K2Ti6O13薄膜电极的制备及其光电化学

采用溶胶-凝胶法制备了隧道状结构的K2Ti6O13薄膜电极. 溶胶-凝胶法解决了K2Ti6O13与导电基材间结合差的难题,实现了该电极良好的导电性能. 在此基础上,通过紫外-可见光吸收光谱结合电化学方法确定了K2Ti6O13薄膜的能带结构. 溶胶-凝胶法制备的TiO2薄膜电极用于验证方法的可靠性,并作为K2Ti6O13薄膜结构和性能特征的参照系. 实验结果表明,制备的K2Ti6O13薄膜电极禁带宽度为3.05 eV,小于K2Ti6O13粉体的禁带宽度(3.45 eV)和TiO2薄膜的禁带宽度(3.22 eV),具有可见光响应能力. 同时,K2Ti6O13薄膜电极的导带电位(-0.77 V, vs. NHE)低于TiO2薄膜电极(-0.61 V, vs. NHE),显示其还原能力优于TiO2薄膜电极,具有较强的光解水产氢潜力. 此外,K2Ti6O13薄膜的电化学表征还表明其具有很好的电子-空穴分离能力和材料稳定性. 因此,制备的K2Ti6O13薄膜在可见光光解水制氢领域将有较好的应用潜力.     

光电化学池降解苯酚溶液制氢

以质子交换膜分隔建立阴/阳双室光电化学池(PEC),溶胶-凝胶+粉末涂覆法制各的ITO负载纳米TiO2薄膜光电极浸入盛有含苯酚污染物的碱性电解液的阳室,铂电极作为对电极浸入盛有酸性电解液的阴室,通过导线建立两室的电子回路.光照Tio2/ITO产生的光电压与阴、阳两室电解液pH差产生的化学偏压叠加,使该体系无需外加偏压直接在阴室将H+还原为H2,并同时降解阳室中的有机污染物苯酚.结果表明:光电化学池中苯酚的存在可以作为电子牺牲剂利于电化学析氢,并表现出比光催化更好的降解率.对该光电化学池外加1.4 V的偏压能显著提高氢的产量及苯酚的降解率.     

纳米TiO_2膜电极上乙醛酸的电催化合成研究

运用电化学循环伏安法 (CV)对纳米TiO2 膜电极 (Ti/nano TiO2 )在硫酸和草酸溶液中的电化学行为进行了研究。在c(H2 SO4 ) =1mol/L溶液中的循环伏安图上Epac1=- 0 .5 6V(vs.SCE)和Epac2 =- 0 96V(vs.SCE)处 ,出现两对可逆氧化还原峰 ,而在相同扫描速度下草酸溶液中的循环伏安曲线上 ,这两对电极反应氧化峰基本消失 ,还原峰电流增大 ,表明Ti/nano TiO2 膜电极对电还原草酸成为乙醛酸的反应具有较高的电催化活性和选择性。常温常压下 ,控制电位Epc=- 1 0V左右电解合成乙醛酸 ,乙醛酸的产率和电流效率分别达到 96 5 %和 90 %。     

TiO2薄膜光电极能带结构和催化活性的初探

以阳极氧化法制得的TiO2薄膜光电极为工作电极，铂环为对电极，饱和甘汞电极为参比电极，组成光电催化降解苯酚体系．运用电化学阻抗图谱(EIS)，测得光电催化过程中TiO2薄膜光电极的空间电荷层电容，计算出半导体能带结构参数——空间电荷层宽度W．结果证明：当空间电荷层宽度W随阳极偏压增加而增大时，TiO2薄膜电极光催化活性提高；当其等于薄膜厚度时，光催化活性最好，此时出现最佳偏压值；继续增加偏压，活性反而有所下降。     

KOH亚熔盐法制备钛酸钾晶须和二氧化钛

研究了以高钛渣为原料、采用KOH亚熔盐法制备钛酸钾晶须和二氧化钛的新方法,探讨了反应温度、初始KOH浓度、反应时间和碱矿比等因素对钛酸钾晶须形貌的影响. 实验结果表明,反应温度、反应时间和碱矿比对钛酸钾晶须的形貌影响较为显著,并得到长度约20~25 mm、长径比约为15~20的钛酸钾晶须. 钛酸钾在pH=10~12间水解并煅烧,制备了八钛酸钾晶须;在pH=1~3间水解并煅烧,制备了二氧化钛晶须.     

