Relationship among the physicochemical properties, electrocatalytic performance and kinetics of carbon supported Pt catalyst for ethanol oxidation

A new carbon supported Pt (Pt/C(b)) catalyst was prepared by reducing H₂PtCl₆ in glycol solution using formic acid as a reducing agent, and has been found in this work to be highly active and stable for the electrochemical oxidation of ethanol. The preparation produces highly dispersed Pt particles, of 2.6 nm average size, and with high electrochemical surface area, 98 m²/g. The apparent activation energy of ethanol oxidation over the Pt/C(b) catalyst electrode is low, 10–14 kJ/mol, over the range of potentials from 0.3 to 0.6 V.     

Pt–NiO/C anode electrocatalysts for direct methanol fuel cells

Pt catalyst was supported on Vulcan XC-72R containing 5 wt.% NiO using NaBH₄ as a reducing agent. The prepared catalyst was heat-treated at 400 °C. XRD, TEM and EDX analyses were applied to characterize Pt–NiO/C electrocatalyst. The introduction of NiO reduces the particle size of Pt crystallites. The electrocatalytic activity of Pt–NiO/C electrocatalysts was examined towards methanol oxidation reaction in 0.5 M H₂SO₄ solution using cyclic voltammetry and chronoamperometry techniques. A three fold increment in the oxidation current density was gained at Pt–NiO/C electrocatalyst compared to Pt/C one. The corresponding chronoamperograms showed high steady state current density values suggesting better stability of Pt–NiO/C electrocatalyst towards the carbonaceous poisoning species. The enhanced electrocatalytic performance and the long-term cycle durability of Pt–NiO/C electrocatalyst are attributed to the strong interaction between Pt and NiO and the formation of small Pt crystals.     

The electrocatalytic properties of an IrO2/SnO2 catalyst using SnO2 as a support and an assisting reagent for the oxygen evolution reaction

Electrocatalysts made of IrO₂/SnO₂ were prepared using the Adams method for solid polymer electrolyte (SPE) water electrolysis. The physicochemical properties of the catalyst were characterized via X-ray diffraction (XRD) and transmission electron microscopy (TEM). The electrochemical properties of the catalyst were investigated using cyclic voltammetry (CV), electrochemical impendence spectroscopy (EIS), chronopotentiometry and Tafel curve measurements in 0.1 mol L^?1 H₂SO₄ at room temperature. The test results showed that the catalytic properties of IrO₂/SnO₂ depended on the mass ratio of iridium to tin, and that the optimal mass ratio was 2:1. The optimized catalyst was applied to a membrane electrode assembly (MEA), and the stationary current–potential relationships were determined. With an IrO₂/SnO₂ (2:1) anode, a 40% Pt/C cathode and a total noble metal (Ir, Pt) loading of 1.2 mg cm^?2, the terminal applied potential difference of the water electrolysis was 1.70 V at 2 A cm^?2 and 80 °C.     

Pt/IrO2/CNT anode catalyst with high performance for direct methanol fuel cells

Carbon nanotube immobilized IrO₂ (IrO₂/CNT) was prepared by a simple oxidation method with hydrogen peroxide as an oxidant and used as an improved catalyst support to load active Pt to prepare Pt/IrO₂/CNT anode catalyst for direct methanol fuel cell. Electrochemical measurement revealed that Pt/IrO₂/CNT exhibits much higher activity for methanol oxidation and better CO tolerance than Pt/CNT. The anodic peak current of methanol oxidation on Pt/IrO₂/CNT (873.1A g_Pt^− 1) is 2.6 times that of Pt/CNT catalyst (335.7A g_Pt^− 1). The enhanced performance of Pt/IrO₂/CNT is attributed to the fact that IrO₂ improves the dispersion of Pt nanoparticles, and lowers the charge transfer resistance in methanol electrooxidation.     

