Photocatalytic degradation of phosphamidon using Ag-doped ZnO nanorods

The photocatalytic degradation of the organo-phosphorous pesticide phosphamidon at low concentration in aqueous solution on Ag-doped ZnO nanorods was investigated. Nanosized Ag-doped ZnO rods were synthesized by using a microwave assisted aqueous method. High molecular weight polyvinyl alcohol was used as a stabilizing agent. Composition and structure were investigated using energy-dispersive X-ray spectroscopy (EDAX) and X-ray diffraction (XRD). The XRD pattern reveals that ZnO nanorods are of hexagonal wurtzite structure. The average crystallite size calculated from Scherrer's relation was found to be 30?nm. The effects of catalyst loading, pH value, and initial concentration of phosphamidon on the photocatalytic degradation efficiency using Ag-doped ZnO nanorods as a photocatalyst have been discussed. The results revealed that Ag-doped ZnO nanorods with a diameter of 30?nm showed highest photocatalytic activity at a surface density of 1?g?dm^?3. The catalyst doped with 0.2?mol% Ag is effective for the degradation of phosphamidon with visible light. This opens a new possibility to decompose pesticides that are present in wastewater.     

活性炭的光催化再生机理

通过研究催化剂的改性、再生温度、外加氧化剂对活性炭光催化再生反应速度的影响,结合光催化与活性炭的吸附理论,分析了活性炭的光催化再生机理．研究表明,活性炭的光催化再生由三个准一级反应组成．再生初期,再生反应速度由TiO2光催化降解吸附质的速率决定;反应的第二个阶段由光催化反应速度和吸附质的解吸速度共同决定;再生后期,再生反应速度由吸附质在活性炭上的解吸速率所决定．活性炭表面及其大孔内负载的Ti0：是使苯酚降解转化分解为无机物的降解中心．正是由于降解中心的存在及其表面苯酚浓度趋于零的状态,使得已吸附于活性炭孔内的苯酚不断向这个中心扩散,形成活性炭孔内苯酚的浓度差．在浓度差的作用下,扩散作用持续进行,导致活性炭内吸附位的逐步空出,从而实现活性炭的光催化再生．     

A simple and cheap method for preparation of coupled ZrO2/ZnO with high photocatalytic activities

The objective of this study was to prepare a new photocatalyst with high activities for degradation of organic pollutants. Coupled ZrO₂/ZnO photocatalyst was prepared with a simple precipitation method with cheap raw materials zinc acetate and zirconium oxychloride, and was characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Reactive brilliant red X-3B was used as a model compound to investigate the photocatalytic activity of synthesized catalysts in water under 254 nm UV irradiation. Results show that the optimal calcination temperature and coupling molar ratio of Zr were 350°C And 2.5%, respectively. At the calcination temperature of 350°C, ZrO₂ was dispersed on the surface of hexagonal ZnO in the form of amorphous clusters. The particle size of ZrO₂/ZnO decreased with the decrease of calcination temperature and the increase of Zr coupling amount. ZrO₂/ZnO has better photocatalytic activity for degradation of reactive brilliant red (RBR) X-3B than pure ZnO and P25-TiO₂.     

金属氧化物MoO3(WO3)和V2O5对烟气脱硝催化性能试验

以纳米级锐钛型TiO2为载体,负载V2O5和WO3(或MoO3)制备催化剂,研究不同催化剂组分对NO和NO2脱除率以及N2O生成量的影响.结果表明,V2O5的加入使得MoO3(WO3)/TiO2催化剂的活性和选择性得到了改善.MoO3(WO3)的加入主要是改善了催化剂表面的活性位数量,从而使得V2O5/TiO2基催化剂表现出更高的活性.     