Superior overall water splitting performance in polypyrrole photoelectrode by coupling NrGO and modifying electropolymerization substrate

We prepare photoelectrodes with mixed metal oxides (TiO₂-RuO₂), polypyrrole (PPy) and N-doped reduced graphene oxide (NrGO) on titanium (Ti) substrate for overall water splitting and methylene blue degradation during two steps; including a sol–gel deposition of mixed metal oxide (MMO) and electrodeposition of PPy or PPy-NrGO films. The as-prepared photoelectrodes are characterized by physical and photoelectrochemical measurements. Ti/MMO/PPy-NrGO photoelectrode exhibit a considerably photocurrent density of −6.97 mA cm⁻² (at 0 V vs. reversible hydrogen electrode [RHE]) and 12.89 mA cm⁻² (at 1.23 V vs. RHE) for hydrogen and oxygen generations, respectively. However, promotion in the H⁺/H₂ efficiency (40.25%) is about 28 orders of magnitude while in the case of H₂O/O₂ (13.77%) is 10 times. The electrochemical impedance spectroscopy and Mott–Schottky measurements reveal that the simultaneous incorporation of MMO and NrGO nanosheets in PPy coating leads to the lowest charge transfer resistance at the photoelectrode/electrolyte interface and an improvement in charge carrier density.     

Stabilizing nanocrystalline Cu2O with ZnO/rGO: Engineered photoelectrodes enables efficient water splitting

The engineered photoelectrodes have received significant attention in the photoelectrochemical (PEC) applications. Herein, we prepared a highly effective photoelectrode based on Cu₂O decorated with ZnO and rGO for efficient PEC water splitting. Firstly, different thickness Cu₂O is sputtered on the FTO substrate (FC). The PEC performance of the FC photoelectrode further improved by depositing the ZnO and rGO protection layers (FCZG). The fabricated photoelectrodes are systematically investigated for their morphological and crystal structure by AFM, FESEM, TEM, XPS, XRD, and RAMAN, UVDRS, and PL analysis. The FCZG hybrid photoelectrode exhibit a photocurrent density of 4.94 mA cm^?2 at 0 V vs. reversible hydrogen electrode (RHE), which is 1.5 times higher than the unmodified photoelectrodes. The improved PEC performance of the FCZG hybrid photoelectrode is due to the high surface roughness, larger electrochemical active surface area, and less radiative recombination rate of the photogenerated charge carriers.     

钛酸钾晶须耐碱多孔陶瓷的制备及表征

The preparation and characterization of alkaline resistant porous ceramics from potassium titanate whiskers are studied. K2Ti4O9 whiskers in the whisker preforms （mixtures of K2Ti6O13 and K2Ti4O9） were completely converted to K2Ti6O13 at 960℃. The alkaline resistance as well as the change in bending strength, porosity and permeability of the ceramics was investigated by altering the composition of the preforms in which the content of K2Ti6O13 whiskers was higher than 50% （molar fraction）. The alkaline resistance of the porous K2Ti6O13 ceramics is found much higher than that of Al2O3 in caustic NaOH solutions, and further study indicates that the K2Ti6O13 ceramics can be stably used in solutions of pH〉2.0. The bending strength increases initially with the content of the raw K2Ti6O13 in the preforms up to 66% （molar fraction） and then decreases, contrary to the behaviors of porosity and permeability. The values of bending strength, porosity and permeability of the ceramics prepared from the preform of 80% （molar fraction） raw K2Ti6O13 whiskers are respectively 56MPa, 29.4% and 330L·m^-2〈h^-1 , which are comparable to those of the porous Al2O3 ceramics.     

多孔TiO2纳米薄膜修饰的镍基光电极的制备和性能

引　言近年来 ,随着全球环境污染的进一步加剧 ,人们对清洁、无毒、可重复使用的能源———氢气的制备、储存及应用的研究日益重视 .其中 ,利用太阳能光解水或光助电解水为最理想的制氢途径 . 1972年 ,Ｆｕｊｉｓｈｉｍａ和Ｈｏｎｄａ[1] 发现光照下ＴｉＯ2 光电极可分解水制氢气 .此后 ,ＴｉＯ2 成为进行光化学转换及光催化降解有机物的重要的半导体材料 .近年来 ,纳米半导体材料的研究日新月异 ,在光催化、光电转换、光化学转换方面表现出诱人的应用前景 .通常制备ＴｉＯ2 的工艺有离子溅射法[2 ] 、热氧化法[3] 、电化学沉积法[4 ] 、化…     