Honeycomb supported Co3O4/CeO2 catalyst for CO/CH4 emissions abatement: Effect of low Pd–Pt content on the catalytic activity

A structured Co₃O₄–CeO₂ composite oxide, containing 30% by weight of Co₃O_4, has been prepared over a cordieritic honeycomb support. The bimetallic, Pd–Pt catalyst has been obtained by impregnation of the supported Co₃O₄–CeO₂ with Pd and Pt precursors in order to obtain a total metal loading of 50 g/ft³.CO, CH₄ combined oxidation tests were performed over the catalyzed monoliths in realistic conditions, namely GHSV = 100,000 h⁻¹ and reaction feed close to emission from bi-fuel vehicles. The Pd–Pt un-promoted Co₃O₄–CeO₂ is promising for cold-start application, showing massive CO conversion below 100 °C, in lean condition.A strong enhancement of the CH₄ oxidation activity, between 400 and 600 °C, has been observed by addition to the Co₃O₄–CeO₂ of a low amount of Pd–Pt metals.     

Pt-CeO2/C anode catalyst for direct methanol fuel cells

In order to develop a cheaper and durable catalyst for methanol electrooxidation reaction, ceria (CeO₂) as a co-catalytic material with Pt on carbon was investigated with an aim of replacing Ru in PtRu/C which is considered as prominent anode catalyst till date. A series of Pt-CeO₂/C catalysts with various compositions of ceria, viz. 40 wt% Pt-3–12 wt% CeO₂/C and PtRu/C were synthesized by wet impregnation method. Electrocatalytic activities of these catalysts for methanol oxidation were examined by cyclic voltammetry and chronoamperometry techniques and it is found that 40 wt% Pt-9 wt% CeO₂/C catalyst exhibited a better activity and stability than did the unmodified Pt/C catalyst. Hence, we explore the possibility of employing Pt-CeO₂ as an electrocatalyst for methanol oxidation. The physicochemical characterizations of the catalysts were carried out by using Brunauer Emmett Teller (BET) surface area and pore size distribution (PSD) measurements, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) techniques. A tentative mechanism is proposed for a possible role of ceria as a co-catalyst in Pt/C system for methanol electrooxidation.     

Platinum supported on reduced graphene oxide as a catalyst for hydrogenation of nitroarenes

Reduced graphene oxide (RGO)-supported platinum (Pt) catalyst was prepared by simple ethylene glycol (EG) reduction and used for hydrogenation of nitroarenes. Characterizations showed that EG as a reductant exhibited more advantages than the widely used hydrazine hydrate to fabricate monodispersed, small sized Pt nanoparticles on the surface of RGO. The yield of aniline over the Pt/RGO-_EG catalyst reached 70.2 mol-_AN/(mol-_Pt min) at 0 ^oC, which is 12.5 and 19.5 times higher than that of multi-walled carbon nanotube- and active carbon-supported Pt catalysts, respectively. When the reaction temperature was increased to 20 ^oC, the catalytic activity of Pt/RGO-_EG jumped to 1138.3 mol-_AN/(mol-_Pt min), and it was also extremely active for the hydrogenation of a series of nitroarenes. The unique catalytic activity of Pt/RGO-_EG is not only related to the well dispersed Pt clusters on the RGO sheets but also the well dispersion of Pt/RGO-_EG in the reaction mixture.     

A new NOx storage-reduction electrochemical catalyst

A new NO_x storage-reduction electrochemical catalyst has been prepared from a polycrystalline Pt film deposited on 8 mol% Y₂O₃-stabilized ZrO₂ (YSZ) solid electrolyte. BaO has been added onto the Pt film by impregnation method. The NO_x storage capacity of Pt-BaO/YSZ system was investigated at 350 °C and 400 °C under lean conditions. Results have shown that the electrochemical catalyst was effective for NO_x storage. When nitric oxides are fully stored, the catalyst potential is high and reaches its maximum. On the other hand, when a part of NO and also NO₂ desorb to the gas phase, the catalyst potential remarkably drops and finally stabilizes when no more NO_x storage occurs but only the reaction of NO oxidation into NO₂. Furthermore, the investigation has clearly demonstrated that the catalyst potential variation versus temperature or chemical composition is an effective indicator for in situ following the NO_x storage-reduction process, i.e. the storage as well as the regeneration phase. The catalyst potential variations during NO_x storage process was explained in terms of oxygen coverage modifications on the Pt.     

