The catalytic effect of platinum on the oxidation of carbon fibres

Ex-PAN based carbon fibres (5C) were oxidized at 500, 550 and 600 °C in dry air while being contained in both silica and platinum specimen holders. The weight loss measurements taken as a function of time revealed that those fibres oxidized in platinum exhibited a much higher oxidation rate than those exposed in silica. Additionally, those fibres oxidized in platinum underwent unusual changes in fibre morphology. Spheres formed along the longitudinal axis of many fibres, and in one instance, a fibre underwent bifurcation, with a sphere forming on each remaining fibril. Likewise, severe surface pitting occurred. It is believed that these changes in microstructure combined with the increased oxidation rate are a result of a catalysed oxidation reaction(s) caused by the presence of platinum, or perhaps by a cocatalytic reaction between platinum and impurities found on the surface of the fibres.     

Shape and composition-controlled platinum alloy nanocrystals using carbon monoxide as reducing agent

The shape of metal alloy nanocrystals plays an important role in catalytic performances. Many methods developed so far in controlling the morphologies of nanocrystals are however limited by the synthesis that is often material and shape specific. Here we show using a gas reducing agent in liquid solution (GRAILS) method, different Pt alloy (Pt-M, M = Co, Fe, Ni, Pd) nanocrystals with cubic and octahedral morphologies can be prepared under the same kind of reducing reaction condition. A broad range of compositions can also be obtained for these Pt alloy nanocrystals. Thus, this GRAILS method is a general approach to the preparation of uniform shape and composition-controlled Pt alloy nanocrystals. The area-specific oxygen reduction reaction (ORR) activities of Pt(3)Ni catalysts at 0.9 V are 0.85 mA/cm(2)(Pt) for the nanocubes, and 1.26 mA/cm(2)(Pt) for the nanooctahedra. The ORR mass activity of the octahedral Pt(3)Ni catalyst reaches 0.44 A/mg(Pt).     

Gold supported on metal oxides for carbon monoxide oxidation

Au has been loaded (1% wt.) on different commercial oxide supports (CuO, La₂O₃, Y₂O₃, NiO) by three different methods: double impregnation (DIM), liquid-phase reductive deposition (LPRD), and ultrasonication (US). Samples were characterised by N₂ adsorption at −196 °C, high-resolution transmission electron microscopy, selected area electron diffraction, energy dispersive X-ray spectrometry, high-angle annular dark-field imaging (Z-contrast), X-ray diffraction, and temperature programmed reduction. CO oxidation was used as a test reaction to compare the catalytic activities. The best results were obtained with Au loaded by DIM on the NiO support, with an activity of 7.2 × 10⁻⁴ mol_CO·g_Au ⁻¹·s⁻¹ at room temperature. This is most likely related to the Au nanoparticle size being the smallest in this catalyst (average 4.8 nm), since it is well known that gold particle size determines the catalytic activity. Other samples, having larger Au particle sizes (in the 2–12 nm range, with average sizes ranging from 4.8 to 6.8 nm), showed lower activities. Nevertheless, all samples prepared by DIM had activities (from 1.1 × 10⁻⁴ to 7.2 × 10⁻⁴ mol_CO·g_Au ⁻¹·s⁻¹, at room temperature) above those reported in the literature for gold on similar oxide supports. Therefore, this method gives better results than the most usual methods of deposition-precipitation or co-precipitation.      

Preparation of platinum nanoparticle and its catalytic activity for toluene oxidation

Colloidal Pt nanoparticles are prepared using H2PtCl6 as a precursor, polyvinylpyrrolidone (PVP: molecular weight = 10,000 and 40,000) and hydrogen as a stabilizing agent and a reducing agent, respectively. The amounts of the precursor and the stabilizing agent and the molecular weight of PVP have an effect on the formation of Pt nanoparticles. Supported Pt catalyst (CSPt) is prepared from colloidal Pt nanoparticles and y-Al2O3. Another supported Pt catalyst (ISPt) is prepared by using the conventional incipient wetness impregnation method with an aqueous H2PtCl6 solution and gamma-Al2O3. The catalytic activities of CSPt and ISPt catalysts are compared for VOC (toluene) oxidation. Transmission Electron Microscopy (TEM), UV-vis, X-ray diffraction (XRD) and temperature programmed reduction (TPR) are used to characterize CSPt and ISPt catalysts. The experimental results reveal that the catalytic activity of CSPt is superior to that of ISPT.     

