Phenol degradation by anodic oxidation on boron-doped diamond electrode combining TiO_2 Photocatalysis

Boron-doped diamond （BDD） electrocatalysis is combined with photocatalysis using titanium dioxide （TiO2） as a catalyst to improve pollutant-oxidation efficiency. Phenol solution is chosen as model wastewater. Different methods involving BDD and/or TiO2 during the degradation processes are compared. Parameters such as the currency density and initial concentration are varied in order to determine their effects on the oxidation process. Moreover, the degradation kinetics of phenol is experimentally studied. The results reveal the superiority of series combination of BDD and TiO2, especially the treatment process of electrocatalysis and succedent photocatalysis, and the optimum working currency density for electrocatalysis is 25.48 mA/cm2. The removal rate decreases with the increase in the initial phenol concentration and the degradation reaction follows quasi-first-order kinetics equation.

Electrochemical incineration of dimethyl phthalate by anodic oxidation with boron-doped diamond electrode

The anodic oxidation of aqueous solutions containing dimethyl phthalate （DMP） up to 125 mg/L with sodium sulfate （Na2SO4） as supporting electrolyte within the pH range 2.0-10.0 was studied using a one-compartment batch reactor employing a boron-doped diamond （BDD） as anode. Electrolyses were carded out at constant current density （1.5-4.5 mA/cm^2）. Complete mineralization was always achieved owing to the great concentration of hydroxyl radical （-OH） generated at the BDD surface. The effects of pH, apparent current density and initial DMP concentration on the degradation rate of DMP, the specific charge required for its total mineralization and mineralization current efficiency were investigated systematically. The mineralization rate of DMP was found to be pH-independent and to increase with increasing applied current density. Results indicated that this electrochemical process was subjected, at least partially, to the mass transfer of organics onto the BDD surface. Kinetic analysis of the temporal change of DMP concentration during electrolysis determined by High Performance Liquid Chromatography （HPLC） revealed that DMP decay under all tested conditions followed a pseudo first-order reaction. Aromatic intermediates and generated carboxylic acids were identified by Gas Chromatography- Mass Spectrometry （GC-MS） and a general pathway for the electrochemical incineration of DMP on BDD was proposed.

Electrochemical oxidation of reactive brilliant orange X-GN dye on boron-doped diamond anode

In this study,the electrochemical oxidation of reactive brilliant orange X-GN dye with a boron-doped diamond(BDD)anode was investigated.The BDD electrodes were deposited on the niobium(Nb)substrates by the hot filament chemical vapor deposition method.The effects of processing parameters,such as film thickness,current density,supporting electrolyte concentration,initial solution pH,solution temperature,and initial dye concentration,were evaluated following the variation in the degradation efficiency.The microstructure and the electrochemical property of BDD were characterized by scanning electron microscopy,Raman spectroscopy,and electrochemical workstation;and the degradation of X-GN was estimated using UV-Vis spectrophotometry.Further,the results indicated that the film thickness of BDD had a significant impact on the electrolysis of X-GN.After 3 h of treatment,100%color and 63.2%total organic carbon removal was achieved under optimized experimental conditions:current density of 100 mA/cm2,supporting electrolyte concentration of 0.05 mol/L,initial solution pH 3.08,and solution temperature of 60°C.

Electrochemical treatment of wastewater containing chlorophenols using boron-doped diamond film electrodes

The electrochemical treatment of wastewater containing chlorophenols （2-monochlorophenol, 4-monochlorophenol, 2,4-dichlorophenol, 2,4,6-trichlorophenol） was carried out experimentally with synthetic boron-d0ped diamond （BDD） thin film electrodes. Current vs time curves under different cell voltages were measured. Removal rate of COD, instant current efficiency （ICE） and energy consumption were investigated under different current densities. The influence of supporting media is reported, which plays an important role in determining the global oxidation rate. The oxidative chloride is stronger than peroxodisulphate. The electrochemical characteristics of boron-doped diamond electrodes were investigated in comparison with active coating Ti substrate anode （ACT）. The experimental results show that BDD is markedly superior to ACT due to its different absorption properties.

