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.

BDD电催化耦合电解析处理载人航天器中冷凝废水的研究

为解决在硼掺杂的金刚石电极(BDD)电催化处理冷凝废水中,由于冷凝废水电导率低而导致处理能耗较高的问题,提出了BDD电催化耦合电解析的新方法处理冷凝废水。在BDD反应器内填充吸附有无机盐的混合阴阳离子交换树脂,电催化处理冷凝废水时吸附在树脂上的离子在电场作用下解析下来进入废水中,并进行交替的吸附、解析及定向运动,从而改善废水的导电性,电极两端电压显著降低,停止加电后,离子又能重新交换吸附在树脂上。以Na_(2)SO_(4),Na_(3)PO_(4)以及NaNO_(3)作为电解质时,对总有机碳(TOC)去除没有影响;而以NaCl作为电解质时,TOC去除率随着NaCl添加量的增加而降低。

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.

Synthesis and characterization of p-type boron-doped IIb diamond large single crystals

High-quality p-type boron-doped IIb diamond large single crystals are successfully synthesized by the temperature gradient method in a china-type cubic anvil high-pressure apparatus at about 5.5 GPa and 1600 K. The morphologies and surface textures of the synthetic diamond crystals with different boron additive quantities are characterized by using an optical microscope and a scanning electron microscope respectively. The impurities of nitrogen and boron in diamonds are detected by micro Fourier transform infrared technique. The electrical properties including resistivities, Hall coefficients, Hall mobilities and carrier densities of the synthesized samples are measured by a four-point probe and the Hall effect method. The results show that large p-type boron-doped diamond single crystals with few nitrogen impurities have been synthesized. With the increase of quantity of additive boron, some high-index crystal faces such as {113} gradually disappear, and some stripes and triangle pits occur on the crystal surface. This work is helpful for the further research and application of boron-doped semiconductor diamond.

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.

Boron-Doped Diamond-Film-Based Two-Dimensional Electrode of Electrophoresis Tank

Chemically robust conductive p-type boron-doped diamond （BDD） films are an important electrode material and have been widely applied in electrochemistry. In this study, BDD films are taken as a two-dimensional （2D） electrode in a eleetrophoresis tank system instead of the conventional one-dimensional platinum wire electrode. The theoretical simulations by finite element numerical analysis reveal that the 2D BDD electrodes have relatively high intensity and uniformity of electric field in the tank. Experimentally, the 2D BDD electrodes with smaller size show excellent properties for the separation of DNA fragments. The advantages of the 2D BDD electrodes with chemical inertness, sustainability, high intensity and uniformity electronic field, as well as reduced small size of electrophoresis tank would open a possibility for realizing new generation, high-performance biological devices.

Ohmic and Schottky contacts of hydrogenated and oxygenated boron-doped single-crystal diamond with hill-like polycrystalline grains

Hill-like polycrystalline diamond grains(HPDGs)randomly emerged on a heavy boron-doped p+single-crystal diamond(SCD)film by prolonging the growth duration of the chemical vapor deposition process.The Raman spectral results confirm that a relatively higher boron concentration(~1.1×10^(21) cm^(-3))is detected on the HPDG with respect to the SCD region(~5.4×10^(20) cm^(-3)).It demonstrates that the Au/SCD interface can be modulated from ohmic to Schottky contact by varying the surface from hydrogen to oxygen termination.The current-voltage curve between two HPDGs is nearly linear with either oxygen or hydrogen termination,which means that the HPDGs provide a leakage path to form an ohmic contact.There are obvious rectification characteristics between oxygen-terminated HPDGs and SCD based on the difference in boron doping levels in those regions.The results reveal that the highly boron-doped HPDGs grown in SCD can be adopted as ohmic electrodes for Hall measurement and electronic devices.

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.

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.

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.

Ti基镶嵌金刚石颗粒掺硼金刚石电极及其性能

利用粉末压片机在Ti片表面镶嵌金刚石颗粒,以此为衬底,通过热丝化学气相沉积技术沉积掺硼金刚石(boron-doped diamond, BDD)薄膜,制备新型Ti基镶嵌金刚石颗粒BDD (Ti/D/BDD)电极,并制备Ti基BDD (Ti/BDD)电极作为对比。采用扫描电子显微镜、拉曼光谱仪和电化学工作站表征电极的形貌、B掺杂水平和电化学性能,利用紫外可见分光光度计测试电极模拟废水降解的效果。结果表明:沉积时间相同时,Ti/D/BDD电极比Ti/BDD电极具有更大的电化学活性面积,更低的薄膜阻抗,使得电极对酸性橙G表现出更高的降解速率,更低的降解能耗。沉积10 h时,Ti/D/BDD电极具有最高的双电层电容(1.87 mF),最低的薄膜电阻(0.4?);降解120 min后,Ti/D/BDD电极的色度移除率比Ti/BDD电极最高可提升53.1%,同时能耗降低14.2%。

A Diamond Electrochemical Cleaning Technique for Organic Contaminants on Silicon Wafer Surfaces

Peroxodiphosphate anion （a powerful oxidant） can be formed in a special water-based cleaning agent through an electrochemical reaction on boron-doped diamond electrodes. This electrochemical reaction was applied during the oxidation,decomposition, and removal of organic contaminations on a silicon wafer surface, and it was used as the first step in the diamond electrochemical cleaning technique （DECT）. The cleaning effects of DECT were compared with the RCA cleaning technique, including the silicon surface chemical composition that was observed with X-ray photoelectron spectroscopy and the morphology observed with atomic force microscopy. The measurement results show that the silicon surface cleaned by DECT has slightly less organic residue and lower micro-roughness,so the new technique is more effective than the RCA cleaning technique.

