Electrochemical oxidation of borohydride on platinum electrodes: The influence of thiourea in direct fuel cells

The electrochemical behaviour of sodium borohydride on a platinum electrode in the absence and presence of thiourea (TU) was investigated by cyclic voltammetry. In the absence of thiourea, several overlapping peaks associated with the hydrolysis of BH₄⁻ appear in the domain of hydrogen oxidation, i.e., in the potential range of −1.25 to −0.50 V versus Ag/AgCl. As a consequence of secondary reactions, the borohydride oxidation in 3 M NaOH solution shows a four to six-electron process, according to its concentration, in direct fuel cells. A conveyable TU/NaBH₄ concentration ratio of 0.6 inhibits the delivery of hydrogen simultaneously with catalytic hydrolysis of BH₄⁻. Thus, the coulombic efficiency in direct fuel cell discharge was increased showing an about eight-electron process for the oxidation of BH₄⁻.     

Cyclic voltammetry investigation of borohydride oxidation at a gold electrode

Sodium borohydride (NaBH₄) is receiving increasing attention during the last decade regarding its possible application in energy systems. NaBH₄ has the dual potential of generating hydrogen on demand or being directly oxidised in a direct borohydride fuel cell (DBFC). Progress on DBFCs relies on the development of systematic studies to allow a more comprehensive characterisation of the borohydride (BH₄⁻) oxidation process. In this paper, cyclic voltammetry (CV) is applied to study systematically the BH₄⁻ electrooxidation on a gold (Au) disc macroelectrode in 2 mol l⁻¹ NaOH solutions. Voltammograms are obtained for various NaBH₄ concentrations [0.03-0.12 mol l⁻¹], working temperatures [25-65 °C], and potential scan rates [0.02-20 V s⁻¹], over a wide potential range [−1.0-0.8 V vs. SCE]. Modelling of CV data indicates that BH₄⁻ oxidation on Au electrode follows a first irreversible electrochemical pathway via the direct BH₄⁻ oxidation reaction, involving nearly 8 mol of exchanged electrons per mole of BH₄⁻. A second pathway, at higher potentials, concerns a yet undetermined oxidation mechanism in the partially oxidised Au surface which, in a third pathway, is reactivated, allowing an electrochemical-adsorption mechanism to take place. Relevant parameters such as transfer coefficient, kinetic rate constant, standard rate constant, charge transfer activation energy, and number of exchanged electrons are estimated. The BH₄⁻ oxidation reaction on Au is found to be first order with respect to BH₄⁻.     

First principles mechanistic study of borohydride oxidation over the Pt(1 1 1) surface

The mechanism of borohydride oxidation and the competing hydrolysis reaction are examined over Pt(1 1 1) using density functional theory (DFT) methods. Adsorption of BH₄⁻ over Au(1 1 1) and Pt(1 1 1) is examined. Adsorption over Pt(1 1 1) is dissociative and extremely exothermic at potentials of interest, leading to a high surface coverage of H^* for which gaseous hydrogen evolution is competitive with oxidation. Elementary surface reactions oxidizing B-containing intermediates are favorable over Pt(1 1 1) at −0.85 V (SHE), consistent with experimental voltammetry results in the literature. The energetics of the initial adsorption step dictate the activity limitation of gold anodes and the selectivity limitation of platinum electrodes. This adsorption energy can be rapidly calculated with DFT methods, enabling screening of pure metals, alloys, poisons, and promoters to optimize borohydride oxidation catalyst design.     

Kinetics of sodium borohydride direct oxidation and oxygen reduction in sodium hydroxide electrolyte: Part I. BH4 electro-oxidation on Au and Ag catalysts

