Confirmation of sulfur tolerance of bimetallic Pd–Pt supported on highly acidic USY zeolite by EXAFS

The sulfur tolerance (i.e., degree of sulfidation) of Pd and Pt in sulfided bimetallic Pd–Pt catalysts (Pd : Pt mole ratio of 4 : 1) supported on USY (ultrastable Y) zeolites (SiO₂/Al₂O₃ = 10.7, 48, and 310) was investigated using an extended X‐ray absorption fine structure (EXAFS) method. The sulfidation of the catalysts was done in a 1000 ppm H₂S–2% H₂/N₂ stream at 573 K for 0.5 h. In the Fourier transforms of Pd K‐edge and Pt L_III‐edge EXAFS spectra, both of the peaks due to metallic Pd and to metallic Pt for the Pd–Pt/USY (SiO₂/Al₂O₃ = 10.7) catalyst remained most after sulfidation. Further, the results of the Fourier transforms confirmed that the sulfur tolerance of both Pd and Pt decreased with increasing SiO₂/Al₂O₃ ratio, suggesting that Pd and Pt become sulfur‐tolerant when Pd–Pt bimetallic particles are supported on highly acidic USY zeolite. This revised version was published online in July 2006 with corrections to the Cover Date.     

Water Denitration over a Pd–Sn/Al2O3 Catalyst

Bimetallic Pd–Sn catalysts were synthesized by incipient-wetness impregnation of the metals on alumina and employed for the reduction of nitrates from aqueous solutions. The catalysts were characterized by FTIR spectroscopy of adsorbed CO, X-ray diffraction (XRD), transmission electron microscopy (TEM), and H₂ chemisorption. The influence of the metal ratio was evaluated in reaction measurements. The bimetallic Pd–Sn catalysts exhibited high selectivity for nitrate removal forming less NO₂⁻ and NH₄⁺ than the Pd–Cu catalysts.     

Control of composition and size for Pd–Ni alloy nanowires electrodeposited on highly oriented pyrolytic graphite

In order to fabricate effective Pd–Ni alloy nanowire arrays with given compositions and size, the process of nucleation and growth and the dependence of alloy composition on deposition potential were investigated. The results reveal that the compositions and sizes of Pd–Ni alloy nanowires can be controlled within a desired range through adjusting suitable nucleation and growth potentials as well as the time. The Ni content in the alloy nanowires was found to vary from 6 to 28% when the deposition potential was changed from −0.3 to −1.9 V. A growth potential of −0.35 to − 0.50 V was applied to fabricate Pd–Ni alloy nanowires with 8–15% Ni content. Continuous and parallel nanowire arrays can be successfully fabricated when nucleation is performed at a potential of −1.2 V for 50 ms with further growth at −0.45 V for 800 s. Pd–Ni crystal phases exist in the alloy structure forms of 〈111〉, 〈200〉, 〈220〉, 〈311〉. The nanowires have an average diameter of 150 nm and a length of 100–450 μm.     

Pd–Ru/C as the electrocatalyst for hydrogen peroxide reduction

Pd–Ru, Pd and Ru nanoparticles supported on Vulcan XC-72 carbon were prepared by chemical reduction of PdCl₂ and/or RuCl₃ in aqueous solution using NaBH₄ as the reducing agent. Transmission electron microscopy measurements showed that Pd–Ru particles were uniformly dispersed on carbon. The particle size of Pd–Ru is around 5–9 nm. X-ray diffraction analysis indicated that Ru formed alloy with Pd in Pd–Ru/C catalyst. The electroreduction of hydrogen peroxide on Pd–Ru/C, Pd/C and Ru/C in H₂SO₄ solution was examined by linear sweep voltammetry and chronoamperometry measurements. Results revealed that Pd–Ru/C catalyst exhibited higher electrocatalytic activity for hydrogen peroxide reduction than Pd/C and Ru/C. All the catalysts showed good stability for hydrogen peroxide electroreduction in H₂SO₄ electrolyte.     