Growth of gem-grade nitrogen-doped diamond crystals heavily doped with the addition of Ba(N_3)_2

Additive Ba（N3）2 as a source of nitrogen is heavily doped into the graphite-Fe-based alloy system to grow nitrogendoped diamond crystals under a relatively high pressure （about 6.0 GPa） by employing the temperature gradient method. Gem-grade diamond crystal with a size of around 5 mm and a nitrogen concentration of about 1173 ppm is successfully synthesised for the first time under high pressure and high temperature in a China-type cubic anvil highpressure apparatus. The growth habit of diamond crystal under the environment with high degree of nitrogen doping is investigated. It is found that the morphologies of heavily nitrogen-doped diamond crystals are all of octahedral shape dominated by {111} facets. The effects of temperature and duration on nitrogen concentration and form are explored by infrared absorption spectra. The results indicate that nitrogen impurity is present in diamond predominantly in the dispersed form accompanied by aggregated form, and the aggregated nitrogen concentration in diamond increases with temperature and duration. In addition, it is indicated that nitrogen donors are more easily incorporated into growing crystals at higher temperature. Strains in nitrogen-doped diamond crystal are characterized by micro-Raman spectroscopy. Measurement results demonstrate that the undoped diamond crystals exhibit the compressive stress, whereas diamond crystals heavily doped with the addition of Ba（N3）2 display the tensile stress.

Preparation, characterization and electrochemical properties of boron-doped diamond films on Nb substrates

A series of boron-doped polycrystalline diamond films were prepared by hot filament （HF） chemical vapor deposition on Nb substrates. The effects of B/C ratio of reaction gas on film morphology, growth rate, chemical bonding states, phase composition and electrochemical properties of each deposited sample were studied by scanning electron microscopy, Raman spectra, X-ray diffraction, microhardness indentation, and electrochemical analysis. Results show that the average grain size of diamond and the growth rate decrease with increasing the B/C ratio. The diamond films exhibit excellent adhesion under Vickers microhardness testing （9.8 N load）. The sample with 2% B/C ratio has a wider potential window and a lower background current as well as a faster redox reaction rate in H2SO4 solution and KFe（CN）6 redox system compared with other doping level electrodes.

Electrochemical Detection of Clenbuterol in Pig Liver at Pyrrole DNA Modified Boron-doped Diamond Electrode

The direct detection of clenbuterol（CL） in pig liver without any extraction separation at a pyrrole-DNA modified boron-doped diamond（BDD） electrode is reported. The pyrrole-DNA modified BDD electrode has a strong electrocatalytic effect on the redox reaction of CL. One oxidization and two reduction peaks of CL appear at 340. 2, 299. 8 and 166. 6 mV（ versus SCE）, respectively. The pyrrole polymer alone cannot electrocatalyze the above reaction at a BDD electrode ; the electrocatalytic effect of a BDD electrode modified with DNA membrane is unsufficient for the analytical detection of CL; the replacement of boron-doped diamond by glass carbon makes the electrocatalytic reaction impossible ; the redox process is pH dependent. The influences of various experimental parameters on the pyrrole-DNA modified BDD electrode were investigated. A sensitive cyclic vohammetric response for CL was obtained in a linear range from 3.4 × 10^-6 to 5 × 10^ -4 mol/L with a detection limit of 8.5 × 10^-7 mol/L. A mean recovery of 102. 7% of CL in the pig liver sample solution and a reproducibility of 3.2% were obtained.

