Electrochemical characterization of adsorbed bilirubin oxidase on Vulcan XC 72R for the biocathode preparation in a glucose/O2 biofuel cell

A new biocathode was built and tested. It consisted of bilirubin oxidase adsorbed on Vulcan XC 72 R and immobilized into a Nafion^® matrix. The possibility of direct electron transfer between bilirubin oxidase and Vulcan XC 72 R was also demonstrated. The kinetics on biocathode were enhanced by including 2,2′-azinobis-3-ethylbenzothiazoline-5-sulfonic acid in the catalytic film. A first order reaction rate was observed for oxygen concentrations lower than 22%. A complete kinetic investigation of the system was shown. A biofuel cell test performed with this biocathode and Au₇₀Pt₃₀ nanoparticles as anode catalyst permitted to reach a power density of 170 μW cm⁻² at a cell voltage of 0.6 V, which is superior to what can be obtained with the concentric design.     

A study on the dissymmetrical microporous layer structure of a direct methanol fuel cell

The effect of carbon type, carbon loading and microporous layer structure in the microporous layer on the performance of a direct methanol fuel cell (DMFC) at low temperature was investigated using electrochemical polarization techniques, electrochemical impedance spectroscopy, scanning electron microscope and other methods. Vulcan XC-72 carbon was found to be most suitable as a microporous layer for low temperature DMFC. Maximum fuel cell performance was obtained utilizing a microporous layer with carbon loading of 1.0 mg cm⁻² when air was used as an oxidant. A membrane electrode assembly with 1.0 mg cm⁻² Vulcan XC-72 carbon with 20 wt.% Teflon in the cathode and no microporous layer in the anode showed a maximum power density of 36.7 mW cm⁻² at 35 °C under atmospheric pressure. The AC impedance study proved that a cell with a dissymmetrical microporous layer structure had lower internal resistance and mass transfer resistance, thus obtaining better performance.     

Novel Pt-Ru nanoparticles formed by vapour deposition as efficient electrocatalyst for methanol oxidation: Part II. Electrocatalytic activity

The methods developed and described in paper—part I are employed to prepare nanometer size Pt-Ru particles on a Vulcan^® XC72R substrate with controlled metal loading. Transmission Electron Microscopy (TEM) confirmed uniform particles size (average diameter 2 nm) and homogeneous dispersion of the particles over the substrate. Energy Dispersive X-ray absorption (EDX) analysis confirmed the compositional homogeneity. The catalytic activity of these supported nanoparticles with regard to methanol electrooxidation is investigated using cyclic voltammetry (CV), chronoamperometry (CA) and CO-stripping voltammetry techniques at temperatures between 25 and 60 °C. Such investigation concerns supported catalysts prepared with ca. 10 and 18 wt.% overall metal loading (Pt + Ru) onto the Vulcan^® XC72R substrate. Comparative testing of our catalysts and a commercial Pt-Ru/Vulcan reveals markedly superior activity for our catalysts. In fact, we observe for the latter a five-fold increase of the oxidation current as compared to a commercial Pt-Ru/Vulcan with equal metal loading. One of the reasons for the greater activity is found to be the very high dispersion of the metals over the substrate, i.e. the large surface area of the active phase. Other reasons are plausibly ascribable to the varied Pt/Ru composition and/or reduced presence of contaminants at the catalyst surface.     

A thermogravimetric analysis/mass spectroscopy study of the thermal and chemical stability of carbon in the Pt/C catalytic system

Vulcan XC72 carbon powder and Pt/Vulcan XC72 catalytic powder were characterized by transmission electron microscopy (TEM) and their reactivity under controlled atmospheres was studied as a function of the temperature. Under air atmosphere, production of water was detected by thermogravimetric analysis coupled with mass spectroscopy (TGA-MS) measurement at m/z 18, which evidenced that hydrogenated surface functions were present on the carbon substrate. Under argon atmosphere, the comparison of TGA-MS measurements performed at m/z 18 and m/z 44 with TEM and XRD results, together with XPS measurements, indicated that platinum surface oxides are rather Pt(OH)₂ than PtO or PtO₂ species. Such reactive surface species is involved in the degradation mechanism of carbon support under air and inert atmospheres. Under H₂(3%)/Ar atmosphere, hydrocarbon production coming from “reforming” reactions of the carbon support started at very low temperatures (below 373 K). TEM images of the same catalytic powder region before and after thermal treatment at 423 K under reducing atmosphere clearly displayed consumption of the carbon substrate. The reaction products may not only affect the intrinsic properties of the support but also the catalytic properties of platinum particles: reaction products could poison the anodic catalyst.     