A kind of new pyrochlore compounds with catalytic activity for the oxidation reaction of carbon monoxide and propylene

A series of new compounds with a formula RE₂M_2/3Nb_4/3O₇ (RE=Nd, Sm, Eu; M=Cu, Co, Zn) have been synthesized by a wet chemical method and the lattice parameters of the compounds have also been determined. The new compounds possess a pyrochlore structure and belong to hexagonal system. Most of the compounds have a certain catalytic activity for the oxidation reaction of carbon monoxide and propylene. The conversion efficiency of carbon monoxide and propylene on the surface of some compounds can be close to 100% at near 450°C. The compounds are insulator and the resistibility also is larger than 10⁵ ohm·cm even if at 500°C. The compounds are a new kind of oxidation catalysts. The catalytic oxidation process of carbon monoxide and propylene on the surface of the compounds involves the oxidation-reduction of the cations in the compound and the catalytic process is a co-catalytic one. The effects of various metal cations in the compounds on the catalytic activity for the oxidation of carbon monoxide and propylene have been discussed.     

Electrocatalysts for methanol oxidation based on platinum/carbon nanofibers nanocomposite

New carbon nanomaterials, i.e., carbon nanotubes and nanofibers, with special physico-chemical properties, are recently studied as support for methanol oxidation reaction electrocatalysts replacing the most widely used carbon black. Particularly, carbon fibrous structures with high surface area and available open edges are thought to be promising. Platelet type carbon nanofibers, which have the graphene layers oriented perpendicularly to the fiber axis, exhibit a high ratio of edge to basal atoms. Different types of carbon nanofibers (tubular and platelet) were grown by plasma enhanced chemical vapour deposition on carbon paper substrates. The process was controlled and optimised in term of growth pressure and temperature. Carbon nanofibers were characterised by high resolution scanning electron microscopy and X-ray photoelectron spectroscopy to assess the morphological properties. Then carbon nanofibers of both morphologies were used as substrates for Pt electrodeposition. High resolution scanning electron microscopy images showed that the Pt nanoparticles distribution was well controlled and the particles size went down to few nanometers. Pt/carbon nanofibers nanocomposites were tested as electrocatalysts for methanol oxidation reaction. Cyclic voltammetry in H2SO4 revealed a catalyst with a high surface area. Cyclic voltammetry in presence of methanol indicated a high electrochemical activity for methanol oxidation reaction and a good long time stability compared to a carbon black supported Pt catalyst.     

Ru-Pt core-shell nanoparticles for preferential oxidation of carbon monoxide in hydrogen

Most of the world's hydrogen supply is currently obtained by reforming hydrocarbons. 'Reformate' hydrogen contains significant quantities of CO that poison current hydrogen fuel-cell devices. Catalysts are needed to remove CO from hydrogen through selective oxidation. Here, we report first-principles-guided synthesis of a nanoparticle catalyst comprising a Ru core covered with an approximately 1-2-monolayer-thick shell of Pt atoms. The distinct catalytic properties of these well-characterized core-shell nanoparticles were demonstrated for preferential CO oxidation in hydrogen feeds and subsequent hydrogen light-off. For H2 streams containing 1,000 p.p.m. CO, H2 light-off is complete by 30 (composite function)C, which is significantly better than for traditional PtRu nano-alloys (85 (composite function)C), monometallic mixtures of nanoparticles (93 (composite function)C) and pure Pt particles (170 ( composite function)C). Density functional theory studies suggest that the enhanced catalytic activity for the core-shell nanoparticle originates from a combination of an increased availability of CO-free Pt surface sites on the Ru@Pt nanoparticles and a hydrogen-mediated low-temperature CO oxidation process that is clearly distinct from the traditional bifunctional CO oxidation mechanism.     