The direct oxidation of sodium borohydride in concentrated sodium hydroxide medium has been studied by cyclic and linear voltammetry, chronoamperometry and chronopotentiometry for silver and gold electrocatalysts, either bulk and polycrystalline or nanodispersed over high area carbon blacks. Gold and silver yield rather complete utilisation of the reducer: around 7.5 electrons are delivered on these materials, versus 4 at the most for platinum as a result of the BH₄⁻ non-negligible hydrolysis taking place on this latter material. The kinetic parameters for the direct borohydride oxidation are better for gold than for silver. A strong influence of the ratio of sodium hydroxide versus sodium borohydride is found: whereas the theoretical stoichiometry does forecast that eight hydroxide ions are needed for each borohydride ion, our experimental results prove that a larger excess hydroxide ion is necessary in quasi-steady state conditions. When the above-mentioned ratio is unity (1 M NaOH and 1 M NaBH₄), the tetrahydroborate ions direct oxidation is limited by the hydroxide concentration, and their hydrolysis is no longer negligible. The hydrolysis products are probably BH₃OH⁻ ions, for which gold displays a rather good oxidation activity. Additionally, silver, which is a weak BH₄⁻ oxidation electrocatalyst, exhibits the best activity of all the studied materials towards the BH₃OH⁻ direct oxidation.Finally, carbon-supported gold nanoparticles seem promising as anode material to be used in direct borohydride fuel cells.     

CO tolerance and catalytic activity of Pt/Sn/SnO2 nanowires loaded on a carbon paper

Electrochemical activities and structural features of Pt/Sn catalysts supported by hydrogen-reduced SnO₂ nanowires (SnO₂NW) are studied, using cyclic voltammetry, CO stripping voltammetry, scanning electron microscopy, and X-ray diffraction analysis. The SnO₂NW supports have been grown on a carbon paper which is commercially available for gas diffusion purposes. Partial reduction of SnO₂NW raises the CO tolerance of the Pt/Sn catalyst considerably. The zero-valence tin plays a significant role in lowering the oxidation potential of CO_ads. For a carbon paper electrode loaded with 0.1 mg cm⁻² Pt and 0.4 mg cm⁻² SnO₂NW, a conversion of 54% SnO₂NW into Sn metal (0.17 mg cm⁻²) initiates the CO_ads oxidation reaction at 0.08 V (vs. Ag/AgCl), shifts the peak position by 0.21 V, and maximizes the CO tolerance. Further reduction damages the support structure, reduces the surface area, and deteriorates the catalytic activity. The presence of Sn metal enhances the activities of both methanol and ethanol oxidation, with a more pronounced effect on the oxidation current of ethanol whose optimal value is analogous to those of PtSn/C catalysts reported in literature. In comparison with a commercial PtRu/C catalyst, the optimal Pt/Sn/SnO₂NW/CP exhibits a somewhat inferior activity toward methanol, and a superior activity toward ethanol oxidation.     

Surface-enhanced IR spectroscopy investigation on the electro-oxidation of CO adlayer at a polycrystalline Pt film electrode in Cl-containing HClO4

The electro-oxidation of CO adlayer on Pt electrode in Cl⁻-containing 0.1 M HClO₄ has been investigated with in situ attenuated-total-reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS). Two potentials were selected for predosing CO on the Pt electrode: one is in the H-UPD region, i.e., 0.1 V (vs. RHE) and the other is in the double-layer region, i.e., 0.45 V (vs. RHE). The broadening of the prewave and the main peak for the CO oxidation is observed, in addition to the positively shifted oxidation potentials. The spectroelectrochemical data suggest the specific adsorption of Cl⁻ starts at a potential as negative as 0.1 V which may compete with the adsorption of OH at CO-unoccupied sites (including but not limited to defect sites) and/or hinder the diffusion of CO to OH adsorption sites on Pt electrode, slowing down the CO oxidation. This competitive Cl⁻ adsorption at lower potentials disrupts the interfacial free H₂O structure on the top of CO adlayer, signaled by a reduced OH stretching band intensity.     

Highly dispersed platinum nanoparticles on carbon nanocoils and their electrocatalytic performance for fuel cell reactions

Highly graphitic carbon nanocoils (GCNC) were synthesized through the catalytic graphitization of carbon microspheres obtained by the hydrothermal carbonization of different saccharides (sucrose, glucose and starch) and were used as a support for Pt nanoparticles. The Pt nanoparticles were deposited by means of a polymer mediated-polyol method. The Pt catalysts were characterized both physically (XRD, TEM, HRTEM and XPS) and electrochemically (electrooxidation of methanol in an acid medium). The electrocatalysts thus prepared show a high dispersion of Pt nanoparticles, with diameters in the 3.0-3.3 nm range and a very narrow particle size distribution. These catalytic systems possess high electroactive Pt surface areas (up to 85 m² g⁻¹ Pt) and they exhibit large catalytic activities towards methanol electrooxidation (up to 201 A g⁻¹ Pt). Moreover, they have a high resistance against oxidation, which is considerably greater than that of the Pt/Vulcan system.     