High sensitive simultaneous determination of catechol and hydroquinone at mesoporous carbon CMK-3 electrode in comparison with multi-walled carbon nanotubes and Vulcan XC-72 carbon electrodes

The simultaneous voltammetric determination of catechol (CC) and hydroquinone (HQ) has been achieved at a mesoporous carbon CMK-3 modified electrode in phosphate buffer solution (pH 7.0). At the electrode both CC and HQ can cause a pair of quasi-reversible and well-defined redox peaks and their peak potential difference increases. In comparison with multi-walled carbon nanotubes (MWCNTs) and Vulcan XC-72 carbon modified electrodes the CMK-3 modified electrode shows larger peak currents and higher adsorbed amounts for the two dihydroxybenzene isomers. This is related to the higher specific surface area of CMK-3. Under the optimized conditions, the linear concentration ranges for CC and HQ are 5 × 10⁻⁷ to 3.5 × 10⁻⁵ M and 1 × 10⁻⁶ to 3 × 10⁻⁵ M, respectively. In the presence of 5 μM isomer, the linear concentration range of CC (or HQ) is 5 × 10⁻⁷ to 2.5 × 10⁻⁵ M (or 5 × 10⁻⁷ to 2.0 × 10⁻⁵ M). The sensitivity for CC or HQ is 41 A M⁻¹ cm⁻² or 52 A M⁻¹ cm⁻², which is close to that without isomer. The detection limits (S/N = 3) for CC and HQ are 1 × 10⁻⁷ M after preconcentration on open circuit for 240 s.     

Effect of potential cycling on structure and activity of Pt nanoparticles dispersed on different carbon supports

Platinum particles synthesized via the Bönnemann methods were dispersed on two different Vulcan XC72 carbon supports. One was used after thermal treatment at 400 °C under nitrogen atmosphere, the other after oxidation of its surface by acid leaching using diluted HNO₃ in water (1/3). Characterization of the carbon support indicated that HNO₃ treatment leads to the decrease of the BET surface and to the increase of the surface acidity of the carbon support. After dispersion of the platinum catalyst, TEM results indicated that the mean particle size was a little higher on the non-oxidized support (Pt/XC72) than that on the functionalized one (Pt/XC72_HNO3), being 2.5 and 2.0 nm, respectively. However, potential cycles from 0.05 to 1.25 V vs. RHE led to a higher increase of the particle size when catalyst is dispersed on the functionalized support, reaching after 400 potential cycles 5.5 nm against 4.0 nm with the non-functionalized one. The effect of the upper limit (1.0 and 1.25 V vs. RHE) of the potential cycles on the active surface area and on the activity towards the oxygen reduction reaction (orr) was determined for both catalysts. Results indicated that the particle growth was not the main degradation process over the whole duration of the electrochemical experiments, but that dissolution/redeposition (Otswald ripening) was also involved. The predominant role of each degradation process depends on the number of cycles, on the upper potential limit and on the carbon surface state, and could be temporally separated. However, the lower activity towards orr was recorded for the (Pt/XC72_HNO3) cycled up to 1.0 V vs. RHE.     

Facile synthesis of bimodal porous silica and multimodal porous carbon as an anode catalyst support in proton exchange membrane fuel cell

A simple and easy sol-gel approach has been developed to directly synthesize in situ three-dimensionally interconnected uniform ordered bimodal porous silica (BPS) incorporating both the macroporosity and mesoporosity in the lattice without extra synthesis process performed in previous work. Multimodal porous carbon (MPC) was fabricated through the inverse replication of the BPS. The unique structural characteristics such as well-developed 3-D interconnected ordered macropore framework with open mesopores embedded in the macropore walls, large surface area (1120 m² g⁻¹) and mesopore volume (1.95 cm³ g⁻¹) make MPC very attractive as an anode catalyst support in polymer exchange membrane fuel cell. The MPC-supported Pt-Ru alloy catalyst has demonstrated much higher power density toward hydrogen oxidation than the commercial carbon black Vulcan XC-72-supported ones.     

