Formation of nanostructured porous Cu-Au surfaces : the influence of cationic sites on (electro)-catalysis

The fabrication of nanostructured bimetallic materials through electrochemical routes offers the ability to control the composition and shape of the final material that can then be effectively applied as (electro)-catalysts. In this work a clean and transitory hydrogen bubble templating method is employed to generate porous Cu–Au materials with a highly anisotropic nanostructured interior. Significantly, the co-electrodeposition of copper and gold promotes the formation of a mixed bimetallic oxide surface which does not occur at the individually electrodeposited materials. Interestingly, the surface is dominated by Au(I) oxide species incorporated within a Cu2O matrix which is extremely effective for the industrially important (electro)-catalytic reduction of 4-nitrophenol. It is proposed that an aurophilic type of interaction takes place between both oxidized gold and copper species which stabilizes the surface against further oxidation and facilitates the binding of 4-nitrophenol to the surface and increases the rate of reaction. An added benefit is that very low gold loadings are required typically less than 2 wt% for a significant enhancement in performance to be observed. Therefore the ability to create a partially oxidized Cu–Au surface through a facile electrochemical route that uses a clean template consisting of only hydrogen bubbles should be of benefit for many more important reactions.

In-situ FT-IR spectroscopic studies of fuel cell electro-catalysis: From single-crystal to nanoparticle surfaces

The work presented in this article shows the power of the variable temperature, in-situ FT-IR spectroscopy system developed in Newcastle with respect to the investigation of fuel cell electro-catalysis. On the Ru(0001) electrode surface, CO co-adsorbs with the oxygen-containing adlayers to form mixed [CO+(2x2)-O(H)] domains. The electro-oxidation of the Ru(0001) surface leads to the formation of active (1x1)-O(H) domains, and the oxidation of adsorbed CO then takes place at the perimeter of these domains. At 20 degrees C, the adsorbed CO is present as rather compact islands. In contrast, at 60 degrees C, the COads is present as a relatively looser and weaker adlayer. Higher temperature was also found to facilitate the surface diffusion and oxidation of COads. No dissociation or electro-oxidation of methanol was observed at potentials below approximately 950mV; however, the Ru(0001) surface at high anodic potentials was observed to be very active. On both Pt and PtRu nanoparticle surfaces, only one linear bond CO adsorbate was formed from methanol adsorption, and the PtRu surface significantly promoted both methanol dissociative adsorption to CO and its further oxidation to CO2. Increasing temperature from 20 to 60 degrees C significantly facilitates the methanol turnover to CO2.

The role of HBF(4) in electro-catalysis: Arsenic contamination and anion adsorption

We present in this work a comprehensive investigation of the role played by dissolved tetrafluoroboric acid on the electrochemical response of a polycrystalline platinum electrode in acidic media. HBF(4) from two different suppliers was employed and characterized in terms of the amount of arsenic contamination by Inductively Coupled Plasma-Optical Emission Spectroscopy. The effect of different amounts of HBF(4) on the voltammetric profile of the Pt vertical bar HClO(4)(aq) interface was investigated by means of electrochemical quartz crystal nanobalance (EQCN). Despite the comparable cyclic voltammograms, the presence of arsenic in one of the two HBF(4) used resulted in dramatic variations in the mass change profile, which evidences the deposition/dissolution of arsenic prior to the surface oxidation. For the arsenic-free HBF(4), its effect on the mass change profile was mainly associated to anion adsorption. The impact of dissolved HBF(4) on the electro-oxidation of formic acid was rationalized in terms of two contributions: current enhancement at low potentials due to the arsenic-assisted formic acid electro-oxidation and inhibition at high potentials due to anion adsorption. (C) 2011 Elsevier B.V. All rights reserved.

Bio-inspired carbon electro-catalysis for the oxygen reduction reaction

We report the synthesis, characterisation and catalytic performance of two nature-inspired biomass-derived electro-catalysts for the oxygen reduction reaction in fuel cells. The catalysts were prepared via pyrolysis of a real food waste (lobster shells) or by mimicking the composition of lobster shells using chitin and CaCO3 particles followed by acid washing. The simplified model of artificial lobster was prepared for better reproducibility. The calcium carbonate in both samples acts as a pore agent, creating increased surface area and pore volume, though considerably higher in artificial lobster samples due to the better homogeneity of the components. Various characterisation techniques revealed the presence of a considerable amount of hydroxyapatite left in the real lobster samples after acid washing and a low content of carbon (23%), nitrogen and sulphur (<1%), limiting the surface area to 23 m2/g, and consequently resulting in rather poor catalytic activity. However, artificial lobster samples, with a surface area of ≈200 m2/g and a nitrogen doping of 2%, showed a promising onset potential, very similar to a commercially available platinum catalyst, with better methanol tolerance, though with lower stability in long time testing over 10,000 s.