Influence of bismuth on the structure and activity of Pt and Pd nanocatalysts for the direct electrooxidation of NaBH4

In the past few years, borohydrides have gathered a lot of attention as an energy carrier for fuel cell application. Numerous investigations on both hydrogen generation and direct oxidation of NaBH₄ have been published. Nonetheless, in our knowledge, only a few catalysts are capable to completely perform the direct oxidation of NaBH₄ at low potentials without hydrogen evolution.In this work, carbon supported Pd_1−xBi_x/C and Pt_1−xBi_x/C nanocatalysts were synthesized by a “water in oil” microemulsion method. The influence of surface modifications of Pt and Pd by Bi on the electrooxidation of sodium borohydride in alkaline media was evaluated. Physical and electrochemical methods were applied to characterize the structure and surface of the synthesized catalysts.It was verified that bismuth is present at the surface of the bimetallic catalysts and that hydrogen adsorption/desorption reactions are strongly limited on Pt and Pd surfaces with high bismuth coverage. Although the onset potential for NaBH₄ oxidation on Pd_xBi_1−x/C catalysts is ca. 0.2 V higher than that for Pd/C, the presence of bismuth on palladium surface influences the reaction mechanism, limiting hydrogen evolution and oxidation in the case of Pd_0.8Bi_0.2 catalyst. On Pt_0.9Bi_0.1 catalyst the onset potential remains unchanged comparing to Pt/C and negligible hydrogen evolution was observed in the whole potential range where the catalyst is active. The number of exchanged electrons was calculated using the Koutecky-Levich equation and it was found that for Pt_0.9Bi_0.1 catalyst, ca. 8 electrons are exchanged per BH₄⁻ ion at low potentials. The presented results are remarkable evidencing that NaBH₄ can be directly oxidized at low potentials with high energy efficiency.     

Direct oxidation of sodium borohydride on Pt, Ag and alloyed Pt–Ag electrodes in basic media. Part I: Bulk electrodes

We studied the borohydride oxidation reaction (BOR) by voltammetry for BH₄⁻ concentrations between 10⁻³ M and 0.1 M NaBH₄ in 0.1–1 M NaOH for bulk polycrystalline Pt, Ag and alloyed Pt–Ag electrocatalysts. In order to compare the different electrocatalysts, we measured the kinetic parameters and the number of electrons exchanged (faradic efficiency). BOR on bulk Pt is more efficient when the concentration of NaBH₄ increases (3e⁻ in 1 mM and 6e⁻ in 10 mM BH₄⁻/0.1 M NaOH). BOR on Pt can occur both in a direct pathway and in an indirect pathway including hydrogen generation via heterogeneous hydrolysis of BH₄⁻ and subsequent oxidation of its by-products (e.g. BH₃OH⁻ and H₂). BOR on Ag strongly depends on the pH: improved faradic efficiency is monitored for high pH (2e⁻ at pH 12.6 and 6e⁻ at pH 13.9 at 25 °C). The BOR kinetics is faster for Pt than for Ag (i_Pt=0.02 A cm⁻², i_Ag=1.4 10⁻⁷ A cm⁻² at E=−0.65 V vs. NHE in 1 mM NaBH₄/0.1 M NaOH, 25 °C) both as a result from Pt high activity regarding the BH₄⁻ heterogeneous hydrolysis and subsequent HOR, above −0.83 V vs. NHE and following direct oxidation of BH₄⁻ or BH₃OH⁻ below −0.83 V vs. NHE. Both Pt–Ag bulk alloys show unique behaviour: the number of electrons exchanged is rather high whatever the BH₄⁻ concentration and pH, while the kinetic parameters are quite similar to that of platinum, showing possible synergistic alloying effect.     