Chemical modification of carbon powders with aminophenyl and aryl-aliphatic amine groups by reduction of in situ generated diazonium cations: Applicability of the grafted powder towards CO2 capture

Aminophenyl, p-aminobenzyl and p-aminoethylphenyl groups were grafted at the surface of carbon Vulcan XC72R by spontaneous reduction of the in situ generated diazonium cations from the corresponding amine. X-ray photoelectron spectroscopy and elemental analysis confirmed an amine loading of about 1 mmol/g. The grafting of amine functionalities leads to a decrease of specific surface area from 223 to about 110 m²/g with a drastic loss of microporosity. Acid-base properties of the surface are also affected by the modification. Aminophenyl grafted groups make the surface more acidic while aryl-aliphatic amines groups tends to render it more basic. The grafted layer shows in each case a good thermal stability up to 250 °C. The affinity of the modified powder towards CO₂ and N₂ has been evaluated by thermal swing adsorption. The maximum adsorption capacity of CO₂ of modified carbons is lower than the unmodified carbon but the presence of the amine functionalities involves a better selectivity of the material towards CO₂ adsorption in comparison of N₂ adsorption.     

Enhancement of oxygen reduction by incorporation of heteropolytungstate into the electrocatalytic ink of carbon supported platinum nanoparticles

Nafion stabilized inks of Vulcan XC-72 supported platinum (20 wt.%) nanoparticles (Pt/XC-72) were utilized to produce electrocatalytic films on glassy carbon. The catalysts were modified (activated) with phosphododecatungstic acid H₃PW₁₂O₄₀ (PW₁₂). Comparison was made to bare (PW₁₂-free) electrocatalytic films. Electroreduction of dioxygen was studied at 25 °C in 0.5 mol dm⁻³ H₂SO₄ electrolyte using rotating disk voltammetry. For the same loading of platinum (≈95 μg cm⁻²) and for the approximately identical distribution of the catalyst, the reduction of oxygen at a glassy carbon electrode modified with the ink containing PW₁₂ proceeded at ca. 30-60 mV more positive potential (depending on the PW₁₂ content), and the system was characterized by a higher kinetic parameter (rate of heterogeneous electron transfer), when compared to the PW₁₂-free electrocatalyst. Gas diffusion electrodes with Pt/XC-72 supported on carbon paper (Pt loading 1 mg cm⁻²) were also tested. Under the same experimental conditions, while the exchange current density and the total resistance contribution to polarization components, computed from the galvanostatic polarization curves were found to be clearly higher and lower, respectively, for the ink modified with PW₁₂ relative to the unmodified system. The results demonstrate that addition of heteropolytungstatic acid (together with Nafion) enhances the electrocatalytic activity of platinum towards reduction of oxygen.     

Electrodepositing Pt on a Nafion-bonded carbon electrode as a catalyzed electrode for oxygen reduction reaction

The research aims to increase the utilization of platinum (Pt) catalysts and thus to lower the catalyst loadings in the electrode for oxygen reduction reaction (ORR). The electrodeposition of Pt was performed on a rotation disk electrode (RDE) of glass carbon (GC), on which a layer of Nafion-bonded carbon of Vulcan XC 72R was dispersed in advance. The behaviors of Pt RDE and GC RDE in an aqueous solution containing HCl and H₂PtCl₆ were firstly studied. It was found that Pt deposition could be achieved if the electrode potential is controlled below −0.20 V versus (saturated-potassium-chloride silver chloride electrode) SSCE. However, quite a high overpotential is necessary if a quick and apparent deposition were required. Unfortunately, at a high overpotential, the hydrogen evolution would be unavoidable and even accelerated by the formation of nanometer size of Pt particles on the RDE. It was found that it is futile to increase platinum deposits just through extending the deposition time. It was also found that too large deposition current is not helpful for increase of platinum deposition because most of the current was consumed on hydrogen evolution in this case. It has been confirmed that it is conducive to richen Pt ions, present in the form of anionic complex in solution, onto the working electrode to be deposited. It is also helpful to eliminate the hydrogen bubbles formed on the working electrode, i.e., uncatalyzed carbon electrode (UCE), by imposing a positive current on the UCE for a length of time in advance of each cathodic deposition. The potential changes during deposition were recorded. Cyclic voltammograms (CV) of electrodes in 0.5 M H₂SO₄ before and after the deposition were used to assess loading of metal catalysts in a wide range of potential from −0.20 to 1.1 V versus SSCE. The results have shown that the performance of such an electrode with loadings estimated to be 50 μg Pt/cm² is much better than those of a conventional electrode with loadings of 100 μg Pt/cm².     

