Boron-doped Diamond Electrode Research Articles

Effect of Pt-Ni deposition sequence on the bimetal-modified boron-doped diamond on catalytic performance for glucose oxidation in neutral media

• The PtNi modified boron-doped diamond were fabricated to detect glucose at neutral pH. • Electrodeposition sequences effect on electrocatalytic properties of Pt-Ni bimetals. • The PtNi biemetal prepared by co-deposition had the highest stability and sensitivity. The growing number of people with diabetes has gained extensive attention over the past decades, driving the need to develop sensitive glucose sensors to monitor glucose levels under physiological pH conditions. Bi-metal (Pt-Ni) modified boron-doped diamond (BDD) electrodes were reported to allow a continuous and stable response measurement of glucose under neutral pH conditions. Effects of the electrochemical deposition sequence on the morphology and electrocatalytic properties of the Pt-Ni bimetal were systematically investigated. Electrochemical tests showed that the Pt-Ni bimetal clusters prepared by the co-deposition (one step) method had higher stability and sensitivity for the glucose detection than those prepared by the two-step deposition method. The PtNi-BDD increased around 19% of the initial signal after 200 consecutive cyclic voltammetry cycles for 2400 s, while as a comparison, Ni/Pt-BDD and Pt-BDD increased 44% and 40% for 2400 s, respectively. In addition, the sensitivity of PtNi-BDD was obtained to be 110.4 μA cm −1 mm −1 in the range of 2–12 mM glucose concentration, around 6.1, 15.5, and 6.0 times higher than that of Pt/Ni-BDD, Ni/Pt-BDD, and single metal Pt, respectively.

Boron-doped diamond electrodes degrade short- and long-chain per- and polyfluorinated alkyl substances in real industrial wastewaters

Electrochemical oxidation (ECO) with boron-doped diamond (BDD) electrode of six legacy perfluoroalkyl substances (PFAS) present in semiconductor fabrication wastewaters was investigated in single-solutes, multi-solutes, and real wastewater matrices. ECO degradation kinetics decreased as carbon length decreased in single-solute systems. Because heterogeneous catalysis involves PFAS interacting at the electrode surface, the impact of PFAS in solution on altering the potential affinity for PFAS itself on the surface was quantified. The BDD electrode surface wettability, defined by the surface contact angle, increased with longer chain length and diminished with increasing PFAS concentration. PFASs with a sulfonated head group degraded 2–3x faster than their carboxylic counterparts. Industrial wastewaters can have high background organic concentrations and have a large pH range prior to discharge, offering different opportunities to treat for PFAS near the semiconductor manufacturing tool or prior to pH adjustment and discharge to sanitary sewers. Increasing pH (up to 12) decreased the evolution of reactive oxygen species on the electrode surface and therefore decreased removal kinetics compared to pH 3 and 7. The presence of surfactants (tetramethylammonium hydroxide [TMAH] and sodium dodecyl sulfonate [SDS]) in the wastewater significantly reduced the degradation efficiency of ECO. However, compared to single-solute PFAS systems, multi-solute solutions (mixture of 6 PFASs) had higher degradation rates during ECO. In a real wastewater (originated from RO concentrate), PFASs were efficiently removed in ~320 min reaction time. These results demonstrated the promise for ECO to treat PFAS contained in industrial manufacturing processes at both tool level and blended wastewater.

Electro-oxidation of Ni (II)-citrate complexes at BDD electrode and simultaneous recovery of metallic nickel by electrodeposition

The simultaneous electro-oxidation of Ni (II)-citrate and electrodeposition recovery of nickel metal were attempted in a combined electro-oxidation-electrodeposition reactor with a boron-doped diamond (BDD) anode and a polished titanium cathode. Effects of initial nickel citrate concentration, current density, initial pH, electrode spacing, electrolyte type, and initial electrolyte dosage on electrochemical performance were examined. The efficiencies of Ni (II)-citrate removal and nickel metal recovery were determined to be 100% and over 72%, respectively, under the optimized conditions (10 mA/cm2, pH 4.09, 80 mmol/L Na2SO4, initial Ni (II)-citrate concentration of 75 mg/L, electrode spacing of 1 cm, and 180 min of electrolysis). Energy consumption increased with increased current density, and the energy consumption was 0.032 kWh/L at a current density of 10 mA/cm2 (pH 6.58). The deposits at the cathode were characterized by scanning electron microscopy (SEM), energy-dispersive spectrometry (EDS), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). These characterization results indicated that the purity of metallic nickel in cathodic deposition was over 95%. The electrochemical system exhibited a prospective approach to oxidize metal complexes and recover metallic nickel.