Porous Carbon as Anode Catalyst Support to Improve Borohydride Utilization in a Direct Borohydride Fuel Cell

Our study explores the use of porous carbon as anode catalyst support to improve borohydride utilization in a direct borohydride fuel cell. Pt catalysts supported by carbon aerogel (CA) and macroporous carbon (MPC) are synthesized by template method. The pores in porous carbon materials catch hydrogen bubbles to regulate the contact of anolyte with catalytic sites, and this leads to the depression of hydrogen evolution during BH₄⁻ electrooxidation. However, the hydrogen bubbles in the pores simultaneously deteriorate charge carrier transport and thus increase anode polarization. The CA‐supported Pt catalyst improves the coulombic efficiency of BH₄⁻ electrooxidation. However, the MPC‐supported Pt catalyst performed better than the CA‐supported Pt catalyst. MPC also has a good pore distribution, which improves the coulombic efficiency of BH₄⁻ electrooxidation without decreasing anode performance.     

From soil to lab: Utilization of clays as catalyst supports in hydrogen generation from sodium borohydride fuel

The stabilized aqueous solution of sodium borohydride NaBH₄ is a promising hydrogen fuel but the stored hydrogen has to be released with the help of a catalyst through hydrolysis. In the present study, we developed Co- and clay-based supported catalysts. Three raw clays were taken from soil in Lebanon. Once purified and annealed, they were used as supports. Two of them, mainly composed of kaolinite and illite respectively, showed to be promising owing to their attractive specific surface areas (58.0 and 67.1 m² g⁻¹) as well as the high reactivity of the corresponding 15 wt.% Co catalysts (i.e. NaBH₄ conversions of 100% and hydrogen generation rates up to ∼31 L(H₂) min⁻¹ g⁻¹(Co)). A kinetic study was also carried out. The main results are reported and discussed herein.     

Electrooxidation of aliphatic alcohols on palladium oxide catalyst prepared by pulsed electrodeposition technique

Palladium film can be deposited on gold polycrystalline electrodes, from a deoxygenated alkaline solution containing 50 mM NaOH plus 0.5 mM K₂Pd(CN)₄. A multipulse sequence of potentials of equal amplitude and duration was used for the palladium deposition process. In particular, an optimized waveform of potentials of E₁ = 1.0 V vs. SCE and E₂ = −1.0 V vs. SCE for the relevant pulse duration of t₁ = 0.05 s and t₂ = 0.05 s, for 30 s, was used. Cyclic voltammetry and scanning electron microscopy (SEM) were employed to characterize the gold-palladium modified electrode (Au-Pd) towards the electrooxidation of aliphatic alcohols in alkaline solutions. The voltammetric study suggests that the kinetics involved in the alcohol electrooxidation at the Pd-Au electrode are sensibly higher than those observed on the bare Pd and Au electrodes. In addition, the most interesting aspect of the electrooxidation of aliphatic alcohols at the Au-Pd electrode was that as the number of methylene groups on the homologous series of aliphatic alcohols increased, the molar response also increased. Under pulsed chronoamerometric conditions (PCC), using an optimized triple pulse waveform of potentials the modified electrode exhibits interesting catalytic currents without any apparent poisoning effects during the oxidation of aliphatic alcohols.     

Development of a sensor based on tetracyanoethylenide (LiTCNE)/poly-l-lysine (PLL) for dopamine determination

The catalytic oxidation of dopamine (DA) at a LiTCNE (lithium tetracyanoethylenide) film modified electrode is studied by electrochemical approaches. The immobilization of LiTCNE was performed by a polymer (poly-l-lysine) to prepare this modified electrode and its application for dopamine (DA) determination is described in detail. The modified electrode showed a high activity for the electrooxidation of dopamine (DA) at E_p = 0.20 V versus SCE. The modified electrode presented a wide linear response range for DA from 0.01 up to 10 μmol l⁻¹ by differential pulse voltammetry (DPV) with a detection limit of 0.5 nmol l⁻¹. The repeatability of the proposed sensor evaluated in term of relative standard deviation was 3.2% for n = 10. The sensor was applied for the determination of dopamine in pharmaceutical formulations and the average recovery for these samples was 101.9 (±0.1)%.     