Methanol and ethanol electro-oxidation on Pt-SnO(2) and Pt-Ta(2)O(5) sol-gel-modified boron-doped diamond surfaces

The search for more efficient anode catalyst than platinum to be used in direct alcohol fuel cell systems is an important challenge. In this study, boron-doped diamond film surfaces were modified with Pt, Pt-SnO(2) and Pt-Ta(2)O(5) nano-crystalline deposits by the sol-gel method to study the methanol and ethanol electro-oxidation reactions in acidic medium. Electrochemical experiments carried out in steady-state conditions demonstrate that the addition of SnO(2) to Pt produces a very reactive electrocatalyst that possibly adsorbs and/or dissociate ethanol more efficiently than pure Pt changing the onset potential of the reaction by 190 mV toward less positive potentials. Furthermore, the addition of Ta(2)O(5) to Pt enhances the catalytic activity toward the methanol oxidation resulting in a negative shift of the onset potential of 170 mV. These synergic effects indicate that the addition of these co-catalysts inhibits the poisoning effect caused by strongly adsorbed intermediary species. Since the SnO(2) catalyst was more efficient for ethanol oxidation, it could probably facilitate the cleavage of the C-C bond of the adsorbed intermediate fragments of the reaction. (C) 2009 Elsevier B.V. All rights reserved.

Enhanced photoelectrocatalytic degradation of an acid dye with boron-doped TiO2 nanotube anodes

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Platinum-macrocycle co-catalyst for electro-oxidation of formic acid

In this work, a new promoter, tetrasulfophthalocyanine (FeTSPc), one kind of environmental friendly material, was found to be very effective in both inhibiting self-poisoning and improving the intrinsic catalysis activity, consequently enhancing the electro-oxidation current during the electro-oxidation of formic acid. The cyclic voltammograms test showed that the formic acid oxidation peak current density has been increased about 10 times compared with that of the Pt electrode without FeTSPc. The electrochemical double potential step chronoamperometry measurements revealed that the apparent activity energy decreases from 20.64 kJ mol(-1) to 17.38 kJ mol(-1) after Pt electrode promoted by FeTSPc. The promoting effect of FeTSPc may be owed to the specific structure and abundant electrons of FeTSPc resulting in both the steric hindrance of the formation of poisoning species (CO) and intrinsic kinetic enhancement. In the single cell test, the performance of DFAFC increased from 80 mW cm(-2) mg(-1) (Pt) to 130 mW cm(-2) mg(-1) after the anode electrode adsorbed FeTSPc.

Benzene electro-oxidation in a PEMFC for phenol and electricity cogeneration

In the present investigation, the electrochemically-assisted oxidation of benzene in a H-2-O-2 proton exchange membrane fuel cell (PEMFC) for electricity and phenol cogeneration is studied. Experiments were carried out in a PEMFC electrochemical reactor using Pd black as cathode electrocatalyst at 60 and 80 degrees C, respectively and 1 atm back pressure. Indeed, it was found that the only product detected under the examined experimental conditions was phenol. The online GC product analysis revealed that it is impossible to produce phenol when the fuel cell circuit is open (I = 0) under all the examined experimental conditions. When the fuel cell circuit was closed, however, the phenol yield was found to follow a volcano-type dependence on the cur-rent of the external circuit. It was found that the maximum phenol yield was 0.35% at 100 mA/cm(2) at 80 degrees C. At the same time, the PEMFC performance was also investigated during the phenol generation process. Furthermore, experiments with the rotating ring disc electrode (RRDE) technique showed that the intermediate oxidation product, i.e. H2O2 existed during the oxygen electro-reduction process. The cyclic voltammograms showed that benzene was strongly adsorbed on the Pd surface, leading to a degradation of the PEMFC performance. (c) 2005 Elsevier B.V. All rights reserved.

Carbon-dispersed Pt-Rh nanoparticles for ethanol electro-oxidation. Effect of the crystallite size and of temperature

This work presents results of studies of carbon-dispersed Pt-Rh (1:1) nanoparticles as electrocatalysts for the ethanol electro-oxidation. The influences of the crystallite size and the cell temperature on the yields of CO2, acetaldehyde and acetic acid are investigated. Metal nanoparticles were prepared by two different routes: (1) impregnation on carbon powder followed by thermal reduction on hydrogen atmosphere and (2) chemical reduction of the precursor salts. The surface active area and the electrochemical activity of the electrocatalysts were estimated by CO stripping and cyclic voltammetry in the absence and in the presence of ethanol, respectively. Reaction intermediates and products were analyzed by in situ Fourier Transform Infra-Red Spectroscopy (FTIR) and Differential Electrochemical Mass Spectrometry (DEMS). The electrochemical stripping of CO and the electrochemical ethanol oxidation were slightly faster on the Pt-Rh electrocatalysts compared to Pt/C. Also, in situ FTIR spectra and DEMS measurements evidenced that the CO2/acetaldehyde and the CO2/acetic acid ratios are higher for the Pt-Rh/C materials in relation to Pt/C. This was ascribed to the activation of the C-C bond breaking by Rh, this being more prominent for the materials with smaller crystallite sizes. (C) 2008 Elsevier B.V. All rights reserved.

