Synthesis,characterization, and visible-light photocatalytic activity of transition metals doped ZTO nanoparticles

Transition metals doping has been proved to be a feasible way for tuning the physical properties on the surface and bulk of nanomaterials and also for the good performance in decontamination of emerging pollutants. In this context, doped samples of zinc tin oxide or zinc stannate nanoparticles (ZTO NPs) by several transition metals were synthesized in order to enhance the optical absorbance with the aims of reducing the band gap and therefore ameliorated their photocatalytic activity. They were characterized by the X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), diffuse reflectance spectroscopy, Raman spectroscopy and photoluminescence. The XRD patterns and the microscopic observations showed the formation of spherical nanoparticles with an average size of about 30 nm and highly pure ZTO phase with an inverse spinel structure. The Raman spectra were dominated by bands relatives to the F2g (2) and A1g symmetries modes of inverse spinel structure. The band gap Eg is estimated to be 3.75 eV for the undoped sample, and 3.67, 3.64, 3.78 and 3.21 eV, for 2% Fe, 2% Mg, 2% Gd, and 2% Mn doped ZTO samples, respectively.Furthermore, the undoped ZTO NPs have the intrinsic problem of recombination of photogenerated charge carriers. We have shown that the reduction of the band gap and oxygen vacancies resulting from the doping effect could be a useful tool for trapping and avoid the recombination of electrons coming from photosensitized rhodamine B (RhB) under visible light irradiation. Owing to the structural advantages and low band gap, 2% Mn doped ZTO NPs, with the kinetic rate constants k of 0.024 min⁻¹, show enhanced performance for the elimination of RhB in aqueous solution compared to undoped and other doped ZTO NPs.     

Visible light-activated degradation of microcystin-LR by ultrathin g-C3N4 nanosheets-based heterojunction photocatalyst

Microcystins (MCs) is a harmful toxin generated by blue-green algae in water, which has seriously threatened the ecological safety of water and human body. It is urgent to develop new catalysts and techniques for the degradation of MCs. A feasible electrostatic self-assembly method was carried out to synthesize BiVO₄/g-C₃N₄ heterojunction photocatalyst with highly efficient photocatalytic ability, where BiVO₄ nanoplates with exposed {010} facets anchored to the g-C₃N₄ ultrathin nanosheets. The morphology and microstructure of the heterojunction photocatalysts were identified by XRD, SEM, TEM, XPS, and BET. The g-C₃N₄ nanosheets have huge surface area over 200 m²/g and abundant mesoporous ranging from 2-20 nm, which provides tremendous contact area for BiVO₄ nanoplates. Meanwhile, the introduction of BiVO₄ led to red-shift of the absorption spectrum of photocatalyst, which was characterized by UV-vis diffuse reflection spectroscopy (DRS). Compared with pure BiVO₄ and g-C₃N₄, the BiVO₄/g-C₃N₄ heterojunction shows a drastically enhanced photocatalytic activity in degradation of microcystin-LR (MC-LR) in water. The MC-LR could be removed within 15 minutes under the optimal ratio of BiVO₄/g-C₃N₄. The outstanding performance of the photocatalyst is attributed to synergetic effect of interface Z-scheme heterojunction and high active facets {010} of BiVO₄ nanoplates, which provides an efficient transfer pathway to separate photoinduced carriers meanwhile endows the photocatalysts with strong redox ability.     