Electrolytic Production of NF3 Using Boron-Doped Diamond Anode in Molten NH4F·2HF

The current efficiency for NF3 formation was independent on the current density in the range of 200 to 1,000 mA·cm^2. The average values of NF3 current efficiencies on the BDD （boron-doped diamond） anode with the boron-concentration of 2,500 ppm were 32.3% at 80℃, 63.3% at 100℃ and 59.7% at 120℃. The best current efficiencies for NF3 formation on the BDD anode with boron-concentrations of 2,500, 5,000 and 7,500 ppm were obtained at 100℃ and those were 63.3%, 73.3% and 56.2%, respectively. Although anode effect occurred on the BDD electrodes covered with a part of the surface of the spiculate structure, which had the boron-concentrations higher than 7,500 ppm, it did not take place on the BDD electrodes covered with the surface of diamond structure, even if the BDD electrode had the boron-concentration of 8,000 ppm.

Structural characteristics of surface-functionalized nitrogen-doped diamond-like carbon films and effective adjustment to cell attachment

Nitrogen-doped diamond-like carbon （DLC：N） films prepared by the filtered cathodic vacuum arc technology are functionalized with various chemical molecules including dopamine （DA）, 3-Aminobenzeneboronic acid （APBA）, and adenosine triphosphate （ATP）, and the impacts of surface functionalities on the surface morphologies, compositions, microstructures, and cell compatibility of the DLC：N films are systematically investigated. We demonstrate that the surface groups of DLC：N have a significant effect on the surface and structural properties of the film. The activity of PC12 cells depends on the particular type of surface functional groups of DLC：N films regardless of surface roughness and wettability. Our research offers a novel way for designing functionalized carbon films as tailorable substrates for biosensors and biomedical engineering applications.

Comparative study of oxidation ability between boron-doped diamond (BDD) and lead oxide (PbO_2) electrodes

The electrochemical oxidation capabilities of two high-performance electrodes,the boron-doped diamond film on Ti （Ti/BDD） and the lead oxide film on Ti （Ti/PbO2）,were discussed.Hydroxyl radicals （·HO） generated on the electrode surface were detected by using p-nitrosodimethylaniline （RNO） as the trapping reagent.Electrochemical oxidation measurements,including the chemical oxygen demand （COD） removal and the current efficiency （CE）,were carried out via the degradation of p-nitrophenol （PNP） under the galvanostatic condition.The results indicate that an indirect reaction,which is attributed to free hydroxyl radicals with high activation,conducts on the Ti/BDD electrode,while the absorbed hydroxyl radicals generated at the Ti/PbO2 surface results in low degradation efficiency.Due to quick mineralization which combusts PNP to CO2 and H2O absolutely by the active hydroxyl radical directly,the CE obtained on the Ti/BDD electrode is much higher than that on the Ti/PbO2 electrode,notwithstanding the number of hydroxyl radicals produced on PbO2 is higher than that on the BDD surface.

Energy consumption of electrooxidation systems with boron-doped diamond electrodes in the pulse current mode

A pulse current technique was conducted in a boron-doped diamond （BDD） anode system for electrochemical waste- water treatment. Due to the strong generation and weak absorption of hydroxyl radicals on the diamond surface, the BDD elec- trode possesses a powerful capability of electrochemical oxidation of organic compounds, especially in the pulse current mode. The influences of pulse current parameters such as current density, pulse duty cycle, and frequency were investigated in terms of chemical oxygen demand （COD） removal, average current efficiency, and specific energy consumption. The results demon- strated that the relatively high COD removal and low specific energy consumption were obtained simultaneously only if the current density or pulse duty cycle was adjusted to a reasonable value. Increasing the frequency slightly enhanced the COD re- moval and average current efficiency. A pulse-BDD anode system showed a stronger energy saving ability than a constant-BDD anode system when the electrochemical oxidation of phenol of the two systems was compared. The results prove that the pulse current technique is more cost-effective and more suitable for a BDD anode system for real wastewater treatment. A kinetic analysis was presented to explain the above results.