Electrodeposition of Pd–Ag alloy nanowires on highly oriented pyrolytic graphite

This paper reports findings of an investigation of Pd–Ag alloy nanowires on the step edges of highly oriented pyrolytic graphite (HOPG) by electrochemical deposition at room temperature. Scanning electron microscopy (SEM) images reveal that these alloy nanowires (109–430 nm) are uniform in diameter, and have lengths up to 100–500 μm. The electrodeposition process involves the initial formation of nanowires induced at the step edges of the oxidized HOPG substrate at a very negative potential and subsequent growth at a constant low current density to coalesce the discontinuous nanowires. Alloy nanowires with a 20–25% silver content can be obtained when the ratio of Pd and Ag in the solution is carefully controlled. The SEM images demonstrate that the alloy nanowire arrays are continuous, parallel, ordered, well-aligned and have a narrow distribution of diameters. The Pd–Ag alloy nanowire arrays are promising materials for fabricating hydrogen nanosensors.     

An easy way to Pd–Zn nanoalloy with defined composition from a heterobimetallic Pd(μ–OOCMe)4Zn(OH2) complex as evidenced by XAFS and XRD

The heterobimetallic lantern complex Pd(μ-OOCMe)₄Zn(OH₂) was found to be readily reduced with H₂ under fairly mild conditions (150–250 °C, 5–10% H₂/He) both in the carbon-supported and crystalline states to afford a Pd–Zn nanoalloy as evidenced by the ICP elemental analysis, EXAFS, XANES and XRD data.      

FTIR study of CO adsorption on coked Pt–Sn/Al2O3 catalysts

Infrared spectra of adsorbed CO have been used as a probe to monitor changes in Pt site character induced by the coking of Pt/Al₂O₃ and Pt–Sn/Al₂O₃ catalysts by heat treatment in heptane/hydrogen. Four distinguishable types of Pt site for the linear adsorption of CO on Pt/Al₂O₃ were poisoned to different extents showing the heterogeneity of the exposed Pt atoms. The lowest coordination Pt atoms (ν(CO) < 2030 cm⁻¹) were unpoisoned whereas the highest coordination sites in large ensembles of Pt atoms (2080 cm⁻¹) were highly poisoned, as were sites of intermediate coordination (2030–2060 cm⁻¹). Sites in smaller two‐dimensional ensembles of Pt atoms (2060–2065 cm⁻¹) were partially poisoned, as were sites for the adsorption of CO in a bridging configuration. The addition of Sn blocked the lowest coordination sites and destroyed large ensembles of Pt by a geometric dilution effect. The poisoning of other sites by coke was impeded by Sn, this effect being magnified for Cl‐containing catalyst. Oxidation or oxychlorination of coked catalyst at 823 K followed by reduction completely removed coke from the catalyst surfaces. This revised version was published online in July 2006 with corrections to the Cover Date.     

Preparation and evaluation of RuO2–IrO2, IrO2–Pt and IrO2–Ta2O5 catalysts for the oxygen evolution reaction in an SPE electrolyzer

IrO₂–RuO₂, IrO₂–Pt and IrO₂–Ta₂O₅ electrocatalysts were synthesized and characterized for the oxygen evolution in a Solid Polymer Electrolyte (SPE) electrolyzer. These mixtures were characterized by XRD and SEM. The anode catalyst powders were sprayed onto Nafion 117 membrane (catalyst coated membrane, CCM), using Pt catalyst at the cathode. The CCM procedure was extended to different in-house prepared catalyst formulations to evaluate if such a method could be applied to electrolyzers containing durable titanium backings. The catalyst loading at the anode was about 6 mg cm⁻², whereas 1 mg cm⁻² Pt was used at the cathode. The electrochemical activity for water electrolysis was investigated in a single cell SPE electrolyzer at 80 °C. It was found that the terminal voltage obtained with Ir–Ta oxide was slightly lower than that obtained with IrO₂–Pt and IrO₂–RuO₂ at low current density (lower than 0.15 A cm⁻²). At higher current density, the IrO₂–Pt and IrO₂–RuO₂ catalysts performed better than Ir–Ta oxide.     

Fabrication of Dense Arrays of Platinum Nanowires on Silica, Alumina, Zirconia and Ceria Surfaces as 2-D Model Catalysts

High-density arrays of platinum nanowires with dimensions 20 nm × 5 nm × 12 μm (width × height × length) have been produced on planar oxide thin films of silica, alumina, zirconia, and ceria. In this multi-step fabrication process, sub-20 nm single crystalline silicon nanowires were fabricated by size reduction lithography. The Si nanowire patterns were then replicated to produce a high density of Pt nanowires by nanoimprint lithography. The width and height of the Pt nanowires are uniform and are controlled with nanometer precision. The Pt surface area is larger than 2 cm² on a 5 × 5 cm² oxide substrate. The catalytic oxidation of CO was carried out on zirconia-supported Pt nanowires. The reaction conditions (100 Torr O₂, 40 Torr CO, 513–593 K) and vacuum annealing (1023 K) did not change the nanowire structures.     

