The anodic behaviour of Ebonex® in oxalic acid solutions

A study of the oxidation of aqueous solutions of oxalic acid in various supporting electrolytes, at an Ebonex^® anode is reported. From data obtained by cyclic voltammetry, linear sweep voltammetry, chronopotentiometry, controlled potential coulometry and gas chramatography it has been shown that oxalic acid oxidation at an Ebonex^® anode, does not proceed, to any significant extent. Data collected using different electrolytes showed that sulphuric acid supported higher current densities at similar electrode potentials. Ebonex^® is essentially a selective oxygen evolver and is thus a suitable anode for the electroreduction of oxalic acid to glyoxylic acid in an undivided cell. The behaviour of a platinized titanium anode is also reported and this material has similar electrochemical characteristics to Ebonex^® in aqueous oxalic acid solutions.     

Using photoelectrochemical measurements for distinguishing between direct and indirect hole transfer processes on anatase: Case of oxalic acid

Photocurrents collected from an interface between polycrystalline anatase and an aqueous solution of oxalic acid were measured as a function of oxalic acid concentration and photon flux at 365 nm. According to a kinetic model previously developed, such data can be used as a diagnostic tool for distinguishing between direct oxidation involving valence band holes and an indirect process, involving (surface bound) OH radicals. In the case of oxalic acid studied here, from the linear relation between initial slopes of photocurrent versus concentration and photon flux, a direct process is indicated.     

Modification of Pt nanoelectrodes dispersed on carbon support using irreversible adsorption of Bi to enhance formic acid oxidation

In this work, formic acid oxidation on Pt nanoelectrodes modified by irreversible adsorption of Bi is presented. The coverage of Bi, as measured by voltammetry and X-ray photoelectron spectroscopy, was controlled from 0.05 to 0.25. Chronoamperometric measurement of the catalytic activities of the Bi-modified Pt nanoelectrodes revealed that the catalytic enhancement depended on oxidation potential and Bi coverage: elemental Bi in the potential range from −0.1 V to 0.6 V enhanced formic acid oxidation by factor of 4, while partially oxidized Bi in the potential range from 0.3 V to 0.7 V increased by factor of 8. The enhancement in the latter potential range was effective only when the Bi coverage was more than 0.18. Single cell performance of the Pt nanoelectrodes modified by Bi increased by factor of 2-3, depending on operation conditions such as formic acid concentration, temperature, and humidity in the feeding gas into cathode. When the Bi coverage was more than 0.18, the single cell performances were nearly identical. Based on measurement of adsorbed CO and catalytic poison from formic acid, an oxidation path not involving catalytic poison in the potential range from 0.5 V to 0.7 V is discussed in detail.     

在1-乙基咪唑三氟乙酸盐离子液体中合成的聚吡咯对草酸的电催化氧化

The electrochemical oxidation of oxalic acid is important in environmental engineering. In this paper, polypyrrole （PPy） was prepared galvanostatically in an ionic liquid 1-ethylimidazolium trifluoroacetate （HEImTfa） and its electro-catalysis function for the electrochemical oxidation of oxalic acid was investigated by using cyclic voltammetry. The results showed that the electro-catalytic activity of PPy prepared in HEImTfa （PPy-HEImTfa） was greatly improved as compared with that prepared in conventional H2SO4 aqueous solution. Therefore, the use of HEImTfa as growth electrolyte and solvent for electro-polymerization of pyrrole resulted in an electrochemically catalytic film of PPy for the electrooxidation of oxalic acid.     

The effect of surface treatment on oxidation of oxalic acid at nanocrystalline diamond films

The surface investigation of undoped and boron doped nanocrystalline diamond (NCD/BDND) films associated to their electrochemical behavior of oxalic acid after four pre-treatments was studied. The films were produced using Hot Filament CVD technique on Si substrate with a gas mixture of CH₄/H₂/Ar. Surface pre-treatments were carried out to analyze the surface chemical changes induced by hydrogen and oxygen plasma and as well as cathodic and anodic treatments performed in 0.1 mol L^? 1 HClO₄. The films wetting analyzed by contact angle presented a strong dependence of their surface before and after each treatment was also confirmed by the electrochemical response from cyclic voltammograms. Independent of the surface pre-treatments, all the electrodes exhibited response for oxalic acid oxidation, but the electrode submitted to hydrogen plasma presented the lowest starting oxidation potential and the highest current density. Nonetheless, the BDND electrode presented higher oxidation current than that for NCD electrodes, after all pre-treatments studied. The use of square wave voltammetry with BDND electrode treated by hydrogen plasma for the analytical determination of oxalic acid is described. The detection limits of 0.75 μmol was obtained from the linear relationship between the peak currents of voltammograms as a function of the oxalic acid concentrations.     