粒径对K2Ti6O13大孔陶瓷的制备及性能影响

以K2Ti6O13晶须、K2CO3和TiO2为原料,通过调变K2Ti6O13晶须的粒径,采用不同尺寸晶须间的混合,制备了孔结构可调的K2Ti6O13大孔陶瓷,考察了陶瓷的纯水通量和机械强度与K2Ti6O13晶须粒径及不同尺寸晶须间的配比关系。研究结果表明,随着K2Ti6O13晶须粒径的减小,K2Ti6O13陶瓷体积密度增大,开孔率和纯水通量随之减小,机械强度逐渐升高。当采用中位粒径为7.50 μm 和1.60 μm的K2Ti6O13晶须以质量比为3:1的比例为原料时,陶瓷物料间形成了大晶须与中细颗粒的搭接,得到了最佳的综合性能,相应的机械强度为42.8±0.2 MPa,开孔率为36.4%,纯水通量为2366 L.m-2.h-1.MPa-1,在分子筛膜领域具有良好的应用前景。     

TiO2薄膜光电催化亚甲基蓝的研究

采用溶胶-凝胶-浸渍法在钛基底上制备了TiO2薄膜,以该薄膜为工作电极,石墨作对电极,饱和甘汞电极为参比电极,建立光电催化反应体系,对亚甲基蓝溶液进行了光电催化降解研究。结果表明：当外加偏压1.0 V,热处理温度500℃时,pH为10.2,TiO2薄膜光电催化活性最好,光电催化亚甲基蓝120 min可使其脱色率达64....     

层状固体酸H2Ti6O13的制备与性能研究

实验采用高温同相法合成K2Ti6O13前驱物,然后通过酸化制备出相应的固体酸K2Ti6O13.并应用X-射线粉末衍射(XRD)、紫外-可见漫反射光谱(UV-vis-DRS)和NH3-TPD等表征手段对层状固体酸的结构、光谱特性和酸性进行研究.结果表明,由高温固相法合成的K2Ti6O13是一种典型的层状化合物,并且是亚纳...     

In situ photoelectrochemistry and Raman spectroscopic characterization on the surface oxide film of nickel electrode in 30 wt.% KOH solution

The oxide films of nickel electrode formed in 30 wt.% KOH solution under potentiodynamic conditions were characterized by means of electrochemical, in situ PhotoElectrochemistry Measurement (PEM) and Confocal Microprobe Raman spectroscopic techniques. The results showed that a composite oxide film was produced on nickel electrode, in which aroused cathodic or anodic photocurrent depending upon polarization potentials. The cathodic photocurrent at −0.8 V was raised from the amorphous film containing nickel hydroxide and nickel monoxide, and mainly attributed to the formation of NiO through the separation of the cavity and electron when laser light irradiates nickel electrode. With the potential increasing to more positive values, Ni₃O₄ and high-valence nickel oxides with the structure of NiO₂ were formed successively. The composite film formed in positive potential aroused anodic photocurrent from 0.33 V. The anodic photocurrent was attributed the formation of oxygen through the cavity reaction with hydroxyl on solution interface. In addition, it is demonstrated that the reduction resultants of high-valence nickel oxides were amorphous, and the oxide film could not be reduced completely. A stable oxide film could be gradually formed on the surface of nickel electrode with the cycling and aging in 30 wt.% KOH solution.     

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.     

纳米Pd修饰WO3电极及其催化析氢性能

将非晶结构Fe-W合金浸泡在0.5 mol/LH2SO4溶液中,在电极表面形成WO3层,厚度约720nm。通过化学法在半导体WO3上沉积金属Pd,扫描电镜和扫描隧道显微镜测试结果表明,沉积5m in后Pd的平均颗粒尺寸约为10 nm。在0.5 mol/LH2SO4溶液中的极化曲线测试结果表明,纳米Pd修饰WO3电极具有优异的电催化及光催化析氢活性,在500W碘钨灯照射下,电流密度为6 A/dm2时电极的析氢过电位减小30 mV以上。     

Potentiostatic electrodeposition of cuprous oxide thin films for photovoltaic applications

Potentiostatic deposition of Cu₂O thin films on glass substrates coated with F-doped SnO₂ from an alkaline electrolyte solution (pH 12.5) containing copper (II) sulfate and lactic acid was studied for fabrication of a Cu₂O/Al-doped ZnO (AZO) heterojunction solar cell. The band gap of the electrodeposited Cu₂O films was determined by photoelectrochemical measurements to be around 1.9 eV irrespective of the applied potentials. The solar cells with a glass/FTO/Cu₂O/AZO structure were fabricated by sputtering an AZO film onto the Cu₂O film followed by deposition of an Al contact by vacuum evaporation. The highest efficiency of 0.603% was obtained with a Cu₂O film deposited at −0.6 V (vs. Ag/AgCl). This was attributed to better compactness and purity of the Cu₂O film than those of the Cu₂O films deposited at other potentials.     