Electrodeposition of platinum nanoparticles onto carbon nanofibers for electrocatalytic oxidation of methanol

Pt/carbon composite nanofibers were prepared by electrodepositing Pt nanoparticles onto electrospun carbon nanofibers and were used as catalysts towards the oxidation of methanol. The morphology and size of Pt nanoparticles were controlled by selectively adjusting the electrodeposition potential and time. SEM and TEM results show that the composite nanofibers were successfully obtained and Pt particle diameters were between 10 and 55 nm. The electrocatalytic activity of the composite nanofibers expressed by current density per Pt particle mass was found to depend on the particle size, showing an increasing activity when the catalyst diameter decreased.     

炭气凝胶负载Pt基催化剂的制备及其甲醇氧化催化性能

以间苯二酚(R)和甲醛(F)为原料,制备R-F炭气凝胶(RF-CAs).继以后者为载体采用浸渍还原法制备铂基催化剂Pt/CA,并比较其与由相同负载工艺制得的以Vulcan XC-72为载体的铂基催化剂Pt/XC72的催化甲醇氧化反应的性能.结果表明,前者具明显高的甲醇氧化催化活性,显示CAs是一种极具潜在竞争力的燃料电池催化剂载体材料.     

CuO impregnated activated carbon for catalytic wet peroxide oxidation of phenol

This paper presents an original approach to the removal of phenol in synthetic wastewater by catalytic wet peroxide oxidation with copper binding activated carbon (CuAC) catalysts. The characteristics and oxidation performance of CuAC in the wet hydrogen peroxide catalytic oxidation of phenol were studied in a batch reactor at 80 °C. Complete conversion of the oxidant, hydrogen peroxide, was observed with CuAC catalyst in 20 min oxidation, and a highly efficient phenol removal and chemical oxygen demand (COD) abatement were achieved in the first 30 min. The good oxidation performance of CuAC catalyst was contributed to the activity enhancement of copper oxide, which was binding in the carbon matrix. It can be concluded that the efficiency of oxidation dominated by the residual H₂O₂ in this study. An over 90% COD removal was achieved by using the multiple-step addition in this catalytic oxidation.     

Templated photocatalytic synthesis of well-defined platinum hollow nanostructures with enhanced catalytic performance for methanol oxidation

Hollow metallic nanostructures exhibit important applications in catalysis, sensing, and phototherapy due to their increased surface areas, reduced densities, and unique optical and electronic features. Here we report a facile photocatalytic process to synthesize and tune hollow platinum (Pt) nanostructures. Through hierarchically structured templates, well-defined hollow Pt nanostructures are achieved. These nanostructures possess interconnected nanoporous framework as shell with high surface area for enhanced catalytic performance/mass transport for methanol oxidation.     

Electrical and catalytic properties of some oxides with the fluorite or pyrochlore structure: Part 2: Catalytic oxidation of carbon monoxide

The catalytic properties of mixed oxides with the fluorite or pyrochlore structure were investigated using CO oxidation. The presence of ions with a variable valence state, the size of the ions and especially the extent of pyrochlore ordering affect kinetic behaviour and activity of the investigated materials.     