掺铅TiO2薄膜的光催化活性及电化学性能

采用溶胶凝胶烧结工艺在玻璃表面制备铅离子多层掺杂的光催化复合TiO2薄膜,用XRD技术表征了该薄膜的晶型,并用电化学方法测定了该薄膜电极的伏安特性及交流阻抗性能．以光催化降解甲基橙溶液为模型反应,采用两种不同方式制备的铅离子多层掺杂TiO2薄膜具有很好的光催化活性,最佳掺杂浓度均为0．5％(Pb／Ti原子百分比),PbD0.5掺铅薄膜的最佳光催化降解甲基橙表观速率常数约是纯TiO2的2．52倍．铅离子掺杂TiO2薄膜表现出近表面处捕获光生电子或空穴,随后被捕获的电子或空穴迁移到TiO2薄膜表向参与光催化反应。     

Carbon nanotubes-incorporated MIL-88B-Fe as highly efficient Fenton-like catalyst for degradation of organic pollutants

CNTs were incorporated into MIL-88B-Fe to get a new Fenton-like catalyst (C@M). Fe(II) was introduced in C@M to get a fast initiation of Fenton-like reaction. Fe(II) content in C@M was related with oxygen-containing functional groups on CNTs. C@M shows efficient catalytic degradation of pollutants over a wide pH range. Iron-based metal organic frameworks have been verified to be efficient heterogeneous Fenton catalysts due to their open pore channels and highly uniform distribution of metallic centers. In these catalysts, however, the iron element is mainly in the form of Fe(III), which results in a process required to reduce Fe(III) to Fe(II) to initiate Fenton reaction. To address this problem, carbon nanotubes (CNTs) with electron-rich oxygen-functional groups on the surface were incorporated into the metal organic frameworks (MIL-88B-Fe) to improve Fe(II) content for an enhanced Fenton-like performance. The prepared CNT@MIL-88B-Fe (C@M) showed much stronger catalytic ability toward H₂O₂ than MIL-88B-Fe. The pseudo-first-order kinetic constant for phenol degradation by C@M (0.32 min^–1) was about 7 times that of MIL-88B-Fe, and even higher than or comparable to the values of reported heterogeneous Fenton-like catalysts. Moreover, the Fenton-like system could effectively degrade various kinds of refractory organic pollutants and exhibited excellent catalytic activity over a wide pH range (4–9). XPS analysis confirmed that Fe(II) content of the catalyst gradually increased with CNT loadings. Electron spin resonance analysis showed that the signal intensity (•OH) of C@M was much higher than MIL-88B-Fe, which was consistent with the degradation efficiency of pollutants. Furthermore, the Fe(II) content of the catalyst gradually increased along with the oxygen-functional group content of CNTs. The result demonstrated that oxygen-containing functional groups of CNTs have a significant impact on the enhanced catalytic performance of C@M. This study provides a new insight to enhance Fenton reaction by using nanocarbon materials.     

无机阳离子对TiO2光催化降解染料的影响

考察了6种无机阳离子对P-25 TiO2光催化降解染料的影响，结果发现，Cu^2 ，Mn^2 和Ni^2 对光催化反应有强烈的抑制作用，Ca^2 ，Mg^2 和Al^3 对光催化反应速率无明显的负影响．经X光电能谱(XPS)的分析，确定锰离子以氧化物的形式沉积在氧化钛表面，使催化剂不可逆的中毒．Cu^2 和Ni^2 通过俘获光致电子导致催化活性降低。     

TiO2,ZnO光催化降解庚烷的活性研究

采用XRD，SPS，XPS，BET技术对TiO2和ZnO超细粉进行了结构、性能测试、考察了不同粒径的超细粉和普通商品（体相）TiO2、ZnO对庚烷的气相光催化反应，结果表明，TiO2（锐钛矿型）光催化活性大于ZnO，锐钛矿型TiO2光催化活性较金红石型TiO2好，对于同一结构的粒子来说，粒径愈小，表面羟基含量愈高，光催化活性愈高，通过反应产物的分析，探讨了反应机理。     

不同活性物种对光催化降解水中邻苯二甲酸二甲酯动力学的贡献研究

采用光催化氧化技术对邻苯二甲酸二甲酯（DMP）进行降解研究,并在基础上考察了催化剂量,溶液pH和溶液初始浓度对降解速率的影响。且采用Langmuir-Hinshelwood动力学模型来描述DMP的光催化降解,研究表明DMP的光催化降解符合假一级动力学。系统研究了光催化降解DMP过程中不同活性物种对光催化反应速率的贡献,实验结果表明：在TiO2光催化降解DMP的过程中,？OH为主要的活性物种,其对DMP的降解速率贡献高于94%,而其它活性物种（ecb-,hvb＋,O2？-和H2O2）对光催化贡献较小。     