Mechanism study of the ethanol oxidation reaction on palladium in alkaline media

In this work, the mechanism of the ethanol oxidation reaction (EOR) on a palladium electrode was studied using the cyclic voltammetry method. The dissociative adsorption of ethanol was found to proceed rather quickly and the rate-determining step was the removal of the adsorbed ethoxi by the adsorbed hydroxyl on the Pd electrode. The Tafel slope was found to be 130 mV dec⁻¹ at lower potentials, which suggests that the adsorption of OH⁻ ions follows the Temkin-type isotherm on the Pd electrode. In comparison, the Tafel slope increased gradually to 250 mV dec⁻¹ at higher potentials. The change in the Tafel slope indicated that, at higher potentials, the kinetics is not only affected by the adsorption of the OH⁻ ions, but also by the formation of the inactive oxide layer on the Pd electrode.     

Electrocatalyst materials for fuel cells based on the polyoxometalates [PMo(12 − n)VnO40] (n = 0-3)

We report on the use of the polyoxometalate acids of the series [PMo_(12 − n)V_nO₄₀]^(3 + n)− (n = 0-3) as electrocatalysts in both the anode and the cathode of polymer-electrolyte membrane (PEM) fuel cells. The heteropolyacids were incorporated as catalysts in a commercial gas diffusion electrode based on Vulcan XC-72 carbon which strongly adsorbed a low loading of the catalyst, ca. 0.1 mg/cm². The moderate activity observed was independent of the number of vanadium atoms in the polyoxometalate. In the anode the electrochemistry is dominated by the V^3+/4+ couple. With a platinum reference wire in contact with the anode, polarization curves are obtained withV_OC of 650 mV and current densities of 10 mA cm⁻² at 100 mV at 80 °C. These catalysts showed an order of magnitude more activity on the cathode after moderate heat treatment than on the anode,V_OC = 750 mV, current densities of 140 mA cm⁻² at 100 mV. The temperature dependence of the catalysts was also investigated and showed increasing current densities could be achieved on the anode up to 139 °C and the cathode to 100 °C showing the potential for these materials to work at elevated temperatures.     

Kinetic study of nitrate reduction on Pt(1 1 0) electrode in perchloric acid solution

The kinetics of electrocatalytic reduction of nitrate on Pt(1 1 0) in perchloric acid was studied with cyclic voltammetry at a very low sweep rate of 1 mV s⁻¹, where pseudo-steady state condition was assumed to be achieved at each electrode potential. Stationary current-potential curves in perchloric acid in the absence of nitrate showed two peaks at 0.13 V and 0.23 V (RHE) in the so-called adsorbed hydrogen region. The nitrate reduction proceeded in the potential region of the latter peak in the pH range studied. The reaction orders with respect to NO₃⁻ and H⁺ were observed to be close to 0 and 1, respectively. The former value means that the adsorbed NO₃⁻ at a saturated coverage is one of the reactants in the rate-determining step (rds). The latter value means that hydrogen species is also a reactant above or on the rds. The Tafel slope of nitrate reduction was −66 mV per decade, which is taken to be approximately −59 mV per decade, indicating that the rds is a pure chemical reaction following electron transfer. We discuss two possible reaction schemes including bimolecular and monomolecular reactions in the rds to explain the kinetics and suggest that the reactants in the rds are adsorbed hydrogen and adsorbed NO₃⁻ with the assistance of the results in our recent report for nitrate reduction on Pt(S)[n(1 1 1) × (1 1 1)] electrodes: the nitrate reduction mechanism can be classified within the framework of the Langmuir-Hinshelwood mechanism.     