A study on utilization of stainless steel wire cloth as a catalyst support

In this work, stainless steel wire cloth (SSWC) for metallic support was thermally treated to increase the adhesive strength of Al₂O₃ by improving superficial roughness. After coating Al₂O₃ on SSWC, Pt particles as a catalytic component were deposited on the Al₂O₃/SSWC. These supports and catalysts were characterized by N₂ gas adsorption, X-ray diffraction (XRD), scanning electron microscopy (SEM) in conjunction with energy dispersive spectroscopy (EDS), and scanning transmission electron microscopy (STEM). The catalytic performance was tested in the ethylene oxidation. The effect of space velocity (GHSV = 2000–8000 h^?1) at different temperatures (190 °C and 210 °C) and reproducibility were investigated. The superficial roughness of SSWC was markedly increased by thermal oxidation at 800 °C for 12 h, and good adherence of Al₂O₃ to the SSWC was observed. The obtained Pt/Al₂O₃/SSWC800 catalyst showed excellent catalytic activity in the ethylene oxidation and showed a good reproducibility and stability even after repeated use.     

Synthesis,structures and catalytic activities of half-sandwich ruthenium complexes based on Schiff Base ligands

A series of half-sandwich ruthenium(II) complexes containing Schiff-base ligands [Ru(p-cymene)LCl] [HL = (E)-4-X-2-((phenylimino)methyl)phenol, X = H (2a); X = CH₃ (2b); X = Cl (2c) and X = Br (2d)] have been synthesized and fully characterized by ¹H and ¹³C NMR spectra, elemental analyses and infrared spectrometry. Moreover, the molecular structures of ruthenium complexes 2b and 2c were confirmed by single-crystal X-ray diffraction methods. These half-sandwich ruthenium complexes are highly catalyzed hydrogenation of nitroarenes to aromatic anilines to proceed in the presence of sodium borohydride reducing agent in ethanol solvent. Notably, complex 2c was found to be a very efficient catalyst toward reduction of nitroarene compounds with wide functional group compatibility and substrate scope.     

Platinum–tin bimetallic nanoparticles for methanol tolerant oxygen-reduction activity

Carbon-supported Pt–Sn/C bimetallic nanoparticle electrocatalysts were prepared by the simple reduction of the metal precursors using ethylene glycol. The catalysts heat-treated under argon atmosphere to improve alloying of platinum with tin. As-prepared Pt–Sn bimetallic nanoparticles exhibit a single-phase fcc structure of Pt and heat-treatment leading to fcc Pt₇₅Sn₂₅ phase and hexagonal alloy structure of the Pt₅₀Sn₅₀ phase. Transmission electron microscopy image of the as-prepared Pt–Sn/C catalyst reveals a mean particle diameter of ca. 5.8 nm with a relatively narrow size distribution and the particle size increased to ca. 20 nm when heat-treated at 500 °C due to agglomeration. The electrocatalytic activity of oxygen reduction assessed using rotating ring disk electrode technique (hydrodynamic voltammetry) indicated the order of electrocatalytic activity to be: Pt–Sn/C (as-prepared) > Pt–Sn/C (250 °C) > Pt–Sn/C (500 °C) > Pt–Sn/C (600 °C) > Pt–Sn/C (800 °C). Kinetic analysis reveals that the oxygen reduction reaction on Pt–Sn/C catalysts follows a four-electron process leading to water. Moreover, the Pt–Sn/C catalyst exhibited much higher methanol tolerance during the oxygen reduction reaction than the Pt/C catalyst, assessing that the present Pt–Sn/C bimetallic catalyst may function as a methanol-tolerant cathode catalyst in a direct methanol fuel cell.     