改性纳米TiO2光催化降解苯酚活性的研究

在装有紫外光的光催化反应器中，用锐钛型纳米TiO2为光催化剂，进行了苯酚水溶液的光催化降解性能的研究。考察了溶液的pH值、纳米TiO2用量、镍（Ni^2＋）掺杂量、苯酚的初始质量浓度等因素对苯酚水溶液光催化降解过程的影响。结果表明，在pH值为7时，苯酚水溶液的降解率达95％以上，强酸和强碱条件均不利于苯酚的降解。当TiO2用量为50mg，UV辐照40min时，200mL质量浓度为50mg／L的苯酚水溶液的降解率为96．3％；当TiO2用量为150mg，UV辐照60min时，200mL质量浓度100mg／L的苯酚水溶液的降解率为95．8％。镍掺杂增加了TiO2的光催化活性，用质量分数为10％的二氯化镍水溶液掺杂制备的复合光催化剂，苯酚水溶液的降解率比未掺杂时增加13．6％。     

二氧化钛纳米晶的制备及光催化活性研究

本文用溶胶—凝胶法制备了不同晶相的TiO2纳米晶，将其负载于镍网上，以苯酚的降解为模型反应，研究对比了不同晶相TiO2纳米晶的光催化活性。结果表明，纯锐钛矿相的TiO2纳米晶的降解能力要强于锐钛矿与金红石混合相的TiO2纳米晶。     

微波热液法制备光催化TiO2功能材料

采用微波加热法，研究了钛配离子热分解水解反应的规律。结果表明，水解产物在大气气氛和300℃下煅烧2h，所得产物为锐钛型TiO2粉末。在紫外线照射下，乙酸经Ti02光催化反应12h后，残余量小于初始量的20％。     

Photoelectrocatalytic humic acid degradation kinetics and effect of pH,applied potential and inorganic ions

This study addresses the removal of humic acid (HA) dissolved in an aqueous medium by a photoelectrocatalytic process. UV₂₅₄ removal and the degradation of color (Vis₄₀₀) followed pseudo‐first order kinetics. Rate constants were 1.1 × 10^?1 min^?1, 8.3 × 10^?2 min^?1 and 2.49 × 10^?2 min^?1 (R² > 0.97) for UV₂₅₄ degradation and 1.7 × 10^?1 min^?1, 6.5 × 10^?2 min^?1 and 2.0 × 10^?2 min^?1 for color removal from 5 mg dm^?3, 10 mg dm^?3 and 25 mg dm^?3 HA respectively. Following a 2 h irradiation time, 96% of the color, 98% of the humic acid and 85% of the total organic carbon (TOC) was removed from an initial 25 mg dm^?3 HA solution in the photoanode cell. Photocatalytic removal on the same photoanode was also studied in order to compare the two methods of degradation. Results showed that the photoelectrocatalytic method was much more effective than the photocatalytic method especially at high pH values and with respect to UV₂₅₄ removal. The effect of other important reaction variables, eg pH, external potential and electrolyte concentration, on the photoelectrocatalytic HA degradation was also studied. Copyright © 2003 Society of Chemical Industry     

Photocatalytic degradation of 2,2‐bis(4‐hydroxy‐3‐methylphenyl) propane (BPP) based on molecular recognition interaction

BACKGROUND: Endocrine disruptors in the aquatic environment and their potential adverse effects are currently issues of concern. One of these endocrine disruptors is 2,2‐bis(4‐hydroxy‐3‐methylphenyl)propane (BPP). In this work the molecular recognition interaction of BPP with β‐cyclodextrin (β‐CD) was studied using IR spectroscopy and steady state fluorescence spectroscopy, and the photocatalytic degradation behaviour of BPP based on molecular recognition interaction was investigated in a TiO₂/UV–visible (λ_max = 365 nm) system. This might provide a new method for the treatment of some organic pollutants in wastewater. RESULTS: β‐CD reacts with BPP to form a 1:1 inclusion complex, the formation constant of which is 4.94 × 10³ L mol^?1. The photodegradation rate constant of BPP after molecular recognition by β‐CD showed a 1.42‐fold increase in the TiO₂/UV–visible (λ_max = 365 nm) system. The photodegradation of BPP depended on the concentration of β‐CD, the pH value, the gaseous medium and the initial concentration of BPP. The photodegradation efficiency of BPP with molecular recognition was higher than that without molecular recognition. After 100 min of irradiation the mineralisation efficiency of BPP after molecular recognition by β‐CD reached 94.8%, whereas the mineralisation efficiency of BPP before molecular recognition by β‐CD was only 40.6%. CONCLUSION: The photocatalytic degradation of BPP after molecular recognition by β‐CD can be enhanced in the TiO₂/UV‐visible (λ_max = 365 nm) system. This enhancement is dependent on the enhancement of the adsorption of BPP, the moderate inclusion depth of BPP in the β‐CD cavity and the increase in the frontier electron density of BPP after molecular recognition. Copyright © 2008 Society of Chemical Industry     

