalytic activity for ammonium perchlorate decomposition

Journal of Nanoparticle Research - In this study, nitrogen-doped ZnO (N-doped ZnO) nanocrystallites with a one-dimensional structure were synthesized successfully via an advanced wet chemical...     

Investigation of metal nanoparticles produced by laser ablation and their catalytic activity

Polydiphenylsilylenemethylene (PDPhSM) thin films, which are difficult to fabricate by conventional methods because of their insolubility and high melting point, have been synthesized by using laser-ablated metal nanoparticles for the thermal ring-opening polymerization of 1,1,3,3-tetraphenyl-1,3-disilacyclobutane (TPDC) in this paper. TPDC was first evaporated on silicon substrates and then exposed to metal (Pt, Cu and Ag) nanoparticles deposition by laser ablation prior to heat treatment. The catalytic activity of Pt, Cu and Ag nanoparticles has been studied. The results showed that the mean diameter of Pt nanoparticles was the smallest, Cu nanoparticles the moderate and Ag nanoparticles the biggest, while the polymerization efficiency for Pt nanoparticles was the highest, Cu nanoparticles the moderate and Ag nanoparticles the lowest. In addition, the penetration behaviours of Pt, Cu and Ag nanoparticles into the TPDC monomer films during laser ablation were different due to the particle size or the chemical interaction between metal nanoparticles and TPDC molecules.     

Influence of pretreatment methods on adsorption and catalytic characteristics of toluene over heterogeneous palladium based catalysts

The adsorption and catalytic characteristics of heterogeneous palladium based catalyst and its modified catalysts with gases (air and hydrogen) and acidic aqueous solution (HCl) were studied for evaluating the influence of pretreatment methods for toluene. The structural and energetic adsorption properties of the parent and pretreated catalysts were analyzed by means of nitrogen adsorption isotherms and gravimetric methods. The light-off curve and the XPS investigation were used for analyzing the catalytic activity and the surface state of palladium. It was clearly shown from the experimental results that hydrogen pretreated catalysts having metallic surface state exhibited the highest adsorption capacity and catalytic activity compared to that of parent and modified catalysts. The adsorption equilibrium data for toluene were obtained at three different temperatures and correlated successfully with the two-site Langmuir molecular isotherm model (L2m). It was also found that the palladium phase has more adsorption affinity for toluene molecules than the alumina support. The isosteric heat of adsorption calculated by using the Clausius-Clapeyron equation significantly changed with the coverage and the lateral interactions between the adsorbate-adsorbate molecules control the system. Furthermore, comparative analysis of the adsorption energy distribution revealed that the parent and its modified catalysts have different types of surface energetic heterogeneities.     

Synthesis,spectral studies,and catalytic and antibacterial activity of Ru(II) complexes with coordinated amides

Twelve Ru(II) complexes with coordinated amides were synthesized and characterized by elemental, IR, ¹H, ¹³C, ³¹P NMR, mass, and electronic spectral analysis, along with magnetic and conductance measurements. Molecular formulas and octahedral structures have been tentatively proposed. These complexes were used as catalysts for the hydrolysis of rivastigmine and neostigmine. The hydrolyzed products were coupled with 3-methyl benzothiazolinone hydrazone reagent in the presence of sodium metaperiodate and the resulting colored products were determined spectrophotometrically. The yields of hydrolyzed products were found to be 98.47% and 99.75% respectively. All the ligands and Ru(II) complexes were screened for antibacterial activity. Published in Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 6, pp. 867–874, November–December, 2008.     

Synthesis of monodisperse In2O3 nanoparticles and their d0 ferromagnetism

Monodisperse indium oxide (In₂O₃) nanoparticles (NPs) with the average diameter of 11 nm were prepared by a solvothermal method. The In₂O₃ NPs were characterized by X-ray diffraction, Raman and transmission electron microscopy. The intrinsic nature of ferromagnetism in In₂O₃ NPs has been established with the experimental observation of magnetic hysteresis loop. Photoluminescence and UV–visible studies were employed to evidence the presence of oxygen vacancies and revealed that the oxygen vacancies contribute to the ferromagnetism. The origin of ferromagnetism in In₂O₃ NPs may be due to exchange interactions among localized electron spin moments resulting from oxygen vacancies.     