Electrochemical oxidation of boron containing compounds on titanium carbide and its implications to direct fuel cells

Electrochemical oxidation of sodium borohydride (NaBH₄) and ammonia borane (NH₃BH₃) (AB) have been studied on titanium carbide electrode. The oxidation is followed by using cyclic voltammetry, chronoamperometry and polarization measurements. A fuel cell with TiC as anode and 40 wt% Pt/C as cathode is constructed and the polarization behaviour is studied with NaBH₄ as anodic fuel and hydrogen peroxide as catholyte. A maximum power density of 65 mW cm⁻² at a load current density of 83 mA cm⁻² is obtained at 343 K in the case of borhydride-based fuel cell and a value of 85 mW cm⁻² at 105 mA cm⁻² is obtained in the case of AB-based fuel cell at 353 K.     

Is carbon-supported Pt-WOx composite a CO-tolerant material?

Pt-WO_x/C composite materials elaborated via a two-step impregnation/electrochemical reduction method have been characterized and tested for the electrooxidation of CO/H₂ mixtures. TEM and EDS measurements revealed that WO_x covered imperfectly the C particles. Nanometer-sized or agglomerated Pt particles were found on the WO_x/C surface. XRD measurements revealed the absence of diffraction peaks characteristic of crystalline WO_x and could indicate that this material is amorphous. No evidence of alloying between the Pt and W was observed. A significant improvement toward the electrooxidation of a CO_ads monolayer was observed for the composite material compared to pure Pt/C electrocatalyst, which is evidenced by a new electrooxidation peak at 0.55 V versus RHE (v=0.02 V s−1). As the electrical charge below this electrooxidation peak is sweep rate dependant, it is probably associated to the electrooxidation of CO_ads on Pt sites at the interface with the WO_x/C support. The performance of the Pt-WO_x/C material for the electrooxidation of CO/H₂ mixtures was tested by polarization curves under steady-state conditions (0.001 V s⁻¹) or potentiostatic measurements under fuel cell relevant conditions and compared with that of commercial 20 wt% Pt/C and Pt-Ru/C materials.     

Mechanistic pathways during oxidation of cyanate on platinum single crystal faces

Adsorption and oxidation processes of cyanate (OCN⁻) were studied on polycrystalline platinum and Pt(1 0 0), Pt(1 1 0) and Pt(1 1 1) surfaces in alkaline solution (pH 9). On Pt(poly), Pt(1 0 0) and Pt(1 1 0), it has been found that cyanate chemisorbs dissociatively, with production of adsorbed CO. Oxidation of cyanate thus follows a pathway involving CO_ad on polycrystalline Pt and these single crystal faces. CO_ad has not been observed during oxidation of cyanate on Pt(1 1 1); thus another pathway, involving direct oxidation of OCN⁻, has been identified for cyanate oxidation on platinum surfaces.     

First insights into the borohydride oxidation reaction mechanism on gold by electrochemical impedance spectroscopy

Direct borohydride fuel cells (DBFC) exhibit some potential regarding the powering of small portable electronic devices, thanks to their high energy density as well as the facile and safe storage of borohydride salts. However, DBFC are hindered because (i) the borohydride oxidation reaction (BOR) is complex, (ii) its mechanism imperfectly determined yet and (iii) no practical electrocatalyst exhibits both fast BOR kinetics and high faradaic efficiency. In this context, we characterized the BOR mechanism for polycrystalline bulk gold (a classical model BOR electrocatalyst) in the rotating disk electrode (RDE) setup. Modeling cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) data, we propose a simplified reaction pathway, the theoretical behavior of which agrees with the experimental findings. This pathway includes at least a first irreversible electrochemical step (E) for BH₄⁻ oxidation, which competes with the electrochemical adsorption reaction (EAR) of OH⁻ anions at high potentials.     