Correlation of the role of boron concentration on the microstructure and electrochemical properties of diamond electrodes

In this article, a series of highly boron-doped diamond ([B] > 1021 cm−3) electrodes with small gradient variations in boron concentration were prepared by hot filament chemical vapor deposition (HF-CVD). Reactive blue 19 (RB-19) dye solution was used as a prototype wastewater. Interestingly, we found that the electrochemical properties (electrochemically active surface area and oxygen evolution potential) and the electrochemical degradation performance did not deteriorate linearly with increasing boron concentration. Specifically, the electrochemically active surface area of the electrode at [B]/[C] = 50,000 ppm was the highest of 9.366 cm2, the chromaticity removal rate of RB-19 dye wastewater reached 100% after 90 min, and the TOC removal rate reached 74.48% after 180 min with the lowest energy consumption.

Anodic Oxidation of Industrial Winery Wastewater Using Different Anodes

Winery wastewater represents the largest waste stream in the wine industry. This deals with the mineralization of the organic matter present in winery wastewater using anodic oxidation and two types of anodes—namely, a boron-doped diamond electrode (BDD) and two mixed metal oxides (MMO), one with the nominal composition Ti/Ru0.3Ti0.7O2 and the other with Ti/Ir0.45Ta0.55O2. To conduct the study, the variability of different quality parameters for winery wastewater from the Chilean industry was measured during eight months. A composite sample was treated using anodic oxidation without the addition of supporting electrolyte, and the experiments were conducted at the natural pH of the industrial wastewater. The results show that this effluent has a high content of organic matter (up to 3025 ± 19 mg/L of total organic carbon (TOC)), which depends on the time of the year and the level of wine production. With MMO electrodes, TOC decreased by 2.52% on average after 540 min, which may be attributed to the presence of intermediate species that could not be mineralized. However, when using a BDD electrode, 85% mineralization was achieved due to the higher generation of hydroxyl radicals. The electrolyzed sample contained oxamic, acetic, and propionic acid as well as different ions such as sulfate, chloride, nitrate, and phosphate. These ions can contribute to the formation of different species such as active species of chlorine, persulfate, and perphosphate, which can improve the oxidative power of the system.

Boron doped diamond electrode in analytical chemistry: methods of electrode surface activation (а short review)

The review is presents to the feature of the use of a boron doped diamond electrode (BDDE) in analytical chemistry. BDDE –one of the most modern material, which is widely used in analytical chemistry and bioanalytical chemistry, as well as for organic synthesis, cleaning of the environment from pollution, medicine, etc. BDDE is becoming increasingly popular for voltammetric determination of residual amounts organic substances in complex objects (medicines, biological fluids, food). Nowadays use rod (disk) and film BDDE. The advantage of film electrodes is their portability and compactness, which, in turn, allows them to be used for rapid analysis of biological fluids, when one drop of sample is enough for analysis. BDDE require surface cleaning and activation, as do other stationary electrodes. In this paper, the main attention is focused on the features of BDDE activation surface for use in the analysis. Activate the electrode surface potentiostatically, galvanostatically and under dynamic conditions. Аlso use different background electrolytes. BDDE is usually electrochemically treated in aqueous solutions, mostly the surface of the electrode is cleaned and activated at the same time. Proper pre-electrochemical treatment can be a valuable way to achieve improved analytical properties of the methods of voltammetric determination. In this case, оbtain a more intense analytical signal, a narrower, clearer peak and/or a useful shift of the peak potential, which increases the sensitivity and selectivity of the determination. For the most part, activation in a medium of sulfuric acid with a sufficiently high concentration of 0.5–1.0 M is chosen as the optimal one. The electrode is polarized alternately anode and cathode (regardless of the chemical structure of the analyte or the nature of the electrode process). However, the method of activation must always be chosen experimentally. The review contains more than 80 references on the features of BDDE surface activation, including monographs, reviews, articles and original works. Keywords: voltammetry, boron doped diamond electrode, activation surface polarization.