Catalytic oxidation of carbon monoxide over radiolytically prepared Pt nanoparticles supported on glass

Platinum nanoparticles have been prepared by radiolytic and chemical methods in the presence of stabilizer gelatin and SiO₂ nanoparticles. The formation of Pt nanoparticles was confirmed using UV-vis absorption spectroscopy and transmission electron microscopy (TEM). The prepared particles were coated on the inner walls of the tubular pyrex reactor and tested for their catalytic activity for oxidation of CO. It was observed that Pt nanoparticles prepared in the presence of a stabilizer (gelatin) showed a higher tendency to adhere to the inner walls of the pyrex reactor as compared to that prepared in the presence of silica nanoparticles. The catalyst was found to be active at ≥150 °C giving CO₂. Chemically reduced Pt nanoparticles stabilized on silica nanoparticles gave ∼7% CO conversion per hour. However, radiolytically prepared Pt nanoparticles stabilized by gelatin gave ∼10% conversion per hour. Catalytic activity of radiolytically prepared platinum catalyst, coated on the inner walls of the reactor, was evaluated as a function of CO concentration and reaction temperature. The rate of reaction increased with increase in reaction temperature and the activation energy for the reaction was found to be ∼108.8 kJ mol⁻¹. The rate of CO₂ formation was almost constant (∼1.5 × 10⁻⁴ mol dm⁻³ h⁻¹) at constant O₂ concentration (6.5 × 10⁻³ mol dm⁻³) with increase in CO concentration from 2 × 10⁻⁴ mol dm⁻³ to 3.25 × 10⁻³ mol dm⁻³. The data indicate that catalytic oxidation of CO takes place by Eley-Rideal mechanism.     

Effect of carbon monoxide and sulphur dioxide on the oxidation state of copper in zeolite

A study is made of the reduction and oxidation of Cu²⁺ in CuNaY zeolites by CO and SO₂, using electron spin resonance. It is observed that the Cu⁺ or Cu^o formed by the reduction of Cu²⁺ with CO can be reoxidized to Cu²⁺ by SO₂ at 400°C. SO₂ can also reduce a fraction of the Cu²⁺ sites in the Cu-exchanged zeolites. SO₂ decomposes and forms elemental S under experimental conditions on the zeolite.     

Influence of catalyst pretreatments on the catalytic oxidation of toluene over nanostructured platinum based spent catalyst

In this study, we regenerated a nano-structured platinum based spent catalyst by applying thermal gas and acid pretreatment and examined the influence of treatment on the catalytic oxidation of toluene. The spent catalysts were pretreated with air, hydrogen and six different acid aqueous solutions (HCl, H2SO4, HNO3, H3PO4, CH3COOH and C2H2O4). The physicochemical properties of the parent and its modified catalysts were characterized by XRD, BET, TEM, and ICP. The results of light-off curves showed that air and hydrogen treated catalysts were more active than the parent catalyst. In addition, the catalytic activities of toluene oxidation for acid aqueous treated samples were identical with the order of Pt/Al ratio.     

Model-based design of low-temperature carbon nanotube synthesis via catalytic oxidation for supercapacitor application

Novel electrochemical double layer capacitors with carbon nanotube (CNT) electrode, often referred to as supercapacitors, have a potential to bridge a power and energy gap between traditional dielectric capacitors and chemical batteries. However, their future is uncertain because current fabrication technologies involve difficult-to-control post-growth manipulations of CNTs. This paper addresses this problem by introducing model-based design of low-temperature CNT synthesis that is suitable for in-situ fabrication of CNT-based supercapacitor electrode. The insight to the surface kinetics during low-temperature CNT synthesis via catalytic oxidation was obtained via coupled Molecular Dynamics and Quantum Semiempirical Hamiltonian simulations. It was determined that the presence of oxygen on the surface of catalyst increases, by several times, the time necessary for the decomposition of hydrocarbons as well as shifts the reaction zone from the surface of catalyst to the catalyst underlayer. Theoretical trends were confirmed by CNT growth experiments. A contact between conducting CNTs and zinc oxide binding layer was analyzed in detail since its properties strongly affect the performance of CNT electrode. It was demonstrated that the formed CNT-zinc oxide interface was free from unbonded oxygen atoms and/or clusters of zinc atoms and was weakly affected by defects in CNTs.     

