Enhancement of photocatalytic activity of sprayed nitrogen-containing ZnO powders by coupling with metal oxides during the acetaldehyde decomposition

Colored N-containing MOx-ZnO (M = W, V) composite powders with high surface area were synthesized by spray pyrolysis. The nitrogen content was controlled from 600 to 3000 ppm by changing the powder ingredients and the spray pyrolysis temperature. Ultraviolet-visible spectra indicated that the N-containing MOx-ZnO powders absorbed not only ultraviolet light like pure ZnO powder, but also some visible-light. Acetaldehyde decomposition was used as a probe reaction to evaluate the photocatalysis of these MOx-ZnO powders. The photocatalytic activity of the N-containing ZnO powder was pronouncedly enhanced by the WO3 or V2O5 addition under both UV and visible-light irradiation. This enhancement was ascribed to the MOx acting as a sink for photogenerated electrons in the UV case, and to a synergistic effect of N-doping and MOx-ZnO coupling in the case of visible-light.     

Synthesis of BiVO4/TiO2 composites and evaluation of their photocatalytic activity under indoor illumination

BiVO₄/TiO₂ composites with different weight ratios have been prepared by coprecipitation-based reactions followed by either thermal or hydrothermal treatment with the aim of evaluating the TiO₂ photosensitization by BiVO₄. The obtained materials present in all cases the desired monoclinic phase of BiVO₄ and anatase phase of TiO₂. Visible light absorption increased with increasing amount of bismuth vanadate. XPS results reveal the surface enrichment of Ti with respect to the bulk composition in samples characterised by a higher content of BiVO₄. The photocatalytic activity of the prepared materials was tested for the degradation of isopropanol in the gas phase under indoor illumination conditions. Although none of the composites was able to improve the activity of TiO₂, the low BiVO₄ containing samples appear as more suitable for further synthesis tuning.     

不同晶面暴露的TiO2光催化降解蒽的性能及途径分析

多环芳烃是一类广泛分布于环境介质中、具有“三致性”的有机污染物,随着工业的迅速发展,其在水体中的污染日趋严重。光催化氧化法是去除这一类难降解有机污染物的有效方法。通过氙灯光源模拟太阳光,以不同晶面暴露的TiO2为催化剂,对蒽进行催化降解,研究其在不同晶面占主导的TiO2催化下的光降解机制,分析降解过程中间产物的生成途径。结果表明,蒽的光降解符合一级反应动力学模型,3种晶面占主导的TiO2降解蒽的速率顺序为：{101} > {010} > {001},用GC-MS检测到反应过程中的中间产物主要为蒽醌和蒽酮等,剖析了蒽在TiO2催化下的光降解途径,并进一步证实空穴和氧气是影响蒽光催化降解效率的主要活性物质,而·OH对其影响很小,其中{001}晶面暴露的TiO2主要通过表面富集的空穴促进蒽的降解及蒽醌的生成,{101}晶面暴露的TiO2主要通过吸附在其表面的氧气作为电子受体,生成超氧自由基等活性物质,进而氧化去除污染物。     

Comparison of methods for evaluation of activity of photocatalytic films

Objective

This work aims to investigate the correlation between the photocatalytic activity determined by methylene blue bleaching (DIN 52980), stearic acid degradation, and degradation of acetone in gas phase.

Method

The photocatalytic TiO₂ coatings included in this investigation ranged from thin commercially available coatings (Activ^TM and BioClean^TM) and ready to use suspensions (Nano-X PK1245) to lab-produced PVD and sol?Cgel coatings. XRD analysis of the photocatalytic coatings showed that all the coatings consisted of nanocrystalline anatase, although the thickness and porosity varied considerably.

Results

The study showed that the reproducibility of the activity measurements was good. However, more importantly, the investigation showed that there is a good correlation between the activities determined by the different methods even though the characteristics of the photocatalytic coatings and the organic probe molecules varied considerably.

Conclusion

The overall findings of this work suggest that there is a good correlation between the investigated methods. These results are promising for the future work concerning standardization of methods for determination of the activity of photocatalytic films.     

Comparison of photocatalytic degradation of dyes in relation to their structure

The photocatalytic degradation of a series of six acid dyes (Direct Red 80, Direct Red 81, Direct Red 23, Direct Violet 51, Direct Yellow 27, and Direct Yellow 50) has been tested compared in terms of color removal, mineralization, and toxicity (Lactuca sativa L. test) after photocatalysis on immobilized titanium dioxide. The dyes were examined at their natural pH and after hydrolysis at pH 12. Results show that hydrolysis decreases strongly the efficiency of color removal, that full mineralization takes much longer reaction time than color removal, and that toxicity is only very partially reduced. Some structural parameters, related to the structure and the topology of the dye molecules, could be correlated with the apparent color removal rates at natural pH.     