Increased generation of electricity in a microbial fuel cell using <Emphasis Type="Italic">Geobacter sulfurreducens</Emphasis>

The microbial fuel cell (MFC) has attracted research attention as a biotechnology capable of converting hydrocarbon into electricity production by using metal reducing bacteria as a biocatalyst. Electricity generation using a microbial fuel cell (MFC) was investigated with acetate as the fuel and Geobacter sulfurreducens as the biocatalyst on the anode electrode. Stable current production of 0.20–0.24 mA was obtained at 30–32 °C. The maximum power density of 418–470 mW/m², obtained at an external resistor of 1,000 Ω, was increased over 2-fold (from 418 to 866 mW/m²) as the Pt loading on the cathode electrode was increased from 0.5 to 3.0 mg Pt/cm². The optimal batch mode temperature was between 30 and 32 °C with a maximum power density of 418–470 mW/m². The optimal temperature and Pt loading for MFC were determined in this study. Our results demonstrate that the cathode reaction related through the Pt loading on the cathode electrode is a bottleneck for the MFC’s performance.     

The First A-Frame-Containing Organometallic Polymer: Taking Advantage of the Site Selectivity in PdPt-Mixed Metal Bimetallics

Abstract ClPd(μ-dppm)₂PtCl (1) reacts with (CNC₆H₄–2-OCH₂–)₂ to form a sparingly soluble and thermally stable orange polymeric material 4. 1 reacts with 1 or 2 equivalents of CNC₆H₄–2-OCH₃ to form the soluble A-frame d⁸–d⁸ model complexes 2 [ClPd(μ-dppm)₂(μ-CNR)PtCl], and 3 [ClPd(μ-dppm)₂(μ-CNR)Pt(CNR)](Cl) (R = C₆H₄–2-OCH₃), respectively. IR (ν(NC) bridging versus terminal) and NMR data reveal an A-frame structure where the terminal CNR ligands are bonded to Pt. 4 which is amorphous (XRD) appears stable up to 290 °C (TGA), but exhibits an exothermic process between 215 and 255 °C upon the first scan in DSC, but disappears upon the second. Two compounds, model 2 (λ_e = 674 nm; τ_e = 0.38 ± 0.01 μs; Φ_e = 0.0079 (±10%)) and polymer 4 (λ_e = 660 nm; τ_e = 0.18 ± 0.01 μs; Φ_e = 0.0056 (±10%)) are luminescent at 77 K in the solid state and in fluid solution (PrCN). Graphical abstract The First A-Frame-Containing Organometallic Polymer: Taking Advantage of the Site Selectivity in PdPt-Mixed Metal Bimetallics Sébastien Clément, Shawkat Mohammed Aly, Karl Gagnon, Alaa S. Abd-El-Aziz, Michael Knorr, Pierre D. Harvey ClPd(μ-dppm)₂Cl₂ reacts with (CN–C₆H₄–O–CH₂–)₂ to form the first A-frame-containing organometallic polymer, which is unambiguously characterized with the use of model compounds. This polymer does not experience any weight loss up to 290 °C based on TGA measurements, but DSC traces reveal an irreversible process at 215 °C (DSC). The novel material is also luminescent at 77 K. For example, λ_e = 660 nm; τ_e = 0.18 ± 0.01 μs; Φ_e = 0.0056 (±10%) in PrCN. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. This article is dedicated to Professor Astruc.     

Determination of selenium,arsenic, iodine and bromine in fish,plant and mammalian oils by cyclic instrumental neutron activation analysis

The concentrations of arsenic, selenium, iodine and bromine in a series of fish, plant and mammalian oils have been determined by cyclic instrumental neutron activation analysis (CINAA). Crude fish oils contain between 0.047 and 0.151 μg Se g⁻¹, 2.36–14.5 μg As g⁻¹, 2.36–9.63 μg Br g⁻¹ and 0.97–4.76 μgI g⁻¹. Seal oil contains the same four elements, but at levels below the lower end of the fish oil ranges. Iodine, bromine and arsenic were not detected in rape-seed or soybean oils and the concentration of selenium varied from < 0.010 to 0.042 μg g⁻¹. The levels of selenium, iodine and bromine are reduced markedly by hydrogenation of the menhaden oils. The CINAA method yielded results which were in agreement with pub-lished values obtained by other methods. The technique was rapid, requiring minimal sample manipulation, and was essentially free from interferences.     