Electrochemical properties of GaN nanowire electrodes--influence of doping and control by external bias

We report on the electrochemical characteristics of GaN nanowire (NW) ensembles grown by plasma-assisted molecular beam epitaxy on Si111 substrates and on the influence of Si and Mg doping. The NW electrochemical properties in terms of surface capacitance (C(S)), surface resistance (R(S)) are extracted from electrochemical impedance spectra. While Mg doping of GaN NWs does not cause a significant variation of these quantities, an increase of the Si concentration leads to an increase of C(S) and a simultaneous decrease of R(S), indicating the presence of charge carriers in the NWs. According to the extracted values for R(S) and C(S) the NWs are classified into resistive and conductive. For conductive NWs charge transfer to a ferricyanide redox couple in the electrolyte is demonstrated and the ensemble average of the flatband voltage was determined. Variation of the lateral surface potential due to application of an external bias via the electrolyte is demonstrated.     

Facile preparation of porous carbon nitride for visible light photocatalytic reduction and oxidation applications

In this work, we have employed melamine, cyanuric acid and thymine to fabricate triazine-based carbon nitrides (CNs) by supramolecular approach. The resultant CNs possess large specific surface area, hierarchical porous structure, better light absorption capacity and high separation rate of photoinduced carriers. Then, the photocatalytic reduction and oxidation performance has been evaluated. The obtained CNs exhibit enhanced photocatalytic reduction performance on water splitting to H₂, the largest hydrogen evolution rate can reach 8466.3 μmol g^?1 h^?1, which is 81.9 times as high as that of bulk CN. Simultaneously, the porous CNs show excellent photocatalytic reduction ability on the conversion of CO₂ to H₂, CO and CH₄. Of particular interest is that they have high selectivity for CO. It’s worth noting that the porous CNs also possess outstanding photocatalytic oxidation ability on high concentration nitric oxide (NO), and the highest NO conversion rate can reach 79.3% under visible light. The enhanced photocatalytic performance for the multifunctional porous CN can be ascribed to the synergic effect of large specific surface area, strong light absorption capacity and fast separation of photoinduced electron–hole pairs. Finally, the photocatalytic reduction and oxidation mechanism of the porous CN is also proposed and discussed.     

On the mechanism of carbon monoxide oxidation on the surface of gold nanoclusters supported on titanium oxide

The process of carbon monoxide (CO) oxidation on the surface of a system comprising nanodimensional gold clusters deposited onto thin films of titanium oxide of variable stoichiometry formed on a Re(1000) single crystal surface has been studied by methods of thermodesorption, IR, and X-ray photoelectron spectroscopy. It is established that oxygen contained in titanium oxide plays an important role in the conversion of CO into CO₂. The efficiency of this process on the Au/TiO _x (x < 2) system surface is significantly higher that that on the Au/TiO₂ system.     

Electrical characterization of carbon monoxide sensitive high temperature sensor diode based on catalytic metal gate-insulator-silicon carbide structure

Field-effect gas sensors based on catalytic metal-insulator-silicon carbide (MISiC) devices are investigated. For the evaluation of the barrier height, the temperature dependence of the current-voltage (I-V) and the capacitance-voltage (C-V) characteristics of MISiC Schottky diodes were investigated in CO and O/sub 2/ atmospheres. Four methods were used to evaluate how a change in gas ambient influences the barrier height of the diode: a change of the intersection current at zero voltage in the forward direction of the I-V curve, a change of the temperature dependence in the forward direction and the reverse direction, respectively, of the I-V curve, and a change of the intersection voltage of 1/C/sup 2/ versus V plot. The four methods gave similar changes in the barrier height for the device in 8000 ppm CO and 4000 ppm O/sub 2/. The values of barrier height obtained from the I-V curves were here normalized by the ideality factor calculated from I-V measurements. The correlation between the barrier height change obtained from the I-V and the C-V measurements, respectively, is discussed regarding the ideality factor.