Memory effect-enhanced catalytic ozonation of aqueous phenol and oxalic acid over supported Cu catalysts derived from hydrotalcite

Mg/Al supported metal (Fe, Co, Ni and Cu) oxide catalysts were prepared by co-precipitation of hydrotalcite-like clay materials as precursors, calcined, and used for the ozonation reaction of phenol and oxalic acid. The reaction was carried out using the catalyst and aqueous solution of phenol or oxalic acid in an O₃/O₂ mixed gas-flow at 20 °C. In the ozonation of phenol, the combination of ozone and supported metal oxide catalysts was effective for the removal of total organic carbon (TOC). Also in the ozonation of oxalic acid as the main TOC component, Cu/Mg/Al catalysts showed the highest activity, followed by Ni/Mg/Al catalyst, while both Fe/Mg/Al and Co/Mg/Al catalysts were not active. Leaching of Cu and Ni, probably due to the chelation of metals by oxalic acid, was significantly observed at the beginning of the reaction. However the metal leaching disappeared at the end of the reaction possibly due to the entire consumption of oxalic acid during the reaction. The best result of oxalic acid mineralization was observed over Cu/Mg/Al catalyst calcined at 600 °C, on which least leaching of the metal was detected. Moreover, a “memory effect” of hydrotalcite accelerated the mineralization of oxalic acid over the Cu/Mg/Al catalyst; oxalate anions were captured and decomposed in the reconstituted hydrotalcite interlayer space on the surface of the Cu/Mg/Al catalyst, resulting in a remarkable enhancement in the catalytic activity of the ozonation.     

Preparation of high purity carbon nanospheres by the chemical reaction of calcium carbide and oxalic acid

The chemical reaction between calcium carbide and oxalic acid has been used to produce high quality carbon nanospheres (CNSs) at the temperature as low as 65 °C without any catalysts. The synthesized CNSs have high purity (>95%), high carbon content (98%) and very uniform size (80-100 nm).     

Catalytic oxidation of maleic and oxalic acids under potential control of platinum catalysts

The oxidation of maleic and oxalic acids in diluted aqueous solutions and with platinum catalysts under potential control was studied with the purpose of defining the influence of potential on the catalytic activity. This control was achieved either by an external device or was spontaneously established in the presence of the reactants. The effect of the composition and of the pH was also investigated.

Oxalic acid can be oxidized in mild experimental conditions (T=333 K, P_O2≤1 bar) and at potential values of the catalyst comprised between 0.7<E<1.8 V/RHE with a maximum catalytic activity at 1.3 V/RHE. The catalytic oxidation of this compound under external control of catalyst potential occurs following the same mechanism as the electrocatalytic oxidation. Oxalic acid is weakly adsorbed and its oxidation is inhibited by strongly adsorbed anions.

Maleic acid needs more severe experimental condition to be oxidized (T=383 K, P_O2=1–5 bars) and catalyst potentials in the range of 0.4≤E<1.1 V/RHE. In the same potential range an active adsorbed species was detected.

The catalytic oxidation of maleic acid follows the same mechanism with and without external control of catalyst potential which should be different from the mechanism of the electrocatalytic oxidation.     

Diesel fuel desulfurization with hydrogen peroxide promoted by formic acid and catalyzed by activated carbon

Desulfurization of diesel fuels with hydrogen peroxide was studied using activated carbons as the catalysts. Adsorption and catalytic properties of activated carbons for dibenzothiophene (DBT) were investigated. The higher the adsorption capacity of the carbons is, the better the catalytic performance in the oxidation of DBT is. The effect of aqueous pH on the catalytic activities of the activated carbons was also investigated. Oxidation of DBT is enhanced when the aqueous pH is less than 2, and addition of formic acid can promote the oxidation. The effect of carbon surface chemistry on DBT adsorption and catalytic activity was also investigated. Adsorption of DBT shows a strong dependence on carboxylic group content. The oxidative removal of DBT increases as the surface carbonyl group content increases. Oxidative desulfurization of a commercial diesel fuel (sulfur content, 800 wt. ppm) with hydrogen peroxide was investigated in the presence of activated carbon and formic acid. Much lower residual sulfur content (142 wt. ppm) was found in the oxidized oil after the oxidation by using the hydrogen peroxide-activated carbon-formic acid system, compared with a hydrogen peroxide-formic acid system. The resulting oil contained 16 wt. ppm of sulfur after activated carbon adsorption without any negative effects in the fuel quality, and 98% of sulfur could be removed from the diesel oil with 96.5% of oil recovery. Activated carbon has high catalytic activity and can be repeatedly used following simple water washing, with little change in catalytic performance after three regeneration cycles.     

