Electrodeposited Ni-Cr2O3 nanocomposite anodes for ethanol electrooxidation

Nanocomposite coatings of Ni-Cr₂O₃ supported on carbon electrodes have been prepared by electrodeposition technique from nickel Watts bath in presence of Cr₂O₃ nanoparticles. Their electrochemical catalytic activities have been evaluated towards electrooxidation of ethanol in 1.0 M NaOH solution by using cyclic voltammetry, chronoamperometry and Tafel plots. The performance of the prepared anodes towards electrooxidation of ethanol as a function of co-deposited Cr₂O₃ content was studied. The catalytic activity of fabricated electrodes increases with increasing the volume fraction percent (V_f%) of Cr₂O₃ in the deposited film up to 7V_f%. The Ni-Cr₂O₃/C (7V_f%) electrode displayed significantly enhanced catalytic activity and stability towards electrooxidation of ethanol compared with Ni/C electrode. The kinetic parameters of Ni(OH)₂/NiOOH and ethanol oxidation at Ni/C and Ni-Cr₂O₃/C electrodes have been evaluated.     

Pt support of multidimensional active sites and radial channels formed by SnO2 flower-like crystals for methanol and ethanol oxidation

SnO₂ nanoflowers and nanorods have been synthesized by the hydrothermal method without using any capping agent. Both types of SnO₂ nanostructures are selected as a support of Pt catalyst for methanol and ethanol electrooxidation. The synthesized SnO₂ nanostructures and SnO₂ supported platinum (Pt/SnO₂) catalysts are characterized by X-ray diffraction, scanning electron microscope and high resolution transmission electron microscope. The electrocatalytic properties of the Pt/SnO₂ and Pt/C catalysts for methanol and ethanol oxidation have been investigated systematically by typical electrochemical methods. The influence of SnO₂ morphology on its electrocatalytic activity is comparatively investigated. The Pt/SnO₂ flower-shaped catalyst shows higher electrocatalytic activity and better long-term cycle stability compared with other electrocatalysts owing to the multidimensional active sites and radial channels of liquid diffusion.     

Electrocatalytic oxidation of methanol on CoNi electrodeposited materials

Cobalt–nickel bimetallic materials electrodeposited on Si/Ti/Ni substrates were evaluated for the oxidation of methanol in alkaline media. CoNi samples were prepared potentiostatically selecting conditions adequate to achieve the desired Co/Ni ratio. All samples were characterized by X-ray fluorescence and cyclic voltammetry to determine their composition and electrochemical behaviour. The electrocatalytical performance of prepared samples was evaluated also by cyclic voltammetry using methanol solutions in alkaline media. Material composition, methanol and NaOH concentration, and temperature were the variables studied. The results indicate that a cobalt excess inhibits the methanol oxidation. In the same way, a significant enhancement of the oxidation current was observed on increasing the NaOH concentration up to 0.5 M, but for higher concentrations the electrocatalytic performance of these materials decreases. With regard to the increase of MeOH concentration or temperature, both variables are related to an improvement of the electrocatalytic performance. Finally, the effect of platinum skin on the CoNi deposits was evaluated, concluding that it favours MeOH oxidation but does not protect the substrate surface from the damage exerted by excessive NaOH concentration.     

Optimization of the Pd–Sn–GNS nanocomposite for enhanced electrooxidation of methanol

Highly dispersed Pd nanoparticles with varying loadings (15–40 wt%) and (20 − x)%Pd–x%Sn (where x = 1, 2, 3 and 5) nanocomposites are obtained on graphene nanosheets (GNS) by a microwave-assisted ethylene glycol (EG) reduction method for methanol electrooxidation in alkaline solution. The electrocatalysts were characterized by XRD, SEM, TEM, cyclic voltammetry, and chronoamperometry. The study shows that the Pd nanoparticles on GNS are crystalline and follow the face centered cubic structure. Introduction of a small amount of Sn (1–5 wt%) shifts the characteristic diffraction peaks for Pd slightly to a lower angle. The electrocatalytic performance of the Pd/GNS electrodes has been observed to be the best with 20 wt% Pd loading; a higher or lower loading than 20 wt% Pd produces an electrode with relatively low catalytic activity. The apparent catalytic activity of this active electrode at E = −0.10 V is found to improve further by 79% and CO poisoning tolerance by 40% with introduction of 2 wt% Sn. Among the electrodes investigated, the 18%Pd–2%Sn/GNS exhibited the greatest electrocatalytic activity toward methanol electrooxidation.     