The effect of the hydrothermal treatment with aqueous NaOH solution on the photocatalytic and photoelectrochemical properties of visible light-responsive TiO2 thin films

The effect of the hydrothermal treatment with aqueous NaOH solution on the photoelectrochemical and photocatalytic properties of visible light-responsive TiO₂ thin films prepared on Ti foil substrate (Vis-TiO₂/Ti) by a radio-frequency magnetron sputtering (RF-MS) deposition method has been investigated. The hydrothermally treated Vis-TiO₂/Ti electrodes exhibited a significant increase in their photocurrent under UV and visible light irradiation as compared to untreated Vis-TiO₂/Ti electrode. SEM investigations revealed that the surface morphology of Vis-TiO₂/Ti are drastically changed from the assembly of the TiO₂ crystallites to the stacking of nanowires with diameters of 30–50 nm with increasing hydrothermal treatment time (3–24 h), accompanying the increase in their surface area. The separate evolution of H₂ and O₂ from water under solar light irradiation was successfully achieved using the Vis-TiO₂/Ti/Pt which is hydrothermally treated for 5 h, while the H₂ evolution ratio was 15 μmol h⁻¹ in the early initial stage, corresponding to a solar energy conversion efficiency of 0.23%.     

Surface graft copolymerization of 2‐hydroxyethyl methacrylate onto low‐density polyethylene film through corona discharge in air

The corona discharge technique was explored as a means of forming chemically active sites on a low‐density polyethylene (LDPE) film surface. The active species thus prepared at atmospheric pressure in air was exploited to subsequently induce copolymerization of 2‐hydroxyethyl methacrylate (HEMA) onto LDPE film in aqueous solution. The results showed that with the corona discharge voltage, reaction temperature, and inhibitor concentration in the reaction solution the grafting degree increased to a maximum and then decreased. As the corona discharge time, reaction time, and HEMA concentration in the reaction solution increased, the grafting degree increased. With reaction conditions of a 5 vol % HEMA concentration, 50°C copolymerization temperature, and a 2.0‐h reaction time, the degree of grafting of the LDPE film reached a high value of 158.0 μg/cm² after treatment for 72 s with a 15‐kV voltage at 50 Hz. Some characteristic peaks of the grafted LDPE came into view at 1719 cm^?1 on attenuated total reflectance IR spectra (C?O in ester groups) and at 531 eV on electron spectroscopy for chemical analysis (ESCA) spectra (O_1s). The C_1s core level ESCA spectrum of HEMA‐grafted LDPE showed two strong peaks at ～286.6 eV (? C ? O? from hydroxyl groups and ester groups) and ～289.1 eV (O?C ? O? from ester groups), and the C atom ratio in the ? C? O? groups and O?C? O groups was 2:1. The hydrophilicity of the grafted LDPE film was remarkably improved compared to that of the ungrafted LDPE film. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2881–2887, 2001     

用MO-CVD技术制备金属氧化物薄膜及其光电化学行为

有机金属化学汽相沉积(MO-CVD)技术是一种新型薄膜材料制备技术,它优于目前通常采用的一般CVD和物理方法。主要优点:采用金属有机化合物为物质源,选择的范围比较大,其中含有易断裂的M-C键,易发生气相热分解氧化反应,成膜温度比较低,反应副产物仅有易挥发的碳氢化合物,使成膜环境无污染,易获得优质膜。因该技术是化学成膜,排除了物理方法中固有的不易控制化学计量的问题,易获得优质膜层。     

Surface activation of manganese oxide electrode for oxygen evolution from seawater

Utilizing the fact that the equilibrium potential of oxygen evolution is lower than that of chlorine evolution, oxygen evolution in seawater electrolysis was enhanced by decreasing the polarization potential under galvanostatic conditions through increasing the effective surface area of manganese oxide electrodes. Electrodes were prepared by a thermal decomposition method. IrO2-coated titanium (IrO2/Ti electrode) was used as the substrate on which manganese oxide was coated (MnOX/IrO2/Ti electrode). Subsequently, oxide mixtures of manganese and zinc were coated (MnOX–ZnO/MnOX/IrO2/Ti electrode). The effective surface area of the MnOX–ZnO/MnOX/IrO2/Ti electrodes was increased by selective dissolution of zinc (leaching) into hot 6M KOH. The oxygen evolution efficiency of the MnOX/IrO2/Ti electrode was 68–70%. Leaching of zinc from the MnOX–ZnO/MnOX/IrO2/Ti electrodes with 25mol% or less zinc led to a significant increase in the oxygen evolution efficiency. The maximum efficiency attained was 86% after leaching of zinc from the MnOX–25mol%ZnO/MnOX/IrO2/Ti electrode. However, large amounts of zinc addition, such as 40mol% or more are detrimental because of a decrease in the oxygen evolution efficiency. This is due to the formation of a double oxide, ZnMnO3, which is hardly dissolved in hot 6M KOH.