BDD电极电化学氧化清洗工艺氧化性研究

为了改进现有的RCA清洗法以及臭氧/过氧化氢湿式清洗技术,利用金刚石膜(BDD)电极的高级电化学氧化技术生成过氧化物氧化有机物,以实现简化清洗设备及节能环保。为研究金刚石膜电极的氧化能力,电解不同浓度的硫酸钾溶液,通过高锰酸钾滴定法进行氧化性的测量,研究原料浓度对生成过氧硫酸盐浓度的影响;通过添加KOH调节pH值,研究pH值对电化学制备过氧化物的影响,用该电化学氧化方法与RCA清洗法进行清洗效果对比。实验结果显示,金刚石膜电化学氧化能力可以通过阳极电解液浓度以及pH值的调整得到控制,清洗效果在Si片表面粗糙度方面明显优于传统的RCA清洗法,而且更加节能环保。

基于炭气凝胶修饰BDD电极的叔丁基对苯二酚的检测

利用炭气凝胶(CAs)修饰硼掺杂金刚石(BDD)电极对抗氧化剂叔丁基对苯二酚(TBHQ)进行检测。首先研究了裸BDD电极和CAs修饰BDD电极在5mM[Fe(CN)6]3-(含0.1M KCl)溶液中的循环伏安行为。与裸BDD电极相比,在CAs修饰BDD电极上,5mM[Fe(CN)6]3-的氧化峰电流提高了118.14%,△Ep降低了0.197V,说明CAs具有较高的电催化活性,可以促进电极表面的电子转移,加快反应速率。1×10-4M TBHQ在不同电极上的差分脉冲伏安结果表明,经CAs修饰后,氧化峰电流从0.53μA增加到11.79μA,峰电位从0.56V负移到0.273V。研究了不同缓冲液和修饰量对电极响应的影响,实验得出最佳缓冲液为0.1M高氯酸(含10%乙醇),最佳修饰量为10μL。在最优条件下,TBHQ的氧化峰电流与其浓度在5-150μM范围内呈线性关系,线性方程为Ip=0.1419c+3.1597(R2=0.995),检出限为0.15μM。采用本方法测定实际样品大豆油中TBHQ的含量,回收率为98.05%-109.48%。

BDD电极在难降解废水处理中的应用研究进展

介绍了BDD电极的电化学特性、氧化机理及制备技术。重点总结了BDD电极在酚类、染料、农药、医药等难降解模拟废水和垃圾渗滤液、印染、制药、城镇污水处理厂出水等实际废水中的应用研究进展。提出开发大面积BDD电极制备技术,提高电极电催化性能和稳定性,增强基底附着力,开发组合工艺技术是未来BDD电极实现工业化应用的研究方向。

电压和电极间距对BDD电极电化学氧化效率的影响

掺硼金刚石（BDD）薄膜电极具有很宽的电势窗口、很小的背景电流、很高的电化学稳定性、其电化学响应在很长时间内保持稳定以及耐腐蚀等优点。采用热丝化学气相沉积（HF—CvD）方法制备掺硼金刚石薄膜，并用金相显微镜、原子力显微镜（AFM）、X射线衍射（XRD）这三种测试方式进行表征。BDD薄膜电极在电解过程中消耗很多能量。从提高氧化效率来降低能耗的角度出发，研究了电压及电极间距对BDD薄膜电极电化学氧化效率的影响。通过实验得出电压在5～13V时电化学氧化效率会随着电压的升高而升高；电极间距在0．5～4cm时电化学氧化效率随着电极间距的增大而降低。

制备双面大面积BDD电极的HFCVD设备流场仿真与结构设计

用热丝化学气相沉积(HFCVD)法制备双面大面积掺硼金刚石(BDD)电极时,沉积系统的气体流场均匀性对薄膜质量均匀性有着重要影响。针对大面积BDD电极制备的设备流场问题,采用仿真分析,研究了相关结构与流场的关系。通过设计均匀分散的进出气口以及在基板四周配置宽度为20 mm的减速板,可以有效消除横向流速差和边缘流速峰值,与结构改进之前相比能显著提高流场均匀性,高低流速差值从0.04 m/s降低到0.005 m/s。研究结果为薄膜的均匀制备提供了必要条件。