Interactive Oxidation of Photocatalysis and Electrocatalysis for Degradation of Phenol in a Photoreactor

TiO2/C particles as photocatalyst were prepared by dipping TiO2 suspension solution with activated carbon and were applied in the photocatalytic-electrocatalytic degradation of phenol, the Ti/SnO2+Sb2O3/PbO2 electrode and oxygen diffusion electrode were used as anode and cathode respectively, and a 250 W ultraviolet lamp (365 nm) as side light source. The SEM results of TiO2/C and Ti/SnO2+Sb2O3/PbO2 anode indicated that the TiO2 on carbon particles was uniform and PbO2 film on the surface of anode was in cauliflower form, the XRD result of oxygen diffusion electrode showed that only crystalline graphite was found. The influential parameters of degradation process such as applied cell voltage (E), initial concentration of phenol (C0), amount of TiO2 catalyst and air flow rate (v) were discussed. Under the following experimental conditions of C0=50 mg/L, pH=6, E=2 V, TiO2 0.98 mg/mL, v=382.2 mL/min, and light intensity I=10.5 mW/cm2, phenol could be entirely degraded, and about 89% of total organic carbon (TOC) was removed after 3 h degradation.     

微弧氧化TiO2膜的电助光催化性能研究

以磷酸钠为电解液,采用微弧氧化技术制备钛基TiO2膜,以该膜为阳极,钛片为阴极与40 W紫外灯和稳压电源组成电助光催化体系,以大红染料模拟废水来评价TiO2膜光电催化能力。研究了酸度和亚铁离子质量浓度等因素对光催化的影响。结果表明:光电催化提高了TiO2膜阳极的降解率;阴极槽内亚铁离子存在会形成电-芬顿体系,有助于提高光电催化降解率。当电解液中支持电解质硫酸钠浓度为0.5 mol/L、pH=3时阳极槽的降解率达到38%,阴极槽亚铁离子质量浓度为3.0mg/L时降解率达到68%。     

Electrochemical characteristics and catalytic activity of polyaniline doped with ferrocene perchlorate

A new‐doped method based on electrochemical polymerization of aniline in the presence of ferrocene perchlorate and perchloric acid was presented. Polyanilines (PAn and PAnFc) were polymerized in the solution of perchloric acid and the solution containing ferrocene perchlorate and perchloric acid, respectively. Both flame atomic absorption spectrometry and infrared spectrum indicated that ferrocene perchlorate was assured to be doped into the polyaniline. We presumed that ferrocene perchlorate was combined via electrostatic adsorption onto the chain of polyaniline. The effect of pH on the electrochemical characteristics of PAn and PAnFc was studied by cycle voltammetry. Compared with PAn prepared in the absence of ferrocene perchlorate, PAnFc prepared in the presence of ferrocene perchlorate has a rather high electrochemical activity at pH > 4. The electrochemical oxidation of ascorbic acid (AA) on both PAn film and PAnFc film modified Pt electrode was also performed. The results indicated that the catalytic activity of the PAnFc film to AA was better than that of the PAn film. The anodic peak currents of AA (measured by constant potential amperometry) increased linearly with the concentration of AA in the range of 8.0 × 10^?5–1.0 × 10^?2 mol/L. The detection limit (S/N = 3) obtained was 1.0 × 10^?5 mol/L. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5633–5639, 2006     

Electrochemical properties of porous bismuth electrodes

The properties of Bi surfaces with different roughnesses were characterized by electron microscopy, cyclic voltammetry, and impedance spectroscopy. Two different strategies were used for preparation of porous bismuth layers onto Bi microelectrode surface in aqueous 0.1 M LiClO₄ solution. Firstly, treatment at potential E < −2 V (vs. Ag|AgCl in sat. KCl) has been applied, resulting in bismuth hydride formation and decomposition into Bi nanoparticles which deposit at the electrode surface. Secondly, porous Bi layer was prepared by anodic dissolution (E = 1 V) of bismuth electrode followed by fast electroreduction of formed Bi³⁺ ions at cathodic potentials E = −2 V. The nanostructured porous bismuth electrode, with surface roughness factor up to 220, has negligible frequency dispersion of capacitance and higher hydrogen evolution overvoltage than observed for smooth Bi electrodes.     

