Photocatalytic defluorination of perfluorooctanoic acid by surface defective BiOCl: Fast microwave solvothermal synthesis and photocatalytic mechanisms

There is an urgent need for developing cost-effective methods for the treatment of perfluorooctanoic acid(PFOA)due to its global emergence and potential risks.In this study,taking surface-defective BiOCl as an example,a strategy of surface oxygen vacancy modulation was used to promote the photocatalytic defluorination efficiency of PFOA under simulated sunlight irradiation.The defective BiOCl was fabricated by a fast microwave solvothermal method,which was found to induce more surface oxygen vacancies than conventional solvothermal and precipitation methods.As a result,the asprepared BiOCl showed significantly enhanced defluorination efficiency,which was 2.7 and33.8 times higher than that of BiOCl fabricated by conventional solvothermal and precipitation methods,respectively.Mechanistic studies indicated that the defluorination of PFOA follows a direct hole(h~+)oxidation pathway with the aid of·OH,while the oxygen vacancies not only promote charge separation but also facilitate the intimate contact between the photocatalyst surface and PFOA by coordinating with its terminal carboxylate group in a bidentate or bridging mode.This work will provide a general strategy of oxygen vacancy modulation by microwave-assisted methods for efficient photocatalytic defluorination of PFOA in the environment using sunlight as the energy source.     

Photocatalytic oxidation of propoxur in aqueous titanium dioxide suspensions

Abstract

The photocatalytic oxidation of propoxur, a nitrogen‐containing pesticide, has been investigated using aqueous TiO₂ suspensions as catalyst in this study. The operating variables considered in the study were initial pH, temperature, [H₂O₂] and TiO₂ loading. Results showed that 1 g/l of TiO₂ was the optimum dosage for oxidizing propoxur in this system. Hydrogen peroxide can increase the oxidation rate with increasing its initial concentration. There was no obvious difference in the rate of propoxur oxidation at the initial pH of 4, 6 and 9, and the final pHs of reaction solutions were around 5.5. However, propoxur degraded slower at initial pH 2, and the pH did not vary during the period of photocatalytic reaction. The photocatalytic oxidation of propoxur using TiO₂ suspensions as the photocatalyst was reaction‐controlled as indicated by the activation energy.     

不同基质负载的TiO2薄膜光催化性能的比较

采用溶胶凝胶法制备出纳米TiO2粉末、ITO导电玻璃和普通玻璃负载的纳米TiO2薄膜光催化刺。通过对乙酸的降解实验表明：镀膜4次的TiO2／ITO薄膜的催化活性大约是TiO2／giass薄膜的2倍,与等负载量的TiO2粉末相比也具有较高的光催化活性。使用10次后,TiO2／ITO薄膜和TiO2／glass薄膜的光催化活性分别降低了25％和12％。但经再生后,催化活性可恢复至90％左右。     

Detoxification of aqueous solutions of the pesticide “Sevnol” by solar photocatalysis

The solar photodegradation of Sevnol, a commercial pesticide, based on carbaryl as active principle, was studied. Experiments have been carried out at laboratory and at pilot plant scale using titanium dioxide as catalyst. Complete dissappearance of carbaryl was achieved, while total mineralisation required longer irradiation. Active sludge respirometry showed significant detoxification of the solution. Finally, results obtained with commercial Sevnol were consistent with those of pure carbaryl, although the reaction was slower.     

Azo-dyes photocatalytic degradation in aqueous suspension of TiO2 under solar irradiation

The photodegradation of two common and very stable azo-dyes, i.e. methyl-orange (C₁₄H₁₄N₃SO₃Na) and orange II (C₁₆H₁₁N₂SO₄Na), is reported. The photocatalytic oxidation was carried out in aqueous suspensions of polycrystalline TiO₂ irradiated by sunlight. Compound parabolic collectors, installed at the “Plataforma Solar de Almería” (PSA, Spain) were used as the photoreactors and two identical reacting systems allowed to perform photoreactivity runs for the two dyes at the same time and under the same irradiation conditions. The disappearance of colour and substrates together with the abatement of total organic carbon content was monitored. The main sulfonate-containing intermediates were found to be in lower number in respect to those obtained under artificial irradiation. In particular there were no more evidence of the presence of hydroxylated transients. The dependence of dye photooxidation rate on: (i) substrate concentration; (ii) catalyst amount; and (iii) initial pH was investigated. The influence of the presence of strong oxidant species (H₂O₂, S₂O₈²⁻) and some ions (Cl⁻, SO₄²⁻) on the process was also studied.     