Development of highly sensitive non-enzymatic sensor for the selective determination of glucose and fabrication of a working model

Copper oxide (CuO)/copper oxalate (CuOx) modified non-enzymatic electrochemical sensor for the detection of glucose in alkaline medium was fabricated by electrochemical anodisation of copper electrodes in potassium oxalate solution. Morphology of the modified copper electrode was studied by Scanning Electron Microscopy (SEM) and its electrochemical behaviour by Cyclic Voltammetry (CV) and Electrochemical Impedance Spectroscopy (EIS). The formation of CuOx on the copper electrode was confirmed by the Infra-red Reflection Absorption Spectrum (IRRAS). The modified electrodes were found to be microporous and rough. Linear Sweep Voltammetry (LSV) and amperometry were adopted to investigate the direct electrocatalytic oxidation of glucose on CuO/CuOx modified electrode in alkaline medium which showed excellent catalytic activity. The best performance of the sensor was obtained at 0.7 V and in 0.1 M sodium hydroxide (NaOH). At this optimum potential, the sensor was highly selective to glucose in the presence of ascorbic acid (AA) and uric acid (UA) which are common interfering species in biological fluids. The sensitivity was found to be very high (1890 μA mM⁻¹ cm⁻²) with excellent linearity (R = 0.9999) up to 15 mM having a low detection limit of 0.05 μM (S/N = 3). The modified electrode was tested for glucose level in blood serum. Based on the optimised conditions, a working model of the sensor was made and successfully tested for glucose.     

Carbon monoxide oxidation and nitrous oxide reduction on Rh/Pt(1 1 1) electrodes

Rhodium adlayers on Pt(1 1 1) substrates have been prepared by electrodeposition from dilute Rh³⁺ acidic solutions. Resulting deposition rates are lower than 0.03 ML min⁻¹. Pseudomorphic growth of the first monolayer has been confirmed by scanning tunneling microscopy (STM) as well as the formation of small compact islands in the submonolayer range. Carbon monoxide oxidation and nitrous oxide reduction have been studied on Rh/Pt(1 1 1) electrodes. The oxidation of carbon monoxide is catalyzed by the presence of very low coverages of rhodium as demonstrated by the negative shift of the CO oxidation profile. Results are compatible with a bifunctional mechanism for catalysis including CO diffusion in the Pt domains toward the edges of the islands (splitting of the voltammetric oxidation profile). The reduction of nitrous oxide occurs at different potential and with different rates on Pt domains, at the center of the Rh islands and at their edges, being the latter sites especially active. In any case, the adsorptive and catalytic activity of the adlayers differ from those of the bulk Pt(1 1 1) and Rh(1 1 1) electrodes. The existence of strain in the film together with a diminution in the coordination number for adatoms at the edges of the islands are considered to be at the origin of the observed behavior.     

Structural features of self-organized nanopore arrays formed by anodization of aluminum in oxalic acid at relatively high temperatures

Anodic aluminum oxide (AAO) membranes with a highly ordered nanopore arrangement typically serve as ideal templates for the formation of various nanostructured materials. A typical procedure of the template preparation is based on a two-step self-organized anodization of aluminum carried out at the temperature of about 1-3 °C. In the current study, AAO templates were fabricated in 0.3 M oxalic acid under the anodizing potential range of 30-65 V at a relatively high electrolyte temperature ranging from 20 to 30 °C. Due to a high rate of porous oxide growth, about 5-10-fold higher than in low-temperature anodizing, the process of the template fabrication can be shorten significantly. Similarly to the low-temperature anodization, the best hexagonal pore arrangement is observed for samples anodized at 40 V. With a prolonged duration of the first anodizing step the order degree of triangular nanoporous lattice, observed after the second anodization, improves considerably. The effects of the anodizing potential and the process duration on the structural features of porous anodic alumina such as: pore diameter (D_p), interpore distance (D_c), porosity (P), pore density (n) and anodizing ratio (B_U) were investigated in details at various temperatures. The obtained results were compared with theoretical predictions and data reported in the literature.     