可充碱锰电池用化学二氧化锰的制备

温度控制在 85～ 95℃ ,在HNO3介质中 ,用KMnO4氧化MnCl2 和Bi(NO3) 3的混合溶液 ,可制得具有良好可充性能的掺铋二氧化锰 (Bi MnO2 ) ,该样品在 9mol/LKOH溶液中有稳定的循环伏安曲线且经X射线衍射分析测得其在不同放电深度均无Mn3O4生成 ,这表明在MnO2 中添加铋可阻止不具有电化学活性的Mn3O4生成 ;用该样品做成的模拟电池做连续充放电实验 ,电极的循环次数由原来的 5～ 6次 ,提高到 60次以上。     

Three-dimensional ordered macroporous bismuth vanadates: PMMA-templating fabrication and excellent visible light-driven photocatalytic performance for phenol degradation

Three-dimension ordered macroporous (3D-OM) bismuth vanadates with a monoclinic crystal structure and high surface area (18-24 m(2) g(-1)) have been prepared using ascorbic acid (AA)- or citric acid (CA)-assisted poly(methyl methacrylate) (PMMA)-templating strategy with bismuth nitrate and ammonium metavanadate as the metal sources, HNO(3) as the pH adjuster and ethylene glycol and methanol as the solvent. The materials were characterized by a number of analytical techniques. The photocatalytic performance of the porous BiVO(4) samples was evaluated for the degradation of phenol in the presence of a small amount of H(2)O(2) under visible light illumination. The effects of the initial phenol concentration and the H(2)O(2) amount on the photocatalytic activity of the photocatalyst were examined. It is shown that the chelating agent, AA or CA, and the amount in which it is added had a significant impact on the quality of the 3D-OM structure, with a "(Bi + V):chelating agent" molar ratio of 2:1 being the most appropriate. Among the as-prepared BiVO(4) samples, the one with a surface area of ca. 24 m(2) g(-1) showed the best visible light-driven photocatalytic performance for phenol degradation (phenol conversion = ca. 94% at phenol concentration = 0.1 mmol L(-1) and in the presence of 0.6 mL H(2)O(2)). A higher phenol conversion could be achieved within the same reaction time if the phenol concentration in the aqueous solution was lowered, but an excess amount of H(2)O(2) was not a favorable factor for the enhancement of the catalytic activity. It is concluded that the excellent photocatalytic activity of 3D-OM BiVO(4) is due to the high quality 3D-OM structured BiVO(4) that has a high surface area and surface oxygen vacancy density. We are sure that the 3D-OM material is a promising photocatalyst for the removal of organics from wastewater under visible light illumination.     

苯酚废水的铈掺杂钛基电极处理工艺

采用热分解方法制备了铈掺杂钛基电极,并以铈掺杂钛基电极为阳极,纯钛板为阴极组成电解池,以苯酚为目标有机污染物进行降解,采用高效液相色谱法检测苯酚的含量。讨论了Ce的掺杂量、电解池中电极间距、电解电压、电解质溶液的pH、电解质浓度、目标物的浓度以及电解时间对苯酚去除率的影响。结果表明该电解池降解苯酚废水的最佳条件：SnCl4·5Hz0、SbCl3、Ce（NO3）,物质的量比为100：10：1、电极间距为4．0cm、电解电压为9V、pH为6．55、电解质NaSO。浓度为10g／L、苯酚浓度为100mg／L、电解时间为6h。在最佳试验条件下苯酚去除率达到100％,完全符合排污标准GB8978--1996,该电极持续使用10d,对苯酚的去除率仍然可以达到85％,降解苯酚的机理趋于直接燃烧。     

The ac and dc polarographic reduction of bismuth(III) in acidic halide and other media