TiO2结构对光催化性能的影响及其提高的途径

文中介绍了TiO2的晶体结构与表面态性质对其光催化活性的影响,综述了近年来有关贵金属沉积、金属离子掺杂、表面光敏化、复合半导体、表面酸化和无机模板合成纳米粒子等改性技术的研究现状.还简单地介绍了电化学、微波场和超声波等外加场辅助光催化的进展.     

Effect of ZnFe2O4 doping on the photocatalytic activity of TiO2

The photocatalytic oxidation of the organic pollutants with the TiO2 as photocatalyst has been widely studied in the world, and many achievements have been got. The degradation of pollutants is highly related with the photocatalytic activity of TiO2. It is demonstrated that doping ions or oxides to TiO2 is one way to enhance the photocatalytic activity of TiO2. In this paper, the ZnFe2O4-doped TiO2 nanoparticles were prepared from butyl titanate by a sol-gel method and characterized by means of X-ray diffraction (XRD) and transmission electron microscopy (TEM). The results showed that when TiO2 was doped with ZnFe2O4, its particle size will decrease and its crystal structure will partly transform from anatase to rutile. The photocatalytic activity of the elaborated powders was studied following the degradation of Rhodamine B. The results showed that doping ZnFe2O4 to TiO2 will enhance the photocatalytic activity of TiO2 and that ZnFe2O4-doped TiO2 in the coexistence of anatase and rutile has higher efficiency for the degradation of Rhodamine B than that in the anatase phase alone. Also the different role of O2 in the direct photolysis and photocatalysis of Rhodamine B was discussed.     

Characteristics of photocatalytic oxidation of toluene, benzene, and their mixture

The investigation of the photocatalytic oxidation (PCO) of multicomponent volatile organic compounds (VOCs) is very important to the application of PCO technology, because there is seldom a single VOC component in indoor air. In this paper, the characteristics of binary indoor VOCs, toluene and benzene, were experimentally studied using a mass transfer based method that we developed. The concentration ranges for toluene and benzene were 4.48-27.4 mg/m3 and 1.82-4.08 mg/m3, respectively. We found the following: (1) the PCO of each individual contaminant studied obeys the unimolecular form of the Langmuir-Hinshelwood (L-H) rate form; (2) the PCO of the binary contaminants follow the competitive adsorption L-H rate form; (3) the reaction-coefficient for PCO of individual contaminants differs from that in the competitive adsorption L-H rate form; and (4) the component impact factor of A to B, put forward in this paper, is a useful parameter describing the influence of A on the reaction coefficient of B, and it was found that the impact factor of toluene (a chemically active component) on benzene (a chemically stable component) is high, and the impact factor of benzene on toluene is low.     

The enhancement of TiO2 photocatalytic activity by hydrogen thermal treatment

In this study, conventional TiO2 powder was heated in hydrogen (H2) gas at a high temperature as pretreatment. The photoactivity of the treated TiO2 samples was evaluated in the photodegradation of sulfosalicylic acid (SSA) in aqueous suspension. The experimental results demonstrated that the photodegradation rates of SSA were significantly enhanced by using the H2-treated TiO2 catalysts and an optimum temperature for the H2 treatment was found to be of 500-600 degrees C. The in situ electron paramagnetic resonance (EPR) signal intensity of oxygen vacancies (OV) and trivalent titanium (Ti3+) associated with the photocatalytic activity was studied. The results proved the presence of OV and Ti3+ in the lattice of the H2-treated TiO2 and indicated that both were contributed to the enhancement of photocatalytic activity. Moreover, the experimental results presented that the EPR signal intensity of OV and Ti3+ in the H2-treated TiO2 samples after 10 months storage was still significant higher than that in the untreated TiO2 catalyst. The experiment also demonstrated that the significant enhancement occurred in the photodegradation of phenol using the H2-treated TiO2.     