Comparative investigation of the resistance to electrochemical oxidation of carbon black and carbon nanotubes in aqueous sulfuric acid solution

The resistance to electrochemical oxidation of carbon black (Vulcan XC-72) and chemical vapor deposited multiwalled carbon nanotubes (CVD-MWNTs), both widely-used as catalyst supports for low temperature fuel cells, is investigated with potentiostatic oxidation in 0.5 mol L⁻¹ H₂SO_4, which mimics the working conditions of low temperature fuel cells. The surface oxygen of oxidized carbon black and MWNTs are analyzed with cyclic voltammetry and X-ray photoelectron spectroscopy (XPS). The increase in surface oxygen on MWNTs during 120 h holding at 1.2 V (versus Reversible Hydrogen Electrode, RHE) is much less than that on carbon black. The conclusion can be reached that CVD-MWNTs are more resistant to electrochemical oxidation than carbon black under the condition in the report. CVD-MWNTs therefore possess a higher potential for low temperature fuel cell applications.     

Ordered mesoporous carbons synthesized by a modified sol-gel process for electrosorptive removal of sodium chloride

Capacitive deionization (CDI) represents an alternative process to remove the ions from the brackish water. In this study two series of ordered mesoporous carbons (OMCs) that demonstrated the potential use for capacitive desalination have been synthesized by a modified sol-gel process involving nickel salts. It was shown that the preferred formation of crown-ether type complexes between nickel ions and triblock copolymers resulted in higher BET surface area and smaller mesopores. As the electrode materials for CDI, OMC obtained by the addition of NiSO₄ · 6H₂O exhibited best electrochemical performance compared with other OMCs and a commercial activated carbon either in 0.1 M NaCl solution or in 0.0008 M NaCl solution, plus the amount of adsorbed ions measured by a flow through apparatus reached 15.9 μmol g⁻¹ and the ions could be fully released into the solution. The excellent electrosorption desalination performance of OMC obtained by the addition of NiSO₄ · 6H₂O was ascribed to its high BET surface area of 1491 m² g⁻¹ and ordered mesopores of 3.7 nm. Based on these results, it is deduced that the modified sol-gel process might be a potential method of obtaining the excellent electrode materials for CDI.     

Study of structural and electrochemical characteristics of Co-based hypo-hyper d-electrocatalysts for hydrogen evolution

Structural and electrochemical characteristics of hypo-hyper d-electrocatalytic materials aimed for preparation of electrodes for hydrogen evolution were studied. The basic catalytic material was prepared of 10% amorphous Co (grain size <2 nm), 18% amorphous TiO₂ and Vulcan XC-72, by sol-gel procedure. A number of modifications were applied aimed at improving the materials performances: (i) TiO₂ was transformed into anatase by heating at 480 °C for 1 h, (ii) multiwalled carbon nanotubes (MWCNT) were used as a catalyst support instead of Vulcan XC-72 and (iii) Mo was added to Co phase in a quantity of 25 at.% (Mo:Co = 1:3).Both, material's intrinsic catalytic activity and surface area were affected by these modifications. As a result, the electrocatalytic activity for hydrogen evolution was improved, e.g. transformation of TiO₂ into anatase form lowers the HER overpotential (η) for 15 mV at 60 mA cm⁻². Introduction of MWCNTs lowered η for 30 mV, while addition of Mo to metallic phase for 40 mV.The complete modification of all three catalyst's components (10% MoCo₃ + 18% anatase + MWCNTs) was the most effective with 60 mV decrease of overpotential.Characterization was made by XRD, SEM, IR and XPS methods. Surface area was measured by means of cyclic voltammetry.     

The efficiency of methanol conversion to CO2 on thin films of Pt and PtRu fuel cell catalysts

Yields were determined for the CO₂ produced upon the electrochemical oxidation of 1.0 M methanol in 0.1 M HClO₄ at the following four fuel cell catalyst systems: Pt black, Pt at 10 wt.% metal loading on Vulcan XC-72R carbon (C/Pt, 10%), PtRu black at 50 at.% Pt, 50 at.% Ru (PtRu (50:50) black), and PtRu at 30 wt.% Pt, 15 wt.% Ru loading on Vulcan XC-72R carbon (C/PtRu, 30 wt.% Pt, 15 wt.% Ru). Samples were electrolyzed in a small volume (50 μl) arrangement for a period of 180 s keeping the reactant depletion in the cell below 1%. The dissolved CO₂ produced was determined ex situ by infrared spectroscopy in a micro-volume transmission flow cell. For the PtRu materials, the efficiencies for CO₂ formation were near 100% at reaction potentials in the range between 0.4 V (versus the reversible hydrogen electrode (RHE), V_RHE ) and 0.9 V_RHE. At the Pt catalysts, the yields of CO₂ approached 80% between 0.8 and 1.1 V_RHE and declined rapidly below 0.8 V_RHE.     