Influencing factors of venlafaxine degradation at boron-doped diamond anode

Degradation of the antidepressant venlafaxine by an effective electrocatalytic process, boron-doped diamond (BDD) electrode, was study. The BDD electrode was selected as the anode, and the degradation efficiency of venlafaxine under different influencing factors was systematically investigated. The preliminary grasp of the degradation law of venlafaxine by anodic electro-degradation using BDD electrode was obtained. The experimental results showed that the electrochemical oxidation technology using BDD anode can effectively degrade venlafaxine and remove total organic carbon (TOC) from the solution, complete venlafaxine degradation and TOC elimination could be achieved within 30 and 120 min of BDD oxidation process, respectively, and it has good stability and reusability. Increasing the electrolyte concentration (≤0.1 mol/L) and current density (≤100 mA/cm 2 ) within a certain range could accelerate the degradation of venlafaxine. HCO 3 – and PO 4 3− could inhibit the degradation efficiency of venlafaxine through of competing for free radicals. It is interesting that the presence of Cl − significantly promoted the degradation efficiency of venlafaxine. The results of this study suggest that the Electro-degradation treatment may provide a promising way to treat venlafaxine contaminated water.

Aqueous phase of thermo-catalytic reforming of sewage sludge – quantity, quality, and its electrooxidative treatment by a boron-doped diamond electrode

Pyrolysis is a promising conversion technology to produce biofuels from residues such as sewage sludge. In this study, the chemical composition and the amount of the resulting aqueous phase from the thermo-catalytic reforming process of sewage sludge at different process parameters are compared to those of non-catalytic fast pyrolysis processes from literature. Furthermore, electrooxidation using a boron-doped diamond (BDD) electrode was investigated as purification technology for the resulting aqueous phase. The results of this study show that the quantity of the aqueous phase strongly depends on the temperature of the thermo-catalytic reforming process and is presumably governed by the influence of secondary gas-carbonisate reactions like the water gas shift reaction. Higher reaction temperatures result in a reduced amount of the aqueous phase. The chemical composition of the aqueous phase of fast pyrolysis processes was comparable to that obtained at the thermo-catalytic reforming process. To reduce the chemical oxygen demand (COD) and the number of refractory substances to a level at which the aqueous phase can be discharged into a conventional wastewater treatment plant, electrooxidation experiments with the aqueous phase of the thermo-catalytic process were carried out using a BDD electrode. The treatment efficiency was investigated in galvanostatic operation varying the applied current density and the flow rate of the aqueous phase. A COD removal of 94.6% was achieved after 0.54kWh at an instantaneous current efficiency of 0.47 at a current density of 50 mA/cm2 and a flow rate of 3.7 L/min. This indicates that electrooxidation by a BDD electrode can be a promising purification technology for the aqueous phase from pyrolysis of sewage sludge. However, the high energy consumption of the process will need to be addressed in future studies to make the process economically feasible.

Insight into electrochemical degradation of Cartap (in Padan 95SP) by boron-doped diamond electrode: kinetic and effect of water matrices.

In this work, the kinetic electrochemical degradation of Cartap (CT) (in Padan 95 SP) at boron-doped diamond (BDD) electrode was investigated. This study indicated that the degradation of CT underwent both direct and indirect oxidations. Water matrices can either accelerate or inhibit the removal efficiency of CT: adding 15 mM Cl- improved kCT from 0.039 min-1 to 0.054 min-1 (increased by 38%), while kCT decreased by 61.5% and 64% when increasing the concentration of HCO3- and humic acid (HA) to 15 mM and 15 mg L-1, respectively. CT degradation was inhibited in the presence of methanol (MeOH) and tert-butanol (TBA) due to the scavenging effect of those chemicals toward reactive species. The contribution of reactive oxidants was calculated as: DET (direct electron transfer) accounted for 15%; •OH accounted for 61.5%; SO4•- accounted for 12.8%; ROS (the other reactive oxygen species) accounted for 8.5%. The transformation pathways of major reactive species were established.

Voltammetric determination of daminozide and its degradation product N,N-dimethylhydrazine using a boron-doped diamond electrode