BiVO4催化剂的离子液体辅助水热合成及其可见光催化活性

采用溴化1-丁基-3-甲基咪唑([Bmim]Br)离子液体辅助水热合成法制备了光催化剂BiVO4。以高压氙灯作为可见光源,亚甲基蓝为目标污染物,考察反应温度、pH、反应时间和离子用量等制备条件对BiVO4的可见光催化活性的影响,确定了最佳制备条件。并采用XRD、SEM和UV-Vis漫反射等分析手段对催化剂的晶相、形貌和光学特性进行了表征。结果表明,在离子液体加入量为2 mL、pH=4、反应温度为180℃、反应时间为4 h 的条件下,制得的BiVO4催化剂的可见光光催化活性最高。制得的BiVO4为单斜相,呈分散的、大小均匀的片状,在200~500 nm范围有一个较宽的强吸收平台,具有良好的可见光催化活性,在可见光照射下对浓度为5 mg/L的亚甲基蓝的光催化脱色率达97%以上。     

Mg-Al-LDHs复合促进CdS光催化剂的可见光催化活性

采用过饱和沉淀法制备了镁铝层状双氢氧化物(Mg-Al-LDHs)载体,并通过水热法将高分散纳米CdS粒子负载于其上,得到了可见光响应和高活性的CdS/Mg-Al-LDHs复合光催化材料。通过XRD、SEM、FT-IR、UV-Vis-DRS和BET等技术对催化剂进行了表征。结果表明,水热过程中,CdS纳米粒子的插层使Mg-Al-LDHs发生了剥离,由于剥离态Mg-AlLDHs较大的负载表面,与纯CdS纳米颗粒相比,负载的CdS纳米粒子的分散度较高、晶粒粒径较小且光吸收明显蓝移,这不仅增加了复合催化剂的活性位点,而且提高了负载CdS纳米粒子的光生电子-空穴对的氧化还原能力,从而使复合催化剂具有较高的反应活性。可见光条件下(λ420 nm),CdS/Mg-Al-LDHs复合材料光催化降解亚甲基蓝(MB)的活性明显高于纯CdS,当CdS的负载量为50%时,降解MB的活性与纯CdS相比提高了2.4倍。     

Carbofuran degraded by iron-doped anatase: Weakening the cholinesterase inhibitory activity in the photoproducts mixture

Carbofuran is a toxic carbamate pesticide, and its use has increased in recent years. While marketing information indicates stability in different chemical media, carbofuran exhibits relative photolability. The aim of this research was to decompose carbofuran and to identify the photoproducts achieved when two different doped titania photocatalysts were employed under UV irradiation. The iron-doped TiO₂ materials were obtained (a) via a hydrothermal method and (b) by an ultrasound-assisted sol–gel method. The precursors were TiOSO₄?xH₂O and Fe₃(NO₃)·9H₂O. X-ray studies confirmed that the anatase phase of the iron-doped TiO₂ resulted from the two preparation methods. The photocatalytic performance of the prepared materials was monitored by LC/ESI-QTOF-MS, enabling the identification of photoproducts: oxo-carbamates, hydroxylated benzofuranes, a carboxamide, and one amine. By using the iron-doped TiO₂ materials, 2,2-dimethyl-2,3-dihydrobenzofuran-3,7-diol was the most abundant photoproduct, and N,2,2-trimethyl-2,3-dihydrobenzofuran-7-amine was the only compound that had not been previously reported in the photolysis and photocatalysis of carbofuran. The product 3-hydroxy carbofuran, a cholinesterase inhibitor, was quantified and was found to be transformed into compounds that lack this inhibitive property.     

石英棒负载TiO2光催化膜的制备、表征与降解性能

利用浸涂法在石英光导棒上制得了TiO2光催化膜.用扫描电镜(SEM)、X射线衍射(XRD)等方法对膜的形貌和晶相组成进行了表征,以苯酚为模型污染物考察了膜的活性.结果表明,所制得的TiO2膜催化剂主要由锐钛矿和金红石2种晶相组成;光催化降解苯酚的效果明显优于直接光解;当苯酚初始浓度为0.98 mg/L时,反应2.5 h后的降解率为86%.     

掺碘二氧化钛薄膜自组装制备、表征及光催化性能

通过自组装技术在低温液相反应体系中制备出大尺寸纳米二氧化钛及其掺碘薄膜。使用XRD、TEM、荧光发射光谱仪、激光拉曼光谱仪等手段对样品进行表征,发现掺I^5＋后的二氧化钛薄膜在可见光区也表现出明显的响应,而且合成的I^5＋／TiO2纳米薄膜在TEMggNT其晶型显示为金红石型,并且碘掺杂后样品的拉曼光谱强度减弱,峰位蓝移且宽化。掺杂I^5＋原溶液浓度为2mmol／L时,其可见光下光催化效果最优,5h后降解率可达到95％,较未掺杂的TiO2纳米薄膜提高了40％,I^5＋掺杂明显提高了TiO2对甲基橙溶液的光催化降解效率。     

B,N和Ce共掺杂TiO2催化剂光催化活性研究

采用溶胶-凝胶法制备出B,N和Ce共掺杂TiO2光催化剂,并用XRD、SEM等表征了其结构特征。以酸性大红染料溶液的光催化降解为探针反应,考察了制备条件对共掺杂TiO2催化剂活性的影响。结果表明,在400℃,当B,N和Ce的原子比为1∶2∶0.1,焙烧3 h时,光催化剂活性最大,大红染料的降解率达到98%。     