Determination of uric acid in the presence of ascorbic acid with hexacyanoferrate lanthanum film modified electrode

A glassy carbon electrode modified with LaHCF was constructed and was characterized by cyclic voltammetry (CV) and electrochemical impedance spectrum (EIS). The resulting LaHCF modified glassy carbon electrode had a good catalytic character on uric acid (UA) and was used to detect uric acid and ascorbic acid (AA) simultaneously. This modified electrode exhibits potent and persistent electron-mediating behavior followed by well-separated oxidation peaks towards UA and AA with activation overpotential. For UA and AA in mixture, one can well separate from the other with a potential large enough to allow the determination of one in presence of the other. The DPV peak currents obtained increased linearly on the UA in the range of 2.0 × 10⁻⁷ to 1.0 × 10⁻⁴ mol/L with the detection limit (signal-to-noise ratio was 3) for UA 1.0 × 10⁻⁷ mol/L. The proposed method showed excellent selectivity and stability, and the determination of UA and AA simultaneously in urine was satisfactory.     

Development of an electrochemical ascorbic acid sensor based on the incorporation of a ferricyanide mediator with a polyelectrolyte-calcium carbonate microsphere

A novel electro-active material was successfully prepared with Fe(CN)₆³⁻ ions loaded by electrostatic interaction onto the layer of poly(allylamine) hydrochloride (PAH), which was first assembled on prepared poly(sodium 4-styrenesulfonate) (PSS)-doped porous calcium carbonate (CaCO₃) microspheres. Further, an electrochemical sensor for use in ascorbic acid (AA) detection was constructed with the use of the above electro-active materials embedded into a chitosan (CS) sol-gel matrix as an electron mediator. The electrocatalytic oxidation of AA by ferricyanide was observed at the potential of 0.27 V, which was negative-shifted compared with that by direct electrochemical oxidation of AA on a glassy carbon electrode. The experimental parameters, including the pH value of testing solution and the applied potential for detection of AA, were optimized. The current electrochemical sensor not only exhibited a good reproducibility and storage stability, but also showed a fast amperometric response to AA in a linear range (1.0 × 10⁻⁶ to 2.143 × 10⁻³ M), a low detection limit (7.0 × 10⁻⁷ M), a fast response time (<6 s), and a high sensitivity (−4.5127 μA mM⁻¹).     

Mechanistic aspects of oxalic acid oxidation by photocatalysis and ozonation

Oxalic acid has been oxidised in acidic aqueous solutions (pH 3) using photocatalysis and ozonation alone or coupled. The simultaneous presence of ozone, titanium dioxide and near UV irradiation increases the oxidation rate of oxalic acid to values greater than those deriving from the single contributions of photocatalysis and ozonation. In particular in the present paper ozonation alone, heterogeneous photocatalysis and also combined ozonation with heterogeneous photocatalysis have been used for the oxidation of oxalic acid at acidic pH in the presence of TiO₂ Degussa P25. A likely mechanism, able to explain both the homogeneous and heterogeneous processes, is discussed.     

Preparation and electrochemical characterization of low-index rhodium single crystal electrodes in sulfuric acid

The electrochemical properties of low-index phase Rh(1 1 1), Rh(1 1 0) and Rh(1 0 0) single crystal bead electrodes, prepared by a novel technique combining electron beam heating with inductive annealing in a controlled atmosphere, have been characterized in 0.1 M H₂SO₄ by cyclic voltammetry and chronoamperometry. Hydrogen and sulfate adsorption as well as surface oxidation depend strongly on the crystallographic orientation of the surface. The potentials of zero total charge (E_pztc) of all three Rh electrodes in 0.1 M H₂SO₄ were determined by the combination of charge displacement and voltammetric experiments. The charge balance reveals unambiguousely that the (√3 × √7) adlayer on Rh(1 1 1) is composed of specifically adsorbed sulfate ions eventually coadsorbed with water molecules. Hydrogen-sulfate coadsorbed with hydronium ions could be excluded. The kinetics of sulfate ion desorption followed by the adsorption of hydrogen at less positive potentials could be represented by a nucleation and growth mechanism coupled with a parallel first order process.The electro-oxidation of irreversibly adsorbed carbon monoxide monolayers was also investigated and revealed distinct structure sensitivity. The reaction pathway on all three low-index phases of Rh proceeds according to a Langmuir-Hinshelwood mechanism and is controlled by nucleation of OH_ads at steps and other defect sites followed by a complex growth process on terrace sites. The low surface mobility of CO_ads leads to a slow and incomplete CO monolayer electro-oxidation on Rh(1 1 1). The high density of step sites on Rh(1 1 0) and the reversible formation of oxygenated species on Rh(1 0 0) at rather low potentials significantly enhance the electro-oxidation activity leading to the following reactivity sequence: Rh(1 1 1) ? Rh(1 1 0) ∼ Rh(1 0 0). The shape of the experimental transients and attempts to model them demonstrate the occurrence of at least two processes occurring in parallel. The long-term response represents clearly a process involving a slow surface-diffusion step.     