Photocatalytic inactivation of cyanobacteria with ZnO/gamma-AIO23 composite under solar light

Cyanobacteria were inactivated by using zinc oxide (ZnO)coated on the surface of gamma-AI2O3 as a photocatalyst and combining with sunlight. In vitro experiments indicate that axenic cultures of planktonic cyanobacteria lost their photosynthetic activity after photocatalyzed with sunlight exposure exceeding 24 hr. As for Oscillatoria tenuisa, nearly 92% of the cells lost their photosynthetic activity and the cell morphology was severely damaged during 24 hr of the reaction. However, in the case of Microcystis aeruginosa, lower photocatalytic inactivity efficiency was observed, which was attributed to extracellular polymeric secretions (EPSs) surrounding the cells. With a high dosage ZnO catalyst, the dissolved organic carbon (DOC) concentration of the Oscillatoria tenuisa suspension was increased by up to about 190% during photocatalysis. The increased suspension of DOC was attributed to increase liberation of extracellular organic and cell-wall polysaccharides during photocatalysis.     

Preparation of effective TiO<Subscript>2</Subscript>/Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> photocatalysts for water treatment

Photocatalytic oxidation using semiconductors is one of the advanced oxidation processes for degradation of organic pollutants in water and air. TiO₂ is an excellent photocatalyst that can mineralize a large range of organic pollutants such as pesticides and dyes. The main challenge is to improve the efficiency of the TiO₂ photocatalyst and to extend TiO₂ light absorption spectra to the visible region. A potential solution is to couple TiO₂ with a narrow band gap semiconductor possessing a higher conduction band such as bismuth oxide. Therefore, here we prepared Bi₂O₃/TiO₂ heterojunctions by the impregnation method with different Bi/Ti ratio. The prepared composites have been characterized by UV–Vis diffused reflectance spectra and X-ray diffraction. The photocatalytic activity of the heterojunction has been determined from the degradation of orange II under visible and UV light. Results show that Bi₂O₃/TiO₂ heterojunctions are more effective than pure TiO₂-anatase under UV-A irradiation, with an optimum for the Bi/Ti ratio of 5 %, for the photocatalytic degradation of Orange II. However, the photocatalytic activity under irradiation at λ higher than 420 nm is not much improved. Under UV–visible radiation, the two semiconductors are activated. We propose a mechanism explaining why our products are more effective under UV–visible irradiation. In this case the charge separation is enhanced because a part of photogenerated electrons from the conduction band of TiO₂ will go to the conduction band of bismuth oxide. In this composite, titanium dioxide is the main photocatalyst, while bismuth oxide acts as adsorbent photosensitizer under visible light.     

Utilization of nano/micro-size iron recovered from the fine fraction of automobile shredder residue for phenol degradation in water

Phenol removal by n/m Fe in the presence of H₂O₂ was highly effective. Increasing the amounts of n/m Fe and H₂O₂?increased the phenol removal rate. Phenol removal was decreased with an increase in the concentration of phenol. The natural pH (6.9) of the solution was highly effective for phenol removal. The pseudo-first-order kinetics was best fitted for the degradation of phenol. The study investigates the magnetic separation of Fe from automobile shredder residue (ASR) (<0.25 mm) and its application for phenol degradation in water. The magnetically separated Fe was subjected to an ultrasonically assisted acid treatment, and the degradation of phenol in an aqueous solution using nano/micro-size Fe (n/m Fe) was investigated in an effort to evaluate the possibility of utilizing n/m Fe to remove phenol from wastewater. The prepared n/m Fe was analyzed by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). The effects of the dosages of n/mFe, pH, concentration of phenol and amount of H₂O₂ on phenol removal were evaluated. The results confirm that the phenol degradation rate was improved with an increase in the dosages of n/mFe and H₂O₂; however, the rate is reduced when the phenol concentration is higher. The degradation of phenol by n/mFe followed the pseudo-first-order kinetics. The value of the reaction rate constant (k) was increased as the amounts of n/m Fe and H₂O₂ increased. Conversely, the value of k was reduced when the concentration of phenol was increased. The probable mechanism behind the degradation of phenol by n/m Fe is the oxidation of phenol through hydroxyl radicals which are produced during the reaction between H₂O₂ and n/m Fe.     