Synthesis and characterization of vanadium nanoparticles on activated carbon and their catalytic activity in thiophene hydrodesulphurization

Vanadium nanoparticles (∼7 nm) stabilized on activated carbon were synthesized by the reduction of VCl₃·3THF with K[BEt₃H]. This material was characterized by inductive coupled plasma-atomic emission spectroscopy (ICP-AES), high-resolution transmission electron microscopy (HRTEM) and X-ray photoelectron spectroscopy (XPS) analyses. The catalytic performance of the carbon-supported vanadium was studied using thiophene hydrodesulfurization (HDS) as model reaction at 300 °C and P = 1 atm. The catalytic activity of the vanadium carbide phase on the activated carbon carrier was more significant than that of the reference catalysts, alumina supported NiMoS. The method proposed for the synthesis of such a catalyst led to an excellent performance of the HDS process.     

Synthesis of graphene oxide sheets decorated by silver nanoparticles in organic phase and their catalytic activity

The graphene oxide(GO) sheets decorated by Ag nanoparticles were prepared using a liquid–liquid two-phase method at the room temperature. The synthesized samples existed in the organic phase and were characterized by X-ray diffraction, transmission electron microscopy, UV–vis spectroscopy and Raman spectra. The results demonstrate that these silver-nanoparticles with diameter of about 10 nm assembled on graphene oxide sheets are flexible and can form stable suspensions in organic phase. Raman signals of graphene oxide sheets are increased by the attached silver nanoparticles, displaying higher surface-enhanced Raman scattering activity. Furthermore, Ag/GO are found to serve as effective catalysts to activate the reduction of 4-nitrophenol (4NP) in the presence of NaBH₄.     

Catalytic activity of Pd ensembles incorporated into Au nanocluster for CO oxidation: A first-principles study

We investigated the catalytic activity of Pd atoms incorporated into Au(111) facet through first-principles calculations, and found that the Pd monomer, dimer, and trimer are highly reactive for the reaction of CO+O₂→CO₂+Ovia association mechanism, in which an intermediate state (OOCO) is formed. Significantly, a low energy barrier (0.19-0.32 eV) was found for the formation of OOCO. The atomic oxygen left by CO+O₂→CO₂+O reaction can be removed by another CO on Pd-decorated Au cluster via Langmuir-Hinshelwood or Eley-Rideal mechanism. Our studies indicate Pd ensembles incorporated into Au(111) facet markedly improve the catalytic activity of gold nanocluster.     

Invariance of activity coefficients for the hydrogen ion with charge-type of fluorescent indicators in aqueous-methanol solutions

Steady-state fluorimetric pH titrations of three fluorescent indicators of differing charge-type were carried out in aqueous methanol solutions containing up to 64 mol% methanol. The plot of the ratio of the relative fluorescence efficiency of the indicator acid to that of its conjugate base versus the product of the formal hydrogen ion concentration and the appropriate Bronsted kinetic activity factor gives straight lines for titrations in each mixed solvent, just as it does in water, but only if the constant terms in the Bronsted factor are modified to account for the bulk dielectric constant in each solvent. The product of the formal charges on the proton and the particular conjugate base studied in each titration must also be included in the Bronsted factor. This supports the hypothesis that a valid operational pH can be defined and kinetic parameters related to proton transfer can be extracted from the fluorimetric titrations in mixed solvents.     

Synthesis and catalytic activity of hybrid metal/silicon nanocomposites

In this Letter we demonstrate that hydrogen‐terminated porous silicon (PSi) layers and powders can serve as highly efficient reductive templates for noble metal salts. The reduction results in metal nanoparticle (NP) formation in the pores of PSi. Gold NP formation has been monitored in‐situ by measuring the plasmon resonance response. Pt NPs, formed in the PSi matrix, were investigated by transmission electron microscopy and energy‐dispersive X‐ray analysis. Furthermore, hybrid Pt/PSi nanocomposites exhibit a high catalytic activity for CO oxidation.