A study of the deactivation of low loading Ni/Al2O3 steam reforming catalyst by tetrahydrothiophene

The steam reforming (SR) of ethanol/phenol mixture (168 g_TOT/N m³, ethanol:phenol 2:1 mol, GHSV = 54,000 h^− 1), assumed as a model for tar mixtures, has been studied over a 5% Ni/Al₂O₃ catalyst (155 m²/g), in the presence and in the absence of 210 ppm tetrahydrothiophene (THT) as a sulphur containing contaminant. The sulphidation of the catalyst by THT has been studied by IR spectroscopy. Infrared spectra of CO adsorbed at low temperature over the oxidized, the reduced and the sulphurized catalyst have also been recorded. The catalyst acts as a bifunctional one, with the behaviour attributed to the uncovered support (alumina modified by nickel ions) at 773 K (dehydration of ethanol to ethylene, dehydrogenation to acetaldehyde and alkylation of phenol with ethanol) that fully disappears at 973 K when steam reforming occurs very selectively. By lowering back the reaction temperature, the support behaviour reappears. THT poisons selectively the Ni component, thus causing the appearance of the support behaviour also at 973 K. IR experiments show that THT deposes sulphur at the catalyst surface with the production of gas-phase 1,3-butadiene, thus converting the catalyst into a “sulphided” SR-inactive state. The steam reforming activity of the poisoned catalyst progressively reappears upon feeding back S-free feed at 973 K. IR study suggests that steam “cleans” the catalyst surface by sulphur, generating a “disordered” surface with dispersed Ni^2 + and Ni⁰ species, that could slowly re-approach the initial active state.     

Electrospun Pt/SnO2 nanofibers as an excellent electrocatalysts for hydrogen oxidation reaction with ORR-blocking characteristic

Pt/SnO₂ nanofibers were synthesized via electrospinning. The unique electrochemical properties were in evidence based on the activity that allowed a hydrogen oxidation reaction and inhibit an oxygen reduction reaction. A high electrochemically active surface area value of 81.17 m²/g-Pt was achieved with ultra-low Pt loading (4.03 wt.%). The kinetics of a hydrogen oxidation reaction was investigated using a linear sweep voltammetry technique under a hydrogen atmosphere. A diffusion-limited current was achieved at 0.07 V and was stable at a high potential. This preparation technique shows great promise for the design of anode electrocatalyst material for fuel cells.     

Anodic catalysts for polymer electrolyte fuel cells: the catalytic activity of Pt/C,Ru/C and Pt-Ru/C in oxidation of CO by O2

The catalytic activity for oxidation of CO by O₂ was investigated on commercial Pt/C, Pt-Ru/C (Pt/Ru atomic ratio = 20, 3, 1, 1/3) and Ru/C. All samples contained 20 wt.% metal. Assuming equal surface and bulk composition, the number of surface Pt and Ru atoms was calculated from the average size of the supported metal particle as determined by TEM. On Pt-Ru/C alloys, the turnover frequency per Ru atom, N_Ru/molecules s⁻¹ Ru-atom⁻¹, was independent of chemical composition. This finding suggests that the active site in these alloys is Ru. In the temperature range 300–400 K, the turnover frequency per active metal atom was 50–300 times higher on Pt-Ru/C than on Pt/C. The turnover frequency was 400 times higher on Ru/C than on Pt/C at 313 K and 90 times higher at 353 K. Addition of water vapor to the reactant mixture left the catalytic activity of Ru/C unchanged but slightly increased the activity of Pt/C. On both catalysts the activation energy and reaction orders were nearly the same as in dry atmosphere. Conversely, the addition of water markedly decreased the activation energy for Pt-Ru(1 : 1)/C alloy (from 19 to 11 kcal mol⁻¹). These findings suggest that fuel cells equipped with Pt-Ru/C anodes perform better than cells with Pt/C anodes. They do so because Ru effectively oxidizes the carbon monoxide present as an impurity in the H₂-reformed fuel.     