Multi-tube Pd–Ag membrane reactor for pure hydrogen production

An experimental apparatus carrying out a membrane process for producing pure hydrogen via ethanol steam reforming has been tested in order to measure the hydrogen production by varying operative parameters such as temperature, pressure and membrane sweeping mode.     

Electrocatalytic activity of Pd–Au nanoalloys during methanol oxidation reaction

Methanol fuel cells are very promising power source due to its high efficiency and low emissions of pollutants but their commercialization is hindered by development of the effective catalysts. Bimetallic nanostructured catalysts have been used to increase the effectiveness of methanol electrooxidation. Their high electrocatalytic activity can be accounted largely by the difference in electronegativity of two metals (e.g. Pd and Au), that resulting in gradual Au^δ+→Au^δ– transition with the increase in Pd content. Therefore, gold-enriched bimetallic Pd-Au_nano were recommended as catalysts for oxidation processes since they are characterized by the presence of Au^δ+ on their surface. Deposition of Pd, Au and Pd–Au nanoparticles (~50–350 nm) were carried out in dimethyl sulfoxide by pulsed mode of electrolysis directly on electrode surface. Cyclic voltammetry was the main method to study catalytic properties of the modified electrode in the anode oxidation process of methanol. It was found that oxidation rate on the electrode surface modified by bimetallic Pd–Au nanoparticles is ~1.5 times higher as compared to that in the case of electrodes modified by Pd or Au monometallic nanoparticles individually. In order to find highly active, selective, and stable catalysts for methanol electrocatalytic oxidation reaction additional studies are needed to understand the role of electrode surface charge and local OH⁻ ions concentration from alkali solution.     

ZnO/Polytyramine nanocomposite film: Facile electrosynthesis and high performance electrocatalytic activity toward methanol oxidation

In the present study, the methanol oxidation reaction was investigated on a nickel ion incorporated to the zinc oxide-sodium dodecyl sulfate-polytyramine (ZnO-SDS-Pty) nanocomposite film by cyclic voltammetry and chronoamperometry. ZnO-SDS-Pty nanocomposite was prepared by using the repeated potential cyclic voltammetry in a solution containing ZnO nanoparticles and tyramine in an acidic solution of SDS by cycling the potential. The electrochemical oxidation of methanol was investigated by a stable redox behavior of the Ni(III)/Ni(II) couple at the potential of 0.4 V, after the immersion of the modified electrode (ZnO-SDS-Pty/G) in an alkaline media (i.e. NaOH 0.1 molL^?1) of nickel chloride solution. The electrochemical characterization of the modified electrode exhibited that the ZnO-SDS-Pty nanocomposite, electrodeposited on the electrode surface, improved the catalytic efficiency of the dispersed nickel ions toward methanol oxidation. The catalytic rate constant and diffusion coefficient of the methanol oxidation reaction were calculated by chronoamperometry. The Ni-ZnO-SDS-Pty nanocomposite displayed a highly stable response during the oxidation of methanol, proving to be a suitable electrode material in methanol fuel cells.     

An in situ Fourier transform infrared spectroelectrochemical study on ethanol electrooxidation on Pd in alkaline solution

The mechanism of ethanol electrooxidation on a palladium electrode in alkaline solution (from 0.01 to 5 M NaOH) has been investigated by cyclic voltammetry and in situ Fourier transform infrared spectroelectrochemistry. The electrode performance has been found to depend on the pH of the fuel solution. The best performance was observed in 1 M NaOH solution (pH = 14), while the electrochemical activity decreased by either increasing or decreasing the NaOH concentration. In situ FTIR spectroscopic measurements showed the main oxidation product to be sodium acetate at NaOH concentrations higher than 0.5 M. The C-C bond cleavage of ethanol, put in evidence by the formation of CO₂, occurred at pH values ≤13. In these conditions, however, the catalytic activity for ethanol oxidation was quite low. No CO formation was detected along the oxidation of ethanol by FTIR spectroscopy.     

Performance of a direct methanol alkaline membrane fuel cell

A study of a direct methanol fuel cell (DMFC) operating with hydroxide ion conducting membranes is reported. Evaluation of the fuel cell was performed using membrane electrode assemblies incorporating carbon-supported platinum/ruthenium anode and platinum cathode catalysts and ADP alkaline membranes. Catalyst loadings used were 1 mg cm⁻² Pt for both anode and cathode. The effect of temperature, oxidant (air or oxygen) and methanol concentration on cell performance is reported. The cell achieved a power density of 16 mW cm⁻², at 60 °C using oxygen. The performance under near ambient conditions with air gave a peak power density of approximately 6 mW cm⁻².     