Ethanol electro-oxidation on carbon-supported Pt-Ru, Pt-Rh and Pt-Ru-Rh nanoparticles

This work investigates the effects of carbon-supported Pt, Pt-Ru, Pt-Rh and Pt-Ru-Rh alloy electrocatalysts oil the yields of CO2 and acetic acid as electro-oxidation products of ethanol. Electronic and structural features of these metal alloys were studied by in situ X-ray absorption spectroscopy (XAS). The electrochemical activity was investigated by polarization experiments and the reaction intermediates and products were analyzed by in situ Fourier Transform Infra-Red Spectroscopy (FTIR). Electrochemical stripping of CO. which is one of the adsorbed intermediates, presented a faster oxidation kinetics on the Pt-Ru electrocatalyst, and similar rates of reaction on Pt-Rh and Pt. The electrochemical current of ethanol oxidation showed a higher value and the onset potential was less positive oil Pt-Ru. However, in situ FTIR spectra evidenced that the CO2/acetic acid ratio is higher for the materials with Rh, mainly at lower potentials. These results indicate that the Ru atoms act mainly by providing oxygenated species for the oxidation of ethanol intermediates, and point out ail important role of Rh on the C-C bond dissociation. (C) 2007 Elsevier Ltd. All rights reserved.

Electrocatalytic activity under oscillatory regime: The electro-oxidation of formic acid on ordered Pt3Sn intermetallic phase

Despite the considerable progress in the understanding of the mechanistic aspects of the oscillatory electro-oxidation of C1 molecules, there are apparently no systematic studies concerning the impact of surface modifiers on the oscillation dynamics. Herein we communicate on the oscillatory electro-oxidation of formic acid on ordered Pt3Sn intermetallic phase, and compare the results with those obtained on a polycrystalline platinum electrode. Overall, the obtained results were very reproducible, robust and allowed a detailed analysis on the correlation between the catalytic activity and the oscillation dynamics. The presence of Sn in the intermetallic electrode promotes drastic effects on the oscillatory dynamics. The decrease in the mean electrode potential and in the oscillation frequency, as well as the pronounced increase in the number oscillations (and also in the oscillation time), was discussed in connection with the substantial catalytic enhancement of the Pt3Sn towards the electro-oxidation of formic acid. The self-organized potential oscillations were used to probe the electrocatalytic activity of the Pt3Sn electrode and compare it with that for polycrystalline Pt. The presence of Sn resulted in a significant decrease (2-11 times, depending on the applied current) of the rate of surface poisoning. © 2012 Elsevier B.V.

Reaction intermediates of ethanol electro-oxidation on platinum investigated by SFG spectroscopy

Although electrochemical oxidation of simple organic molecules on metal catalysts is the basic ingredient of fuel cells, which have great technological potential as a renewable source of electrical energy, the detailed reaction mechanisms are in most cases not completely understood. Here, we investigate the ethanol-platinum interface in acidic aqueous solution using infrared-visible sum frequency generation (SFG) spectroscopy and theoretical calculations of vibrational spectra in order to identify the intermediates present during the electro-oxidation of ethanol. The complex vibrational spectrum in the fingerprint region imply on the coexistence of several adsorbates. Based on spectra in ultra-high-vacuum (UHV) and electrochemical environment from the literature and our density functional theory (DFT) calculations of vibrational spectra, new adsorbed intermediates, never before observed with conventional infrared (IR) spectroscopy, are proposed here: g2-acetaldehyde, g2-acetyl, ethylidyne, monodentate acetate, methoxy, tertiary methanol derivative, COH residue, g2-formaldehyde, mono and bidentate formate, CH3 and CH2 residues. In addition, we present new evidences for an ethoxy intermediate, a secondary ethanol derivative and an acetyl species, and we confirm the presence of previously observed adsorbates: a tertiary ethanol derivative, bidentate acetate, and COad. These results indicate that the platinum surface is much more reactive, and the reaction mechanism for ethanol electro-oxidation is considerably more complex than previously considered. This might be also true for many other molecule-catalyst systems.