Properties of electrolytes in the micropores of activated carbon

The dependence of the composition of aqueous electrolytes in the pore system of activated carbon on the potential has been determined by monitoring the amount of ions exchanged with the external electrolyte upon immersion and upon changing the electrode potential. From the investigation with KF solutions, a quantity δ/√? = 4 × 10⁻¹⁰ m is evaluated where δ is half the width of the micropores, and ? the (relative) permittivity. This is in accordance with δ ≈ 1 nm and ? ≈ 7 applying to essentially immobilized water and fits into the results with the other electrolytes. Anions are adsorbed in the cases of sodium perchlorate and potassium hydroxide, while protons are adsorbed in the case of acids (HCl, H₂SO₄). The adsorption of ClO₄⁻ seems to result from electrostatic interaction with the solid, while H⁺ and OH⁻ are strongly chemisorbed, probably at surface groups like >CO. Ionic mobilities of ions in the micropores have been determined from conductance measurements concerning the pore electrolyte of a single spherical particle of activated carbon. Mobilities are more than one order of magnitude lower than those in bulk electrolyte, probably due to an increased viscosity of the liquid in the narrow pores and/or to the coulombic interaction with charged domains of the solid. The rate of charging of the capacitor (solid/micropore electrolyte) is assisted by macropores distributing ions throughout the carbon material.     

MnxCu1−xCo2O4 used as bifunctional electrocatalyst in alkaline medium

Composite film electrodes containing mechanically mixed Mn_xCu_1−xCo₂O₄ (0 ≤ x ≤ 1) particles, carbon black Vulcan XC72R and poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP) were formed on the glassy carbon disk surface of a rotating ring-disk electrode (RRDE) and studied for the oxygen reduction and evolution reactions (ORR and OER, respectively) in 1 M KOH solution. The electrocatalytic activities for both reactions were observed to depend strongly on the Mn content in CuCo₂O₄. An opposite trend was observed for the apparent and intrinsic electrocatalytic activities for the ORR; the simultaneous presence of Cu and Mn was found to be detrimental to the intrinsic charge density, but beneficial to the geometric charge density with a maximum for Mn_0.6Cu_0.4Co₂O₄. The latter was characterized by the highest total number of electrons exchanged per O₂ molecule, n, close to 4, greater k₁ (4e⁻ process)/k₂ (2e⁻ process) ratios, and by a unique and low Tafel slope (−41 mV dec⁻¹). The results obtained for the OER showed that the intrinsic electrocatalytic activity is determined by the number of active sites (Co⁴⁺) electrochemically formed at the oxide surface prior to the OER, from Co³⁺ cations. The partial substitution of Cu by Mn in CuCo₂O₄ was found to decrease the OER activity.     

Fabrication of bimodal mesoporous carbons from petroleum pitch by a one-step nanocasting method

A one-step nanocasting method to prepare a bimodal mesoporous carbon from a highly hydrophobic carbon precursor, i.e., petroleum pitch, has been successfully developed by adopting tetrahydrofuran and hydrofluoric acid as solvent and catalyst, respectively, for the gelation reaction of tetraethyl orthosilicate and water. Experimental results show that the introduction of proper amounts of petroleum pitch does not hamper this gelation reaction, thus forming a uniform silica/carbon composite. It was found that the as-prepared nanoporous carbon has a three-dimensional 3.4 nm-sized wormholelike mesoporous network with well-distributed 17.1 nm-sized particlelike mesopores. Such a bimodal mesoporous carbon has a high Brunauer-Emmett-Teller surface area (782 m² g⁻¹) and a very large total pore volume (3.0 cm³ g⁻¹).