微波辅助光催化降解氯酚类污染物的研究

研究了溶液中4-氯酚(4CP)、2-氯酚(2CP)、4-氯-3-甲基酚(4C3MP)、2,4-二氯酚(2,4-DCP)、2,4,6-三氯酚(2,4,6-TCP)和五氯酚(PCP)的微波辅助光催化降解(MW/PCO).结果表明,6种氯酚(CPs)光降解速率与分子中Cl原子取代的数目、位置等分子结构性质有关,单氯酚比多取代氯酚易光解.MW/PCO降解4CP的主要中间产物为苯酚、氯苯、对苯醌、对苯二酚等,降解PCP的主要中间产物为2,3,5,6-四氯对苯醌、2,3,4,6-四氯对苯二酚、四氯酚.CPs降解的机制是紫外光降解和羟基自由基 (·OH)亲电子加成脱氯过程.     

光催化降解甲胺磷的研究

用离子色谱法检测光催化降解甲胺磷的最终产物PO4^3-、SO4^2-、NH4^ 、NO3^-，它们随光照时间的生成量不同，80min时甲胺磷分子中的N原子已完全矿化为NH4^ 和NO3^-，而P、S原子矿化为PO4^3-、SO4^2-则较慢且不同步，刚开始，SO4^2-生成量大于PO4^3-，100min后则PO4^3-生成量大于SO4^2-，经气相色谱及CODCr分析，均表明在甲胺磷光催化降解过程中存在中间产物，用气质联用仪（GC-MS）检测出中间产物CH3-SO2-SCH3及CH3S-SCH3，提出光催化降解甲胺磷的可能途径。     

半导体光催化降解气态三氯甲烷的研究

以１５Ｗ主波长为２５４ｎｍ的紫外杀菌灯为光源，锐钛型二氧化钛为催化剂、能够使气态三氯甲烷发生半导体光催化降解反应。空气流量和光强对反应有较大影响。反应产物中氯离子和氢离子浓度基本相符。     

利用太阳光与固定床型光反应器处理有机废水的研究

自制了一种模拟工业处理废水的光催化反应器。该反应器将TiO2固定在玻璃板上，以太阳光为光源，以邻氯苯酚为处理对象，研究了邻氯苯酚水溶液光降解的可行性。结果表明，在实验条件下，该系统能对邻氯苯酚水溶液进行有效的光解。光照60分钟后．其降解率可达87％。此外还探讨了流速、邻氯苯酚溶液初始浓度和初始pH值对光解反应的影响。     

Photocatalytic degradation of aqueous Methyl Orange using nitrogen-doped TiO2 photocatalyst prepared by novel method of ultraviolet-assisted thermal synthesis

A nitrogen-doped titanium dioxide composite photocatalyst(N–TiO_2) with heterojunction structures is synthesized by three different approaches: a novel UV-assisted thermal synthesis, annealing, and microwave technique. Photocatalytic activities of synthesized photocatalysts are evaluated by the degradation of Methyl Orange under ultraviolet light types A(UV-A), B(UV-B), and C(UV-C), visible light, and direct sunlight irradiation. Results show that by using N–TiO_2 photocatalyst prepared by the UV-assisted thermal synthesis and annealing, the degradation increases by 16.5% and 20.4%, respectively, compared to that by bare TiO_2. The best results are obtained at a nitrogen to TiO_2 mass ratio of 0.15(N:TiO_2). The enhancement of the photocatalytic activity observed in the visible range is mainly attributed to the increasing separation rate of photogenerated charge carriers. The novel UV-assisted thermal synthesis has produced encouraging results as a preparation method for the nitrogen-doped TiO_2 photocatalyst; thus, further studies are recommended for process optimization, immobilization, and scale-up to evaluate its applicability in wastewater treatment.