Effect of Rh content on carbon-supported PtRh catalysts for dehydrogenative electrooxidation of cyclohexane to benzene over polymer electrolyte membrane fuel cell

Electrochemical dehydrogenative oxidation of cyclohexane to benzene was studied over carbon-supported PtRh (PtRh/C) electrocatalysts, which were prepared with different Pt:Rh atomic ratios from 4:1 to 1:4 using a borohydride reduction method combined with freeze-drying procedure at room temperature. The bimetallic PtRh/C catalysts were characterized by various physicochemical analyses such as X-ray diffraction (XRD), transmission electron microscopy (TEM), and X-ray absorption-near-edge spectroscopy (XANES). The variation of Rh content over the PtRh alloy formation caused significant structural and electronic modifications on the catalyst phase, which could be associated with consistent changes in electrocatalytic activities over a polymer electrolyte membrane (PEM) fuel cell. The Pt₄Rh₁/C catalyst as the anode electrocatalyst showed a maximum power density of ca. 8.5 mW cm^?2. Here, both the structural modification via lattice parameter change and the electronic modification through charge transfer from Rh to Pt could kinetically facilitate the sluggish electrode reaction with an increased exchange current density on the dehydrogenative electrooxidation of cyclohexane to benzene over the PtRh/C anodes of cyclohexane fuel cell.     

Excellent electrocatalytic performance of Pt nanoparticles on reduced graphene oxide nanosheets prepared by a direct redox reaction between Na2PtCl4 and graphene oxide

A simple and environment-friendly method was used to prepare Pt/reduced graphene oxide (Pt/RGO) hybrids. This approach used a redox reaction between Na₂PtCl₄ and graphene oxide (GO) nanosheets and a subsequent thermal reduction of the material at 200 °C for 24 h in a vacuum oven. In contrast to other methods that use an additional reductant to prepare Pt nanoparticles, the Pt²⁺ was directly reduced to Pt⁰ in the GO solution. GO was used as the reducing agent, the stabilizing agent and the carrier. The resulting Pt/RGO hybrid was characterized by X-ray diffraction, thermo-gravimetric analysis, X-ray photoelectron spectroscopy, transmission electron microscopy and energy-dispersive X-ray spectroscopy. Electrochemical measurements showed that the Pt/RGO hybrids exhibit good activity as catalysts for the electro-oxidation of methanol and ethanol in acid media. Interestingly, the Pt/RGO hybrids showed better electrocatalytic activity and stability for the oxidation of methanol than Pt/C and Pt/RGO hybrids made from other Pt precursors. This indicates that the Pt/RGO hybrids should have great potential applications in direct methanol and ethanol fuel cells.     

Selective hydrogenation of cinnamaldehyde over reduced graphene oxide supported Pt catalyst

Highly dispersed platinum nanoparticles (NPs) were fabricated on the surface of few-layered reduced graphene oxide (Pt/RGO) via direct ethylene glycol reduction of PtCl₆^2 − in aqueous solution. This well-defined Pt/RGO catalyst was highly selective and active for the hydrogenation of cinnamaldehyde (CAL) to corresponding cinnamyl alcohol (COL) under mild conditions. It was found that the selectivity of COL remained 85.3% at 97.8% CAL conversion in ethanol. These results could be ascribed to the well dispersed Pt NPs on RGO sheets, well dispersion of Pt/RGO in ethanol and ethanol can inhibit the generation of acetals.     