Effect of deposition temperature on properties of boron-doped diamond films on tungsten carbide substrate

Boron-doped diamond(BDD)films were deposited on the tungsten carbide substrates at different substrate temperatures ranging from 450 to 850°C by hot filament chemical vapor deposition(HFCVD)method.The effect of deposition temperature on the properties of the boron-doped diamond films on tungsten carbide substrate was investigated.It is found that boron doping obviously enhances the growth rate of diamond films.A relatively high growth rate of 544 nm/h was obtained for the BDD film deposited on the tungsten carbide at 650°C.The added boron-containing precursor gas apparently reduced activation energy of film growth to be 53.1 kJ/mol,thus accelerated the rate of deposition chemical reaction.Moreover,Raman and XRD analysis showed that heavy boron doping(750 and 850°C)deteriorated the diamond crystallinity and produced a high defect density in the BDD films.Overall,600-700°C is found to be an optimum substrate temperature range for depositing BDD films on tungsten carbide substrate.

Evolution of nitrogen structure in N-doped diamond crystal after high pressure and high temperature annealing treatment

In this paper, we have reported an investigation on the evolution of nitrogen structures in diamond crystals which contain nitrogen donor atoms in the range of 1500 ppm-1600 ppm following an annealing treatment at a high pressure of about 6.5 GPa and high temperatures of 1920 K-2120 K. The annealing treatment was found to completely transform nitrogen atoms originally arranged in a single substitutional form （C-center）, into a pair form （A-center）, indicated from infrared （IR） spectra. The photoluminescence （PL） spectra revealed that a small fraction of nitrogen atoms remained in C-center form, while some nitrogen atoms in A-center form were further transformed into N3 and H3 center structures. In addition, PL spectra have revealed the existence of two newly observed nitrogen-related structures with zero phonon lines at 611 nm and 711 nm. All these findings above are very helpful in understanding the formation mechanism of natural diamond stones of the Ia-type, which contains nitrogen atoms in an aggregated form.

The properties of N-doped diamond-like carbon films prepared by helicon wave plasma chemical vapor deposition

In this paper, N-doped diamond-like carbon(DLC) films were deposited on silicon substrates by using helicon wave plasma chemical vapor deposition(HWP-CVD) with the Ar/CH_4/N_2 mixed gas. The surface morphology, structural and mechanical properties of the N-doped DLC films were investigated in detail by scanning electron microscopy(SEM), x-ray photoelectron spectroscopy(XPS), Raman spectra, and atomic force microscopy(AFM). It can be observed from SEM images that surface morphology of the films become compact and uniform due to the incorporation of N. The maximum of the deposition rate of the films is 143 nm min^(-1), which is related to the high plasma density. The results of XPS show that the N incorporates in the films and the C-C sp^3 bond content increases firstly up to the maximum(20%) at 10 sccm of N_2 flow rate, and then decreases with further increase in the N_2 flow rate. The maximum Young's modulus of the films is obtained by the doping of N and reaches 80 GPa at 10 sccm of N_2 flow rate, which is measured by AFM in the scanning probe microscope mode. Meanwhile, friction characteristic of the N-doped DLC films reaches a minimum value of 0.010.

Synthesis of Boron-doped Diamond/Porous Ti Composite Materials——Effect of Carbon Concentration

Highly boron-doped diamond films were deposited on porous titanium substrates by hot filament chemical vapor deposition technique. The morphology variation of highly boron-doped diamond films grown on porous titanium substrates was investigated, and the effects of carbon concentration on nucleation density and diamond growth were also studied. The continuous change of surface morphology and structure of diamond film were characterized by scanning electron microscopy. The structures of diamond film and interlayer were analyzed by X-ray diffraction. The quality of boron-doped diamond film was confirmed by visible Raman spectroscopy. The experimental results reveal that surface morphology and quality of boron-doped diamond films are various due to the change of carbon concentration. The thickness of intermediate layer decreases with the carbon concentration increasing.