Nucleation of Sn and Sn-Cu alloys on Pt during electrodeposition from Sn-citrate and Sn-Cu-citrate solutions

The initial stages of Sn and Sn-Cu electrodeposition from Sn-citrate and Sn-Cu-citrate solutions on Pt were studied using both current-controlled and potential-controlled electrochemical techniques. For both Sn-citrate and Sn-Cu-citrate solutions, when the current density is controlled to lower than 15 mA/cm², potentials remain almost constant which is appropriate to plate dense and uniform films. When the current density is controlled to between 25 and 35 mA/cm², potentials drop quickly initially, followed by a gradual increase to a constant value. When current density is controlled to higher than 50 mA/cm², potential oscillation happens, and significant hydrogen evolution prevents the formation of dense and continuous Sn and Sn-Cu films. A constant transition time constant indicates a diffusion-controlled process. The diffusion coefficient calculated from the Sand equation is about 3.8 × 10⁻⁶ cm²/s for the Sn-citrate solution and 4.1 × 10⁻⁶ cm²/s for the Sn-Cu-citrate solution. The morphology of both Sn and Sn-Cu deposits plated under different potentials was examined by atomic force microscopy (AFM) and the distribution of each element were analyzed using Auger imaging. Analysis of both the electrochemical results at −0.72, −1.1 and −1.5 V and AFM images for both Sn and Sn-Cu deposits at −1.1 and −1.5 V suggested progressive nucleation controlled by diffusion for both Sn and Sn-Cu electrodeposition. Tin reacted with Pt to form PtSn₄, and co-deposited with Cu to form Cu₆Sn₅ during nucleation, with more Sn forming at higher applied potentials.     

Electrochemical characterization of kinked Pt(7 5 1) surface in acidic media

Kinked Pt(7 5 1) surface was prepared and its electrochemical behaviors under different pretreatment conditions in acidic media were investigated systematically by using cyclic voltammetry. The results demonstrated that the upper limit of potential scanning and cooling atmospheres after the Pt(7 5 1) having been flame-annealed significantly influence the voltammetric behavior of Pt(7 5 1) electrode. The electric charge of hydrogen adsorption-desorption slightly increases with increasing the upper limit of potential scanning. Different cooling atmospheres give rise impacts to the surface structure of Pt(7 5 1) electrode, but hardly change the amount of hydrogen adsorption-desorption sites on the electrode. In addition, the so-called third oxidation peak appears near −0.08 V in H₂SO₄ media and −0.05 V in HClO₄ solution because of the presence of (1 1 0) terrace sites on this surface, and a plausible mechanism for the formation of this current peak is discussed. The results are of importance in understanding the electroadsorption properties of the kinked Pt(7 5 1) surface, as well as in further exploration of this kinked electrode in electrocatalysis.     

An enzyme-based microfluidic biofuel cell using vitamin K3-mediated glucose oxidation

Viamin K₃-modified poly-l-lysine (PLL-VK₃) was synthesized and used as the electron transfer mediator during catalytic oxidation of NADH by diaphorase (Dp) at the anode of biofuel cell. PLL-VK₃ and Dp were co-immobilized on an electrode and then coated with NAD⁺-dependent glucose dehydrogenase (GDH). The resulting enzymatic bilayer (abbreviated PLL-VK₃/Dp/GDH) catalyzed glucose oxidation. Addition of carbon black (Ketjenblack, KB) into the bilayer enlarged the effective surface area of the electrode and consequentially increased the catalytic activity. An oxidation current of ca. 2 mA cm⁻² was observed when the electrochemical cell contained a stirred 30 mM glucose, 1.0 mM NAD⁺, pH 7.0 phosphate-buffered electrolyte solution. The performance of glucose/O₂ biofuel cells, constructed as fluidic chips with controllable fuel flow and containing a KB/PLL-VK₃/Dp/GDH-coated anode and an Ag/AgCl or a polydimethylsiloxane-coated Pt cathode, were evaluated. The open circuit voltage of the cell with the PDMS-coated Pt cathode was 0.55 V and its maximum power density was 32 μW cm⁻² at 0.29 V when a pH 7.0-buffered fuel containing 5.0 mM glucose and 1.0 mM NAD⁺ was introduced into the cell at a flow rate of 1.0 mL min⁻¹. The cell's output increased as the flow rate increased. During 18 h of continuous operation of the cell with a load of 100 kΩ, the output current density declined by ca. 50%, probably due to swelling of the enzyme bilayer.