A new synthesis procedure for titanium-containing zeolites under strong alkaline conditions and the catalytic activity for partial oxidation and photocatalytic decomposition

A new synthesis procedure for titanium-containing aluminosilicate zeolites has been obtained using a clear colloidal dispersion (sol) which was prepared with titanium isopropoxide, water, hydrochloric acid and colloidal silica, Ludox. When NaY, KL, offretite, mordenite and ZSM-5 zeolites were crystallized from the sol following conventional hydrothermal crystallization procedures, all the aluminosilicate zeolites showed the same X-ray absorption fine structure at the Ti K edge indicating framework Ti. The zeolites showed remarkable catalytic activity for the partial oxidation of cyclohexene using H₂O₂ as an oxidant and the photocatalytic decomposition of trichloroethene using water.     

同轴电纺法TiO2/g-C3N4的制备及光催化性能研究

传统的静电纺丝法使用单一的毛细管状喷头喷丝,通常用于制备实心且表面光滑单一组分的纳米纤维,无法得到具有多种功能性结构的复合材料,应用范围较窄。以酞酸丁酯和尿素为原料,采用同轴静电纺丝法成功制备了TiO₂/g-C₃N₄复合材料,并用X射线衍射（XRD）、傅里叶变换红外光谱（FTIR）、紫外可见漫反射光谱（UV-vis DRS）、场发射扫描电子显微镜（SEM）和Brunauer-Emmett-Teller （BET）分析对样品进行了表征,通过光催化降解亚甲基蓝溶液（MB）研究了不同g-C₃N₄添加量对TiO₂/g-C₃N₄复合材料光催化性能的影响。实验结果表明,采用同轴静电纺丝法结合500℃煅烧工艺成功制备了大比表面积及高光催化性能的TiO₂/g-C₃N₄复合材料。当g-C₃N₄添加量为0.15 g时,TiO₂/g-C₃N₄复合材料对亚甲基蓝溶液（MB）的光催化降解效率可达93.8%,且经过5次重复实验后降解率仍可达80%以上。     

WO3/C/Ag3PO4复合材料光催化降解双酚A

以磷酸法制备的活性炭、WO3、AgNO3、Na2HPO4为原料,采用共沉淀法制备WO3/C/Ag3PO4复合材料。采用X 射线衍射（XRD）、傅里叶红外光谱（FT-IR）、光电子能谱（XPS）、扫描电镜（SEM）、透射电镜（TEM）和固体紫外漫反射（UV-DRS）技术对其进行表征。结果表明,Ag3PO4与WO3之间形成异质结。在可见光照射下,以双酚A(BPA)模拟污染物,评价WO3/C/Ag3PO4复合材料的光催化降解性能,并提出 WO3/ C/Ag3PO4 复合材料对BPA的光降解机理。结果表明,在一系列光催化剂中, 23% WO3/ 7% C/ Ag3PO4 复合材料在可见光下对10 mg/L BPA水溶液的降解率在90 min分钟达到95%,明显高于单一的Ag3PO4和WO3。经过3次循环重复,BPA的降解率仍能保持在74%,表明WO3/C/Ag3PO4光催化剂具有良好的稳定性。光催化机理表明,自由基?O- 2和h 在降解过程中起主要作用。