Simultaneous detection of ascorbic acid, uric acid and homovanillic acid at copper modified electrode

The copper was deposited on glassy carbon (GC) and indium tin oxide (ITO) electrodes by electrochemical method. The copper structures on electrode were characterized by atomic force microscope, X-ray diffractometeric pattern and differential pulse voltammetric studies. Optimal conditions for uniform growth of copper structures on the electrode were established. Voltammetric sensor was fabricated using the copper deposited GC electrode for the simultaneous detection and determination of uric acid (UA) and homovanillic acid (HVA) in the presence of excess concentrations of ascorbic acid (AA). The voltammetric signals due to AA and UA oxidation were well separated with a potential difference of 400 mV and AA did not interfere with the measurement of UA and HVA at the GC/Cu electrode. Linear calibration curves were obtained in the concentration range 1-40 μM for AA and 20-50 μM for UA at physiological pH and a detection limit of 10 nM of UA in the presence of 10-fold excess concentrations of AA was achieved. The simultaneous detection of submicromolar concentrations of AA, UA and HVA was achieved at the GC/Cu electrode. The practical utility of the present GC/Cu modified electrode was demonstrated by measuring the AA content in Vitamin C tablet, UA content in human urine and blood serum samples with satisfactory results.     

Influence of underpotentially deposited Sb onto Pt anode surface on the performance of direct formic acid fuel cells

We first reported on electrocatalytic activity and stability of antimony modified platinum (PtSb_upd) as anode catalyst in direct formic acid fuel cells. Sb modified Pt (PtSb_upd) was prepared by underpotential deposition technique applying constant potential of 0.2 V (vs. Ag/AgCl, 3M KCl) and its modified surface was characterized by XRD and XPS. The electrocatalytic oxidation activity by cyclic voltammograms and the single cell power performance of Sb modified Pt were measured and their results were compared with the data of unmodified Pt electrode. PtSb_upd induced lower onset potential of formic acid oxidation and twice higher power density of 250 mW cm⁻² was observed.     

Selective determination of L-dopa in the presence of uric acid and ascorbic acid at a gold nanoparticle self-assembled carbon nanotube-modified pyrolytic graphite electrode

Gold nanoparticle-functionalized carbon nanotubes (AuNP-CNT) have been prepared by a novel self-assembly method. The new material has been characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD) and utilized for constructing AuNP-CNT-modified pyrolytic graphite electrode (AuNP-CNT/PGE) to investigate the electrochemical behavior of L-dopa in neutral phosphate buffer solution. Compared to bare PG electrode, AuNP-CNT/PGE shows novel properties towards the electrochemical redox of L-dopa in phosphate buffer solution at pH 7.0. The oxidation potential of L-dopa shows a significant decrease at the AuNP-CNT/PGE. The oxidation current of L-dopa is about 5-fold higher than that of the unmodified PGE. Using differential pulse voltammetry (DPV) method, the oxidation current is well linear with L-dopa concentration in the range of 0.1-150 μM, with a detection limit of about 50 nM (S/N = 3). The proposed electrode can also effectively avoid the interference of ascorbic acid and uric acid, making the proposed sensor suitable for the accurate determination of L-dopa in both pharmaceutical preparations and human body fluids.     

Electrochemical removal of gallic acid from aqueous solutions

Removal of gallic acid from aqueous solutions of different concentrations has been performed by electroprecipitation using a sacrificial iron anode, by indirect electrochemical oxidation carried out via electro- and photoelectro-Fenton processes using an oxygen-diffusion cathode, and by a combination of the first two methods (peroxicoagulation process). In all cases, chromatographic analyses have shown a very quick disappearance of gallic acid and its aromatic by-products within 30-90 min of electrolysis, depending on the method. A pseudo first-order kinetic decay of gallic acid was always observed under galvanostatic conditions. A decay of TOC and COD close to 90 and 95% is observed with electroprecipitation and peroxicoagulation processes, respectively, after electrolysis time lower than 2 h. The specific charge utilised in these two processes was about half of that theoretically required for the complete direct oxidation process (mineralisation). During electrolyses some carboxylic acids have been detected as main intermediates, which completely disappear at the end of the process, except oxalic acid in the case of electro-Fenton method.