Evaluating the photocatalytic activity of Pt/TNT film catalyst

TiO₂ nanotubes (TNT) were prepared by a hydrothermal method from the commercially available TiO₂-P25. Five types of TNT were produced at different temperatures (120 °C, 130 °C, and 150 °C) and by using different reaction times (12 h, 24 h, and 30 h). The photocatalytic reactor that was used is a film catalytic reactor, in which the height of the catalyst is 1.0 mm. The BET and FESEM analysis results showed that TNT130-24 (130 °C, 24 h) and TNT150-12 (150 °C, 12 h) possessed well-formed tubular structures with a high specific surface area (282.9–316.7 m² g⁻¹) and large pore volumes (0.62–0.70 cm³ g⁻¹). However, TNT120-30 (120 °C, 30 h) presented the best photocatalytic activity upon CO removal due to the synergistic effect of TiO₂ nanotubes and TiO₂ particles. After the TNT catalysts were modified with Pt particles, the removal efficiency was in the order of Pt/TNT120-30>Pt/TNT130-24>Pt/P25. Pt/TNT120-30 showed 99% removal efficiency in a continuous photoreactor with a high space velocity of 1.79×10⁴ h⁻¹. The results of the TEM and DRS analyses confirmed that the Pt particles enhanced the photocatalytic reaction, which was attributed to the well-dispersed nature of the 1 nm nanoscaled Pt particles on the surfaces of the TNT catalysts, and narrowed the band gap from 3.22 eV to 3.01 eV.     

Outstanding efficiency of indium in bimetallic catalysts for hydroconversion of bioacids to bioalcohols

Step by step reduction of acetic acid (AA) to ethanol was investigated over novel bimetallic catalysts (PtIn/Al₂O₃) for the processing of VFAs (volatile fatty acids) that can be produced simply by thermochemical or biological biomass degradation. A fixed bed flow-through reactor was applied with hydrogen stream at 21 bar total pressure in the temperature range of 220–380 °C. AA hydroconversion activity of the parent alumina supported Pt catalyst and the yield of selectively produced alcohol can be increased drastically by In₂O₃ addition. Appearance of metallic indium creating a bimetallic catalyst can direct the consecutive catalytic reduction to ethanol formation inhibiting hydrodecarbonylation. Comparing the In-containing bimetallic catalysts studied recently, NiIn-catalyst showing similar activity to that of the PtIn-catalyst can be a cheap substitute for the expensive Pt catalysts in the reduction carboxylic acids.     

Impact of support oxide and Ba loading on the NOx storage properties of Pt/Ba/support catalysts: CO2 and H2O effects

A series of 1 wt.%Pt/_xBa/Support (Support = Al₂O₃, SiO₂, Al₂O₃-5.5 wt.%SiO₂ and Ce_0.7Zr_0.3O₂, x = 5–30 wt.% BaO) catalysts was investigated regarding the influence of the support oxide on Ba properties for the rapid NO_x trapping (100 s). Catalysts were treated at 700 °C under wet oxidizing atmosphere. The nature of the support oxide and the Ba loading influenced the Pt–Ba proximity, the Ba dispersion and then the surface basicity of the catalysts estimated by CO₂-TPD. At high temperature (400 °C) in the absence of CO₂ and H₂O, the NO_x storage capacity increased with the catalyst basicity: Pt/20Ba/Si < Pt/20Ba/Al5.5Si < Pt/10Ba/Al < Pt/5Ba/CeZr < Pt/30Ba/Al5.5Si < Pt/20Ba/Al < Pt/10BaCeZr. Addition of CO₂ decreased catalyst performances. The inhibiting effect of CO₂ on the NO_x uptake increased generally with both the catalyst basicity and the storage temperature. Water negatively affected the NO_x storage capacity, this effect being higher on alumina containing catalysts than on ceria–zirconia samples. When both CO₂ and H₂O were present in the inlet gas, a cumulative effect was observed at low temperatures (200 °C and 300 °C) whereas mainly CO₂ was responsible for the loss of NO_x storage capacity at 400 °C. Finally, under realistic conditions (H₂O and CO₂) the Pt/20Ba/Al5.5Si catalyst showed the best performances for the rapid NO_x uptake in the 200–400 °C temperature range. It resulted mainly from: (i) enhanced dispersions of platinum and barium on the alumina–silica support, (ii) a high Pt–Ba proximity and (iii) a low basicity of the catalyst which limits the CO₂ competition for the storage sites.