Boron-Doped Diamond Films Deposited on Silicon Substrates by MPCVD

High quality, good adhesion and p-type diamond films are obtained by microwave plasma chelincal vapordeposition. The area of the films is 20 x 20 nun. The structural morphologies, bonding mechanism and surfacemol'Phology are characterized by X-ray diffraction (XRD), Raman scattering and scanning Electron microscopy(SEM) respectively. The resistance, Hall coefficient, mobility, etc. are also measured. Tile factors related tonucleation and other properties of diamond films are discussed.

Application of Boron-doped Diamond Film Electrode in Fast Detection of Samonella in Water

[Objective] The study aimed to discuss the application of boron-doped diamond （BDD） film electrode in fast detection of samonella in water. [ Method] Boron-doped diamond film electrode was prepared and used as the working electrode in fast detection of salmonella in water using chronoamberometry, and the oxidation mechanism of the electrode acting on salmonella was discussed. [ Result] Compared with traditional biologi- cal methods, chronoamperometry could detect the number of salmonellae in water more simply, rapidly and sensitively. [ Conclusion] The method of using BDD electrode to detect salmonella quantity will be widely applied in future.

Electroanalytical Investigation on Paracetamol on Boron-Doped Diamond Electrode by Voltammetry

An electroanalytical method was developed for the direct quantitative determination of paracetamol in tablets based on its oxidation behavior. The electrochemical oxidation and determination of paracetamol were easily carried out on born-doped diamond (BDD) electrode using two voltammetric techniques (CV and DPV). The electrochemical measurements performed by cyclic voltammetric (CV) and differential pulse voltammetry (DPV) techniques were carried out using a cathodically pretreated boron-doped diamond electrode in HClO4 and KClO4 electrolytes. HClO4 was then selected for analytical purposes and scan rate studies were also completed. The oxidation of the paracetamol is found to be irreversible and a diffusion-controlled nature of the paracetamol oxidation peak was established. A linear calibration curve for DPV analysis was constructed in the paracetamol concentration range from 0 μM to 13.87 μM, with 0.16 μM and 0.55 μM as the detection and quantification limit respectively.

Analytical Determination of Benzophenone-3 in Sunscreen Preparations Using Boron-Doped Diamond Electrodes

A new electroanalytical procedure was developed for the determination of Benzophenone-3 (BENZO) in commercial sunscreen as the active ingredient. The procedure is based on the use of electrochemical methods as cyclic and square-wave voltammetry, with boron-doped diamond (BDD) electrodes. The reduction of BENZO in Britton-Robinson buffer (0.1 mol●L–1) using this type of electrode gives rise to one irreversible peak in –1.30 V (versus Ag/AgCl) in presence of cationic surfactant cetyltrimethylammonium bromide (CTABr). The proposed electrochemical method was successfully applied to the analysis of commercially available pharmaceutical preparations.

Suppression and compensation effect of oxygen on the behavior of heavily boron-doped diamond films

This work investigates the suppression and compensation effect of oxygen on the behaviors and characteristics of heavily boron-doped microwave plasma chemical vapor deposition(MPCVD)diamond films.The suppression effect of oxygen on boron incorporation is observed by an improvement in crystal quality when oxygen is added during the diamond doping process.A relatively low hole concentration is expected and verified by Hall effect measurements due to the compensation effect of oxygen as a deep donor in diamond.A low acceptor concentration,high compensation donor concentration and relatively larger acceptor ionization energy are then induced by the incorporation of oxygen;however,a heavily boron-doped diamond film with high crystal quality can also be expected.The formation of an oxygen–boron complex structure instead of oxygen substitution,as indicated by the results of x-ray photoelectron spectroscopy,is suggested to be more responsible for the observed enhanced compensation effect due to its predicted low formation energy.Meanwhile,density functional theory calculations show that the boron–oxygen complex structure is easily formed in diamond with a formation energy of-0.83 eV.This work provides a comprehensive understanding of oxygen compensation in heavily boron-doped diamond.