Some aspects of the ac and dc polarographic reduction of Bi(III) in acidic perchlorate, nitrate and halide media have been examined and results from this and investigations by other workers have been used to elucidate the electrode processes occuring in non-complexing and complexing media. The equivalence of the ac and dc electrode processes is suggested, and the dependence of ac-wave height and independence of dc-wave height upon ligand concentration is used as a guide to the role of complex formation in altering the rate of the electrode process. In acidic perchloric acid, the major species is thought to be Bi(aq)³⁺ and the electrode process Bi(aq)3e? Bi(amalgam) + aq is believed to be slow due to kinetically slow removal of co-ordinated water. Formation of covalently bonded ligands can increase the rate of removal of water and the rate of the electrode process increases substantially. Evidence for this comes from addition of nitrate to perchloric acid solutions. Bismuth(III) forms uncommonly stable nitrate complexes and the unusual ability of nitrate to catalyse strongly the bismuth(III) electrode process would appear to be related to nitrate complex formation. The halides also form strong bismuth(III) complexes, but because they are strongly adsorbed at mercury electrodes complex formation in the double layer can occur as well as in the bulk solution. For chloride, as with nitrate, complex formation at the electrode is not thought to be significant; however for the other halides, complex formation both in solution and the double layer appear to be important.     

The feasibility of using a rechargeable MnO2 cathode with a metal hydride anode

The feasibility of using a manganese dioxide cathode with a metal hydride anode is discussed. MnO2 cathodes doped with bismuth compounds were rechargeable. The cathode material was prepared in its discharged state from MnO and bismuth compounds, thus matching the metal hydride anode in terms of initial state of charge, formation cycles and balance of self-discharge. It is believed that the presence of bismuth in the cathode prevents formation of spinel manganese oxide and lowers the activation energy (overpotential) for the second electron reduction and oxidation of MnO2. Hydrogen recombination with MnO2 was also studied to enable balancing of the self discharge rates of cathode and anode during storage.     

可见光响应的Bi-TiO_2的制备及其对间苯二酚的降解作用

以钛酸四丁酯、硝酸铋为原料,采用水热法制备铋掺杂TiO2光催化剂（Bi-TiO2）。所得材料用X射线衍射、透射电子显微镜、X射线能谱、X射线荧光光谱、UV–Vis漫反射等测试手段分析。结果显示水热法可以直接合成锐钛型纳米TiO2。铋在TiO2中的掺杂方式为Bi3＋替位取代TiO2中Ti4＋。样品具有较大的比表面积,其最大达31.2 m2/g。铋掺杂能引起TiO2光催化剂的吸收光谱明显红移,从而具备较好的可见光响应性。以降解间苯二酚为探针反应研究其可见光催化性能,纯TiO2光催化活性极低,而Bi-TiO2具有较高的可见光催化性能,当铋掺杂量为1.00%时光催化性能最佳。UV–Vis光谱和高效液相色谱显示间苯二酚在70W金卤灯下反应120min能完全分解。     

掺杂铁的二氧化铅电极的制备及性能研究

主要研究了不锈钢/PbO₂电极和掺杂的不锈钢/Fe-PbO₂电极的制备,用其对有机废水的处理效果及影响因素来评价该电极的性能。实验结果表明:采用恒流阳极电沉积技术制备的PbO₂电极,掺杂和不掺杂铁的电极主要成分都是β-PbO₂;两电极外观都没有明显的裂纹等缺陷,掺杂铁的二氧化铅镀层颗粒大小镶嵌,很好地清除了内应力,保证了基材与镀层不易脱落,未掺杂铁的二氧化铅镀层颗粒细小、均匀,内应力有些大;将Fe（NO₃）₂添加至电沉积溶液中,致使PbO₂电沉积层的析氧电位向正方向移动,改善了PbO₂电极的电催化活性,以至于更有利于氧化降解有机物。用改性的Fe-PbO₂电极和常规的PbO₂电极分别降解初始浓度相同的邻苯二酚和苯酚有机物废水,改性的Fe-PbO₂电极对苯酚和邻苯二酚的去除率均高于常规的PbO₂电极。掺杂铁的二氧化铅电极较未掺杂电极有更好的电催化活性,更高的析氧电位,更适宜于用作电催化阳极。     

The anodic characteristics of manganese dioxide electrodes prepared by thermal decomposition of manganese nitrate

Manganese dioxide electrodes were prepared by a thermal decomposition of manganese nitrate solution on a titanium or a platinum substrate, and their anodic characteristics were investigated mainly in 1N H₂SO₄ and 1N KOH. The platinum-supported manganese dioxide electrode shows the good anodic characteristics with a relatively low overvoltage for oxygen evolution while the use of the titanium-supported one as an anode needs further modification to reduce its high resistivity resulting from the thick film of titanium dioxide in spite of good adhesion of the oxide film with the titanium substrate.The primary water or hydroxide ion discharge step is rate-controlling in the anodic evolution of oxygen on the platinum-supported manganese dioxide electrode in both acidic and alkaline solutions. The oxygen overvoltage is raised and the mechanical strength of the catalytic oxide on the platinum substrate is weakened by the anodic polarization in acidic solution. These phenomena are explicable on the basis of an increase in the oxygen content in the oxide. In conclusion, the presented results suggest that the manganese dioxide film is a practical usable material for the anodic evolution of oxygen as well as chlorine, especially in alkaline solutions.     