Thermal decomposition of 3,3,6,6,9,9-hexaethyl-1,2,4,5,7,8-hexaoxacyclononane in solution and its use in methyl methacrylate polymerization

The kinetics of the thermal decomposition reaction of diethylketone triperoxide (3,3,6,6,9,9-hexaethyl-1,2,4,5,7,8-hexaoxacyclononane, DEKTP) in ethylbenzene solution were studied in the temperature range of 120.0–150.0 °C and at an initial concentration range of 0.01–0.10 M. This peroxide was used as a new initiator in methyl methacrylate (MMA) polymerization process at high temperatures (110.0–140.0 °C) in ethylbenzene solution. The effects of initiator concentration and reaction temperature on the polymerization rate were investigated in detail. Thus, activation parameters of the solution polymerization process (ΔE _d* = 83.3 kJ mol⁻¹ and ΔE _p* − ΔE _t*/2 = 54.0 kJ mol⁻¹) will be obtained. DEKTP can effectively act as initiator in MMA polymerization and its performance is similar to that presented by a multifunctional initiator resulting in high-molecular weight polymethylmethacrylate with a high reaction rate.     

Synthesis, characterization, and controllable drug release of dendritic star-block copolymer by ring-opening polymerization and atom transfer radical polymerization

A series of well-defined dendritic star-block copolymers were successfully synthesized by combination of living ring-opening polymerization (ROP) and atom transfer radical polymerization (ATRP) with the hydroxyl-terminated dendrimer polyester. Dendritic star-shaped poly(l-lactide)s (PLLAs) were prepared by bulk polymerization of l-lactide (l-LA) with dendrimer polyester initiator and tin 2-ethylhexanoate catalyst. The number-average molecular weight of these polymers linearly increased with the molar ratio of l-LA to dendrimer initiator. Dendritic star-shaped PLLA was converted into a PLLABr macroinitiator with 2-bromopropionyl bromide. Dendritic star-block copolymers could be obtained via ATRP of 2-(N,N-dimethylamino)ethyl methacrylate (DMAEMA). The molecular weight distributions of these copolymers were narrow. The molecular weights of dendritic star-shaped polymers and star-block copolymers could be controlled by the molar ratios of monomer to initiator and monomer conversion. The thermal properties of these dendritic star-shaped polymers and star-block copolymers were investigated. The behavior of model drug chlorambucil release from the copolymer indicated that the rate of drug release could be effectively controlled by altering the pH values of the environment.     

Preparation of Pt–Co alloy catalysts by electrodeposition for oxygen reduction in PEMFC

Direct current (DC) and pulse current (PC) electrodeposition of Pt–Co alloy onto pretreated electrodes has been conducted to fabricate catalyst electrodes for oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFC). The effect of plating mode and pulse plating parameters on the Pt–Co alloy catalyst structure, composition and electroactivity for the ORR in PEMFC has been investigated. The electrodeposited Pt–Co alloy catalyst indicates higher electrocatalytic activity towards the ORR than the electrodeposited Pt catalyst. The activity of the electrodeposited Pt–Co catalysts is further improved by applying the current in a pulse waveform pattern. The electrodeposition mode and the pulse plating parameters do not have the significant effect on the Pt:Co composition of deposited catalysts, but show the substantial effect on the deposit structures produced. The Pt–Co catalysts prepared by PC electrodeposition have finer structures and contain smaller Pt–Co catalyst particles compared to that produced by DC electrodeposition. By varying the Pt concentration in deposition solution, the Pt:Co composition of the electrodeposited catalyst that exhibits the highest activity is found. The Pt–Co alloy catalyst with the Pt:Co composition of 82:18 obtained at the charge density of 2 C cm⁻², the pulse current density of 200 mA cm⁻², 5% duty cycle and 1 Hz was found to yield the best electrocatalytic activity towards the ORR in PEMFC.     

Catalytic reactivity and surface chemistry of polyaniline(EB)–Pd–H2O systems

Catalytic reactivity and surface chemical effects induced by the presence of water in the molecular system polyaniline(EB)–Pd–H₂O were investigated. The polyaniline(EB) doped with palladium reveals its high activity and selectivity in the semihydrogenation: hexyne → hexenes (→ hexane). However, to demonstrate these effects, the specimen has to be submitted to a special treatment to lose most of its water. The XPS analysis allowed identification of the catalytically active sites of the studied system. They were ascribed to the [PdCl₄]²⁻ complex anions present at the surface of the dry specimens. This revised version was published online in August 2006 with corrections to the Cover Date.     