• First study of direct oxidation of plant growth stimulator daminozide (DMZ) on BDDE. • Mechanism of the electrochemical oxidation of DMZ was proposed. • Sensitive direct voltammetric method for DMZ determination was developed. • Process of DMZ degradation product N , N -dimethylhydrazine (DMH) elimination was developed. • New method was successfully applied for determination of DMZ and DMH in real samples. • Isolation and concentration technique was also proposed. The simultaneous determination of growth regulator daminozide (DMZ) and its degradation product N , N -dimethylhydrazine (DMH) via their direct electrochemical oxidation was investigated for the first time and the mechanism of DMZ oxidation has been proposed. With regard to the very positive values of the oxidation potentials of both substances, a boron doped diamond electrode (BDDE) was used as the working electrode and Britton-Robinson buffer of pH 9 was applied as the suitable supporting electrolyte. First, a differential pulse voltammetric method for DMZ determination was developed, which provided a very low detection limit ( LOD = 4.56 × 10 −7 mol L −1 ). DMH could also be determined under the same experimental conditions ( LOD = 2.16 × 10 −7 mol L −1 ). The proposed extraction technique then allowed the determination of concentrations up to 50 times lower. In case of the mixture analysis, while the determination of DMH was not affected by the presence of DMZ, the results of the DMZ analysis were significantly influenced by the presence of its degradation product. Therefore, a method for removing DMH from a sample was also developed in this work. Finally, real samples of a commercially available pesticide preparation and spiked natural and rinsing waters were successfully analyzed.

Determination of Copper and Iron in Real Sample of Water and Ethanol Using Square Wave Voltammetry with a Micro/Nano Boron-Doped Diamond Electrode

Currently, the search for a more economical alternative with adequate selectivity, sensitivity and reproducibility in the determination of metallic ions is important for the development of reliable methodologies for the determination of these contaminants. This work investigates a boron-doped micro/nano diamond electrode, with different morphology and structure compared to those discussed in the literature, for the detection of copper and iron in aqueous and ethanolic environments. Internal validation of the Square Wave Voltammetry was applied. The methodology was submitted to validation by: selectivity, linearity, precision (interday test), accuracy (percentage of recovery) and detection and quantification limits. The results indicated that this type of electrode showed good response to determinations in aqueous and ethanolic environments, with good selectivity, linearity, accuracy (recovery between 70% and 110%) and precision, presenting the best detection and quantification limits for the aqueous. The methodology using a boron-doped diamond micro/nano electrode was suitable for the determination of copper and iron metals in both matrices.

Electrochemical Epoxidation Catalyzed by Manganese Salen Complex and Carbonate with Boron-Doped Diamond Electrode

Electrochemical Epoxidation Catalyzed by Manganese Salen Complex and Carbonate with Boron-Doped Diamond Electrode

Electrogenerated chemiluminescence of luminol at a boron-doped diamond electrode for the detection of hypochlorite.

Electrogenerated chemiluminescence (ECL) of luminol at a boron-doped diamond electrode has been used for hypochlorite determination. The presence of H2O2 induces the generation of the ECL signals of luminol. In contrast, the presence of hypochlorite oxidizes luminol directly to decrease the ECL signals of luminol. Accordingly, a decrease of the ECL signals of luminol in the presence of H2O2 was used as the signal response for hypochlorite detection. A linear decrease of ECL signals with the NaClO concentration in the range from 0 to 20 μM was observed with a sensitivity of 18.56 a.u. μM-1 cm-2. An estimated detection limit of 0.88 μM was achieved, which is around one order lower than the detection limit obtained using the normal electrochemical method with the same electrode. The system also provides a good selectivity towards Cu2+ and Na+. A reproducibility of 3.40%RSD was noted for 15 repetitive measurements. The analytical performance was found to be favourable in comparison to those of other typical electrochemical and electrochemiluminescence methods, indicating that it is applicable for real sample detection.

A rapid and simple electrochemical detection of the free drug concentration in human serum using boron-doped diamond electrodes.

Monitoring drug concentration in blood and reflecting this in the dosage are crucial for safe and effective drug treatment. Most drug assays are based on total concentrations of bound and unbound proteins in the serum, although only the unbound concentration causes beneficial and adverse events. Monitoring the unbound concentration alone is expected to provide a means for further optimisation of drug treatment. However, unbound concentration monitoring has not been routinely used for drug treatment due to the long analysis time and the high cost of conventional methods. Here, we have developed a rapid electrochemical method to determine the unbound concentration in ultrafiltered human serum using boron-doped diamond (BDD) electrodes. When the anticancer drug doxorubicin was used as the test drug, the catalytic doxorubicin-mediated reduction of dissolved oxygen provided a sensitive electrochemical signal, with a detection limit of 0.14 nM. In contrast, the sensitivity of glassy carbon (GC) was inferior under the same conditions due to interference from the dissolved oxygen reduction current. The signal background ratio (S/B) of BDD and GC was 11.5 (10 nM doxorubicin) and 1.1 (50 nM), respectively. The results show that a fast measurement time within ten seconds is possible in the clinical concentration range. Additionally, in the ultrafiltered human serum, the obtained values of unbound doxorubicin concentration showed good agreement with those quantified by conventional liquid chromatography-mass spectrometry. This approach has the potential for application in clinical settings where rapid and simple analysis methods would be beneficial.