氮掺杂纳米TiO2的制备及其光催化降解酸性红B的研究

以钛酸丁酯和氨水为原料,无水乙醇为溶剂,硝酸为抑制剂,采用湿法水解制备氮掺杂TiO2纳米微粒,并用XRD、TEM对其进行了表征。在紫外光照射下,考察了氮掺杂催化剂光催化降解酸性红B的催化性能。以高压汞灯为光源对有机染料酸性红B进行了光催化降解实验,并研究了催化剂的类型、催化剂的用量、溶液初始浓度对酸性红B降解的影响。研究结果表明：氮掺杂纳米TiO2的光催化性能明显优于纯纳米TiO2的光催化性能。     

4种DSA阳极的制备及其电催化性能比较

制备了Ti/SnO2+Sb2O3, Ti/PbO2, Ti/Fe-PbO2和Ti/SnO2+Sb2O3/Fe-PbO2四种形稳阳极材料,对其表面形貌进行了表征,同时测试了其在H2SO4溶液中的极化曲线. 以苯酚为目标污染物,用其进行了电催化降解实验. 结果表明,Ti/SnO2+Sb2O3/Fe-PbO2电极催化活性最好,苯酚降解率可达95%. 添加锡锑中间层后,Ti/SnO2+Sb2O3/Fe-PbO2电极寿命显著提高,可达16 h. 苯酚在4种阳极上的电催化降解反应遵循一级反应动力学规律.     

钛阳极氧化过程中直接附载光敏剂工艺研究

基于电化学阳极氧化的方法,将光敏剂直接附载到具有纳米孔的阳极氧化钛薄膜上。将金属钛作为阳极,在添加了光敏剂5,10,15,20-对四羧基四苯基卟啉的硫酸水溶液中进行阳极氧化,制备出附载了光敏剂的具有纳米孔结构的敏化氧化钛薄膜。通过对附载前后氧化钛薄膜荧光、紫外等光谱特性表征,结果表明,电压、温度等因素对敏化氧化钛薄膜的光谱性质有很大的影响。     

Aluminium alloys for aluminium primary cell

Aluminium has not widely been used for anode material for primary cells, despite its attractive properties. Aluminium loses a great part of the potential when anodically polarized, and is easily coroded in aqueous solution with hydrogen evolved. Aluminium alloys derived from high purity aluminium (99.999%) were prepared for application to primary dry cell. Small amounts of the following elements were added to aluminium: Zn, Sn, Bi, In, Mg. The electrode potential, the anode Faradaic efficiency and the rate of corrosion of the alloy specimen sheet (10 × 10 × 0.5) were measured in 1 M AlCl₃ aqueous solution. The rate of corrosion significantly increased after anodic polarization (anodic dissolution). The electrode potentials at open circuit and anodic polarization (10 mA cm⁻² shifted remarkably in the negative direction by alloying. The anode Faradaic efficiency and the rate of corrosion depended upon the alloy composition. The alloy, Al-3.0 Zn-0.13 Sn-0.01 Ga-0.07 Bi (% w/w), gave the best results. The anode efficiency amounted to 99.7% as compared with 87.4% for 99.999% Al. The average rate of corrosion was reduced to 0.03 mg cm⁻² h⁻¹ (short term) and 0.01 mg cm⁻² h⁻¹ (long term). These electrochemical properties will improve the characteristics of aluminium dry cells.     