Cultivation impacts nitrogen transformation in Indian forest ecosystems

Two forests and two croplands, converted from the forest ecosystem were studied for 2 years to quantify inorganic N, nitrification, N-mineralization and microbial-N. The available N-pool ranged from 15.23 μg g⁻¹ to 19.84 μg g⁻¹, microbial-N from 20.6 μg g⁻¹ to 80.02 μg g⁻¹ with maximum values in summer season and minimum values in the rainy season. The trend for nitrification and N-mineralization was opposite to that of the size of available N-pool. Mean annual net nitrification rates ranged from 7.07 μg g⁻¹ month⁻¹ to 44.84 μg g⁻¹ month⁻¹ (0.17–1.39 μg g⁻¹ day⁻¹) and net N-mineralization from 6.56 μg g⁻¹ month⁻¹ to 48.53 μg g⁻¹ month⁻¹ (0.21–1.56 μg g⁻¹ day⁻¹). On an average, the pool of available N was slightly higher by 4.81%, while the microbial-N was declined substantially by 41.78% after the conversion of forest into cropland. Cultivation reduced the mean annual net nitrification and net N-mineralization, respectively by 50.71% and 47.67%. Interestingly, seasonal moisture content is negatively correlated to microbial-N and inorganic N and positively related to nitrification and N-mineralization.     

The effect of catalyst film thickness on the magnitude of the electrochemical promotion of catalytic reactions

The effect of catalyst film thickness on the magnitude of the effect of electrochemical promotion was investigated for the model catalytic reaction of C₂H₄ oxidation on porous Pt paste catalyst-electrodes deposited on YSZ. It was found that the catalytic rate enhancement ρ is up to 400 for thinner (0.2 μm) Pt films (40,000% rate enhancement) and gradually decreases to 50 for thicker (1 μm) films. The Faradaic efficiency Λ was found to increase moderately with increasing film thickness and to be described semiquantitatively by the ratio 2Fr _o/I ₀, where r _o is the unpromoted rate and I ₀ is the exchange current of the catalyst–electrolyte interface. The results are in good qualitative agreement with model predictions describing the diffusion and reaction of the backspillover O^2- species, which causes electrochemical promotion.     

A hydroxylamine electrochemical sensor based on electrodeposition of platinum nanoclusters on choline film modified glassy carbon electrode

A sensitive hydroxylamine sensor was developed based on electrodeposition of Pt nanoclusters on choline film modified glassy carbon electrode (nano-Pt/Ch/GCE). The properties of the composites were characterized by field emission scanning electron microscope, X-ray photoelectron spectroscopy, powder X-ray diffraction, and electrochemical investigations. The designed nano-Pt/Ch/GCE showed a high sensing performance for hydroxylamine in a wide concentration ranges of 5.0 × 10⁻⁷–1.1 × 10⁻³ M and 1.1 × 10⁻³–19 × 10⁻³ M. The detection limit was 0.07 μM (s/n = 3). The proposed electrode presented excellent operational and storage stability for the determination of hydroxylamine. Moreover, the sensor showed good sensitivity, selectivity, and reproducibility properties. All the results indicated the designed sensor had a good potential application in the determination of hydroxylamine.     

Effect of Iron Addition on the Durability of Pd–Pt-Loaded Sulfated Zirconia for the Selective Reduction of Nitrogen Oxides by Methane

The effects of adding iron to Pd–Pt/sulfated zirconia (SZ) on the selective NO _x reduction by methane were examined based on durability tests under conditions simulating natural gas combustion exhaust. While Pd–Pt/SZ was severely deactivated at 500 °C, Pd–Pt/Fe-SZ maintained a NO _x conversion higher than 70% for over 2400 h under the same conditions. Methane conversion on Pd–Pt/Fe-SZ was significantly lower than that on Pd–Pt/SZ. XRD analysis of fresh and used catalysts showed that a part of the SZ had transformed to monoclinic ZrO₂ and that adding Fe suppressed the transformation. These results suggested that the improvement in NO _x conversion by adding Fe was due to the suppression of methane combustion and the stabilization of SZ against transformation to ZrO₂.