可见光响应型CuO/BiVO4的光催化活性研究

采用浸渍法制备了CuO/BiVO4光催化剂,通过X射线衍射(XRD)、热重/差示扫描量热(TG/DSC)和傅立叶红外光谱(FTIR)对其进行了表征,并在可见光照射下考察了其光催化氧化亚甲基蓝(MB)的动力学特性。结果表明,Cu的掺杂并未改变BiVO4的晶型结构;Cu(NO3)2/BiVO4在热处理(30～300℃)过程中,NO3-已经完全分解,Cu最终以CuO的形式存在于CuO/BiVO4光催化剂体系中;掺杂不同量Cu的CuO/BiVO4中的Cu2+/Bi+(摩尔比)实测值与理论值相近,该系列光催化剂的合成过程具有较高的可信度;在可见光照射下,CuO/BiVO4光催化降解MB反应符合表观一级反应动力学特征;当Cu2+/Bi+为0.050时,反应动力学速率常数(k)达到最高值(0.4334h-1),此时的k比单体BiVO4作用下的提高了1.04倍;由于异质结的存在,CuO/BiVO4与单体BiVO4相比,电子和空穴的利用率大大增加,使得CuO/BiVO4的光催化活性较单体BiVO4有了大幅度提高。     

TiO2纳米管的水热合成表征及其光催化性能研究

采用水热化学反应的方法制备了TiO2纳米管,并采用TEM、XRD等分析手段对TiO2纳米管的形貌和晶相进行了表征,对比了管与粉的光催化性能.结果表明,采用该方法制得的TiO2纳米管的管径小、管形均匀,TiO2纳米管的光催化性能明显高于TiO2纳米粉.     

络合凝胶法合成Al掺杂纳米ZnO及其光催化性能

氧化锌(ZnO)纳米粉体是一种重要的可用来降解有机污染物的光催化剂。然而,纯的ZnO仅仅能够吸收紫外光和部分可见光,不能够充分利用太阳光。采用了一种络合凝胶法来合成掺杂Al的ZnO纳米粉体。所制备出来的纳米颗粒尺寸在20～50 nm之间,它不仅对波长范围在200～400 rm之间的紫外光有很强的吸收,而且对波长范围在4...     

Study on the photocatalytic reduction of dichromate and photocatalytic oxidation of dichlorvos

In this paper, dichromate and dichlorvos are selected as the deputies of inorganic and organic pollutants, respectively, and TiO2/beads is used as a photocatalyst. The effects of various parameters, such as the amount of the photocatalyst, H2O2 concentration, metal ions, anions, pH value, and organic compounds on the photocatalytic reduction of dichromate and photocatalytic oxidation of dichlorvos are studied. From the studies, the differences of the parameters effect on the photocatalytic degradation of organic and inorganic pollutants are obtained. The results show that the optimum amount of the photocatalyst used is 6.0 g cm(-3) for the photocatalytic reactions. With the addition of a small amount of H2O2, the photocatalytic reduction of dichromate is inhibited while the photocatalytic oxidation of dichlorvos is accelerated. With the addition of trace amounts of Fe3+ or Cu2+, both the reactions are accelerated, and with the addition of Zn2+ and Na+, no obvious effects on the reactions are observed. Acidic solution is favorable for the photocatalytic reduction of dichromate; and acidic and alkaline solutions are favorable for the photocatalytic oxidation of dichlorvos. Adding SO4(2-), the photocatalytic oxidation is accelerated and adding Cl- the reaction is inhibited; and with the addition of trace amounts of SO4(2-), Cl- and NO3-, no obvious effects on the photocatalytic reduction of dichromate are observed. With the addition of methanol and toluene, the photocatalytic reduction of dichromate is accelerated, and the photocatalytic oxidation of dichlorvos is inhibited. The possible roles of the additives on the reactions are also discussed.     

离子液体辅助水热法合成锡酸锌及其光催化性能

采用离子液体辅助水热法制备锡酸锌,考察了离子液体添加量对锡酸锌晶相、形貌及光催化性能的影响。通过XRD、TEM分别对锡酸锌的晶相和形貌进行研究。通过在紫外光照射下光催化降解亚甲基蓝溶液对锡酸锌的光催化性能进行表征。当[Emim]BF4添加量为0.5 mmol时,制得的八面体锡酸锌结晶度高且对染料亚甲基蓝有较高光催化降解能力。自由基捕获实验证明羟基自由基是光催化反应的主要活性物种。