Ethanol electro-oxidation: Cyclic voltammetry,electrochemical impedance spectroscopy and galvanostatic oscillation

In the present work, ethanol electro-oxidation reaction on Pt electrode has been studied in details by measuring and analyzing the cyclic voltammetries (CV), the dependence of the electrochemical impedance spectroscopies (EIS) on the applied potentials and the galvanostatic potential oscillation. The CV measurement has exhibited a bistable characteristic. The origin of all the oxidation and reduction peaks has been analyzed. The origin of the bistable characteristic has also been studied by measuring the EIS at different potentials. In addition, the dependence of the galvanostatic oscillation on the applied potential and the ethanol concentration has been reported.     

Electrochemical degradation of Nafion ionomer to functionalize carbon support for methanol electro-oxidation

An effective electrochemical route to produce functional groups on carbon surface is demonstrated. Cyclic voltammetric (CV) sweeps are performed in 0.5 M H₂SO₄ electrolyte on electrodes containing carbon cloth, Vulcan XC72R, and Nafion ionomer. With supply of ambient oxygen, the generation of hydroxyl radicals from the oxygen reduction reaction during CV cycles initiates the decomposition of Nafion ionomer that leads to formation of oxygenated functional groups on the carbon surface. Ion chromatography confirms the dissolution of sulfate anions upon CV scans. Raman analysis suggests a minor alteration for the carbon structure. However, X-ray photoelectron spectroscopy indicates a significant increase of oxygenated functional groups in conjunction with notable reduction in the fluorine content. The amount of the oxygenated functional groups is determined by curve fitting of C 1s spectra with known constituents. These functional groups can also be found by immersing the as-prepared electrode in a solution containing concentrated residues from Nafion ionomer decomposition. The functionalized electrode allows a 170% increment of Pt ion adsorption as compared to the reference sample. After electrochemical reductions, the functionalized electrode reveals significant improvements in electrocatalytic abilities for methanol oxidation, which is attributed to the oxygenated functional groups that facilitates the oxidation of CO on Pt.     

H2 production by low pressure methanol steam reforming in a dense Pd–Ag membrane reactor in co-current flow configuration: Experimental and modeling analysis

The aim of this work is to generate a pure or CO_x-free hydrogen stream by using a dense Pd-based packed bed membrane reactor (PBMR) during methanol steam reforming (MSR) reaction and developing a valid model that can provide a tool for deeper analyses of the reaction parameters in the PBMR. Therefore, in this study, a dense Pd–Ag membrane reactor (MR) is used to carry out MSR at different gas hourly space velocity (GHSV), feed molar ratio and sweep gas factor (SF) and for low reaction pressures (1.5–2.5 bar). For a better analysis, a traditional packed bed reactor (PBR) is operated at the same PBMR conditions. In the PBMR setup, a dense Pd–Ag membrane with a thickness of 50 μm is used and also a commercial Cu/ZnO/Al₂O₃ catalyst is packed in both kinds of reactors. Methanol conversion equal to 100% is experimentally achieved in the PBMR at 280 °C, H₂O/CH₃OH = 3/1 and 2.5 bar, while at the same conditions the PBR reaches 91% methanol conversion. Moreover, 46% CO_x-free hydrogen on total hydrogen produced is collected by using sweep gas in the PBMR permeate side. Furthermore, a 1-dimensional and isothermal model is developed for theoretically analyzing MSR performance in both PBMR and PBR, validated by the combined experimental campaign.     