Simultaneous electrochemical detection of ozone and free chlorine with a boron-doped diamond electrode.

O3 and free chlorine play significant roles in disinfection and organic degradation. There are numerous reports about their mixed-use, yet detection of the residual concentrations is not easily accomplished, whilst the interactions between them remain unclear. Herein, we develop a detection method using a boron-doped diamond (BDD) electrode to achieve the simultaneous determination of O3 and free chlorine, which benefits from the unique property of the wide potential window of BDD electrodes. It is indicated that O3 can always be accurately determined at 0.35 V vs. Ag/AgCl in an acidic solution (pH = 4-5), whether or not free chlorine is present in the solution, whereas free chlorine can be precisely monitored at -0.78 V vs. Ag/AgCl only after the O3 is completely depleted. Furthermore, in a basic solution (pH = 9-10), the reduction peak of O3 at 0.57 V vs. Ag/AgCl promptly disappears accompanied by a decrease in the peak current of free chlorine at 1.41 V. All the phenomena observed in the acidic and basic solutions are concurrently confirmed in a quasi-neutral solution. Based on these complementary measurements, a mechanism is proposed, in which the O3 reduction results in partial oxidation of the BDD surface, hindering the reduction of free chlorine in the acidic mixture; whereas O3 reacts quickly with free chlorine in the basic solution, which causes the co-consumption of both of them. It is hoped these results will give us a guide as to how better utilize mixtures and more precisely simultaneously determine O3 and free chlorine in the mixture.

Core–shell copper-gold nanoparticles modified at the boron-doped diamond electrode for oxygen sensors

Bimetallic copper–gold (Cu@Au) nanoparticles were synthesized and utilised to modify boron-doped diamond (BDD) electrodes for an application in oxygen sensor.

Electrochemical determination of cefotaxime, a cephalosporin group drug, at a boron-doped diamond electrode

Electrochemical determination of cefotaxime, a cephalosporin group drug, at a boron-doped diamond electrode

Ultrasonication-Assisted Preparation of a Composite of Neodymium Oxide-Carbon Nanoballs@Nanotubes for the Construction of a Voltammetric Platform Based on Boron Doped Diamond Electrodes for the Sensitive Determination of Caffeic Acid in Locally Grown Grapes

Ultrasonication-Assisted Preparation of a Composite of Neodymium Oxide-Carbon Nanoballs@Nanotubes for the Construction of a Voltammetric Platform Based on Boron Doped Diamond Electrodes for the Sensitive Determination of Caffeic Acid in Locally Grown Grapes

A High-Efficiency Electrochemical Degradation of Diclofenac in Water on Planar and Microstructured 2d, and Macroporous 3d Boron-Doped Diamond Electrodes: Identification of Degradation and Transformation Products

A High-Efficiency Electrochemical Degradation of Diclofenac in Water on Planar and Microstructured 2d, and Macroporous 3d Boron-Doped Diamond Electrodes: Identification of Degradation and Transformation Products

Electrooxidation of Iohexol in Its Commercial Formulation Omnipaque on Boron Doped Diamond Electrode

This study investigated the electrochemical behavior of iohexol in its commercial formulation omnipaque on a boron-doped diamond electrode using cyclic voltammetry and chronoamperometry. The dependence of the anodic peak current density vs. iohexol concentration is linear and can be applied to the determination of the substrate concentration in environmental samples and pharmaceuticals. The iohexol electrooxidation on boron-doped diamond electrode is diffusion-controlled process and proceed via two ways: a direct electron transfers at the surface of boron-doped diamond electrode and an indirect oxidation mediated by in situ oxidative species. The iohexol electrooxidation in pH range from 2 to 6 includes exchange of 4 electrons and 1 proton, at pH superior to 6 it includes an exchanged of 2 electrons and 1 proton. The values of activation energy, anodic transfer coefficient, heterogenous rate constant, diffusion coefficient and the catalytic rate constant were 14.164 kJ mol-1, 0.428, 1.06 s-1, 4.47 cm2 s-1 and 3.61 M-1 s-1 respectively. It appears from those results that, on our electrode, for the high potential scan rates, few actives sites mainly those located at the electrode surface are involved in the iohexol oxidation process. As the potential scan rate decreases, more actives sites are involved in the process.