不同金属氧化物膜电极上苯酚的电催化氧化

分别以自制的金属氧化物膜电极Ti/SnO2+Sb2O3、Ti/SnO2+Sb2O3/PbO2和Ti/SnO2+Sb2O3/RuO2+PbO2为阳极，恒电流电解低浓度苯酚溶液，研究了不同金属氧化物阳极对苯酚电催化氧化过程的影响。实验结果表明：在实验条件下，苯酚溶液在3种金属氧化物膜电极上的电催化氧化过程的宏观动力学符合一级反应动力学规律，但不同金属氧化物阳极上苯酚电催化氧化过程的表观反应速率及电流效率有明显的差异。25℃下苯酚在Ti/SnO2+Sb2O3、Ti/SnO2+Sb2O3/PbO2和Ti/SnO2+Sb2O3/RuO2+PbO2电极上电催化氧化的表观反应速率常数k分别为6.66×10-2min-1、2.49×10-2min-1和9.76×10-3min-1;瞬时电流效率随电解时间的增长而下降，初始电流效率分别为78.7%、38.9%、13.2%。以Ti/SnO2+Sb2O3电极为阳极电解60 min后，苯酚浓度从初始浓度2.13×10-3mol·L-1降至3.27×10-5mol·L-1，苯酚的转化率达98.5%;而在相同的反应条件下，以Ti/SnO2+Sb2O3/PbO2和Ti/SnO2+Sb2O3/RuO2+PbO2为阳极时，苯酚的转化率只有82.7%和29.8%。对3种电极在苯酚溶液中的伏安特性的研究表明，Ti/SnO2+Sb2O3电极具有比Ti/SnO2+Sb2O3/PbO2和Ti/SnO2+Sb2O3/RuO2+PbO2高的析氧电位，因此有利于有机物的氧化和过程电流效率的提高。     

不同金属氧化物阳极组合降解苯酚过程比较分析

钛基氧化铱电极为代表的活性阳极析氧过电位低,钛基氧化铅电极为代表的非活性电极析氧过电位高。以钢板为阴极,选取了Ti/Ir-RuO_x作为单一阳极类型和Ti/Ir-RuOx_Ti/PbO_2作为双阳极类型,对比处理苯酚模拟废水的效果,从电流密度、pH值、苯酚模拟废水初始浓度和电解质类型4个方面来比较对苯酚处理效果的影响。实验表明,在电流密度为10 mA/cm~2、pH为7、苯酚模拟废水初始浓度为100 mg/L和加入少量NaCl为电解质的条件下,双阳极类型组合对苯酚模拟废水的处理效果要好于单阳极,去除率达到98%。     

Ti/SnO2+Sb2O3/PbO2电极在硫酸溶液中Cr3+氧化的电化学性能

对用聚合前驱体溶液通过热分解法制备的Ti/SnO2+Sb2O3/PbO2电极在硫酸溶液中Cr3+电化学氧化的电化学性能进行了研究. 分别测定了以Ti/SnO2+Sb2O3/PbO2和PbO2为阳极，硫酸介质中Cr3+电化学氧化过程的极化曲线、抗腐蚀性以及不同操作电流密度、Cr3+浓度、反应温度、硫酸浓度下的电流效率. 实验结果表明，聚合前驱体溶液通过热分解法制备的Ti/SnO2+Sb2O3/PbO2电极与PbO2电极相比具有更高的电催化活性和抗腐蚀性.     

Effects of polyethylene glycol and gelatin on the crystal size, morphology, and Sn-sensing ability of bismuth deposits

The influences of citric acid (CA), ethylenediaminetetraacetic acid (EDTA), polyethylene glycol (PEG), and gelatin on the deposition behavior of Bi were systematically investigated through the linear sweep voltammetric (LSV) analysis. Based on the LSV results, deposits plated from a typical solution containing 0.05 M Bi(NO₃)₃·5H₂O and various combinations of complex agents and additives with pH = 3.5 at 1 and 30 mA cm⁻² were characterized by scanning electron microscopic (SEM) and X-ray diffraction (XRD) analyses. The adhesion of deposits and the formation of dendrites were respectively improved and inhibited by the adsorption of PEG onto Bi deposits. With adding the above four compounds, a synergistic effect was shown to reach a nano-sized, sphere-like, porous morphology of a Bi deposit at 30 mA cm⁻². The crystal size and morphology of Bi deposits were found to affect the sensing ability of Sn²⁺ through the square-wave anodic stripping voltammetric (SWASV) analysis.