Sodium borohydride as an additive to enhance the performance of direct ethanol fuel cells

The effect of adding small quantities (0.1-1 wt.%) of sodium borohydride (NaBH₄) to the anolyte solution of direct ethanol fuel cells (DEFCs) with membrane-electrode assemblies constituted by nanosized Pd/C anode, Fe-Co cathode and anion-exchange membrane (Tokuyama A006) was investigated by means of various techniques. These include cyclic voltammetry, in situ FTIR spectroelectrochemistry, a study of the performance of monoplanar fuel cells and an analysis of the ethanol oxidation products. A comparison with fuel cells fed with aqueous solutions of ethanol proved unambiguously the existence of a promoting effect of NaBH₄ on the ethanol oxidation. Indeed, the potentiodynamic curves of the ethanol-NaBH₄ mixtures showed higher power and current densities, accompanied by a remarkable increase in the fuel consumption at comparable working time of the cell. A ¹³C and ¹¹B {¹H}NMR analysis of the cell exhausts and an in situ FTIR spectroelectrochemical study showed that ethanol is converted selectively to acetate while the oxidation product of NaBH₄ is sodium metaborate (NaBO₂). The enhancement of the overall cell performance has been explained in terms of the ability of NaBH₄ to reduce the PdO layer on the catalyst surface.     

nPt (Hx−2nMoO3) as a promising catalyst for the oxidation of methanol. Synthesis and electrocatalytic properties

A new method for the synthesis of the catalyst systems Pt–Mo was suggested. nPt⁰(H_x−2nMoO₃)/GC electrodes were prepared by a redox reaction between the hydrogen-containing molybdenum bronzes and potassium tetrachloroplatinate (II) in acid solutions at open circuit potential. The electrodes were characterized by CVA, SEM, X-ray microanalysis, XRD, XPS and ICP-AES. Pt⁰conglomerates formation with nonuniform distribution over the molybdenum bronzes surface has been revealed. nPt⁰(H_x−2nMoO₃)/GC electrodes showed high catalytic activity (not inferior to Pt–Ru-catalyst) in the oxidation of carbon monoxide and methanol as compared with Pt/GC-electrodes. Catalytic effect is apparently achieved by effective oxidation of strongly chemisorbed species (CO_ads, HCO_ads), which occurs at boundaries platinum – molybdenum oxide. Therefore nPt⁰(H_x−2nMoO₃) can be considered as one of perspective catalysts for DMFC.     

Improvement of methanol electro-oxidation activity of PtRu/C and PtNiCr/C catalysts by anodic treatment

The effect of an anodic treatment on the methanol oxidation activity of PtRu/C (50:50 at.%) and PtNiCr/C (Pt:Ni:Cr = 28:36:36 at.%) catalysts was investigated for various potential limits of 0.9, 1.1, 1.3 and 1.4 V (vs. reference hydrogen electrode, RHE). NaBH₄ reduced catalysts were further reduced at 900 °C for 5 min in an argon balanced hydrogen flow stream. Improved alloying was obtained by the hydrogen reduction procedure as confirmed by X-ray diffraction results. In the PtRu/C catalyst, a decrease of irreversible Ru (hydrous) oxide formation was observed when the anodic treatment was performed at 1.1 V (vs. RHE) or higher potentials. In chronoamperometry testing performed for 60 min at 0.6 V (vs. RHE), the highest activity of the PtRu/C catalyst was observed when anodic treatment was performed at 1.3 V (vs. RHE). The current density increased from 1.71 to 4.06 A g_cat.⁻¹ after the anodic treatment. In the PtNiCr/C catalyst, dissolution of Ni and Cr was observed when potentials ≥1.3 V (vs. RHE) were applied during the anodic treatment. In MOR activity tests, the current density of the PtNiCr/C catalyst dramatically increased by more than 13.5 times (from 0.182 to 2.47 A g_cat.⁻¹) when an anodic treatment was performed at 1.4 V. On an A g_{noble metal}⁻¹ basis, the current density of PtNiCr-1.4V is slightly higher than the best anodically treated PtRu-1.3V catalyst, suggesting the PtNiCr catalyst is a promising candidate to replace the PtRu catalysts.     

Facile synthesis of a Bi-modified PtRu catalyst for methanol and ethanol electro-oxidation in alkaline medium

In this work a facile synthesis for a high-performance PtRuBi/C catalyst was presented through a simple mixture of commercial PtRu/C and Bi(NO₃)₃. Most of the Bimodified the PtRu particle surface via irreversible adsorption and deposition processes. X-ray photoelectron spectroscopy analysis indicated that Bi₂O₃ was the main form in the catalyst and that there exists an interaction between Bi₂O₃ and Pt. The current density of PtRuBi/C (1:1:0.2 for Pt:Ru:Bi) in the cyclic voltammograms for methanol or ethanol oxidation is over 2.6 times higher than that of PtRu/C. The anti-poisoning ability of this catalyst was also greatly improved. The Bi-containing catalyst had abundant oxygenated species and facilitated removal of poisonous intermediate species.