碘铈共掺杂纳米TiO_2的制备及可见光光催化性能

采用溶胶凝胶法制备了不同原料比例碘铈共掺杂纳米TiO2催化剂,运用X射线光电子能谱（XPS）,X射线衍射（XRD）,透射电镜（TEM）等检测手段对催化剂进行了初步表征.结果表明,经过450℃煅烧处理得到的TiO2、铈掺杂TiO2以及碘铈共掺杂TiO2催化剂均为锐钛矿相,掺杂的Ce和I原子可能以I—Ce—O及O—Ti—I等键合方式进入TiO2晶格内部,此外,I-Ce离子共掺杂能有效降低TiO2表面的电子-空穴对的复合.以染料罗丹明B（Rhodamine B,RhB）和无色小分子水杨酸（Salicylic acid,SA）为降解的目标化合物,发现碘铈共掺杂的最佳物质的量之比为nCe∶nI∶nTi=0.04∶0.05∶1,即I0.05Ce0.04TiO2催化剂在可见光照射下（λ〉420 nm）降解目标化合物其光化学活性明显优于单掺铈的TiO2催化剂和未掺杂的TiO2.该催化反应涉及到空穴氧化,并伴有羟基自由基（.OH）、超氧自由基（O2.-）及H2O2等氧化物种的产生.     

高级催化氧化法去除水中邻苯二甲酸酯的研究进展

普遍认为,邻苯二甲酸酯类物质（Phthalic Acid Esters,PAEs）是内分泌干扰物质（Endocrine Disrupting Chemicals,EDCs）,被广泛应用于增塑剂、化妆品中,具有致畸性,致癌性,致突变性以及拟/抗雌激素活性、拟/抗甲状腺激素活性等内分泌干扰特性。邻苯二甲酸酯类物质很容易扩散到环境中,在土壤、大气、水环境中均有检出,是环境中常见污染物,严重威胁人体健康和生态环境,已经引起国内外的广泛关注。在综述邻苯二甲酸酯类物质的物理化学性质、毒性影响、国内外天然水体、地下水和生活污水中的污染现状的基础上,讨论消除水环境中PAEs污染的强化混凝、吸附、膜处理、生物处理和高级氧化技术。高级氧化技术因其能够快速有效地去除饮用水和污水中不同种类的有机污染物而备受关注,且发展迅速。重点介绍了高级催化氧化法对水环境中PAEs的去除,包括催化湿式过氧化物氧化过程,催化臭氧氧化过程,光催化氧化过程,超声波、微波辅助催化氧化过程以及高级纳米催化氧化过程。其中,Fenton催化氧化技术在氧化过程中通过使用催化剂或协同紫外光等方式产生高度反应性羟基自由基,可无选择性地将PAEs完全降解为无毒无害的小分子物质,对PAEs的氧化去除效果最好。虽然在高级氧化过程中应用催化剂可大大提高氧化效率和降解程度,但催化氧化法耗能较大、催化剂消耗量大、受水体pH值的影响,且研究大多限于实验室阶段,未能大量投入工业应用,需要进一步发展创新。因此,开发新型高效催化剂、提高催化剂选择性、优化催化氧化反应条件、优化设计催化反应器、与其他技术耦合是水体中PAEs类环境激素污染控制技术的发展方向。     

TiO2光催化剂的超临界CO2萃取法制备及其降解甲基橙的活性

用超临界二氧化碳萃取TiO2醇凝胶制备纳米二氧化钛粉体，对萃取工艺条件进行了讨论，并用XRD，FT-IR，BET和DRS对上述粉体进行表征．以光催化降解甲基橙为模型反应，结果表明，与超临界二氧化碳干燥所得的粒子比较，该工艺干燥的TiO2粉体粒径小，比表面积大，光催化活性较高。     

Study of the biodegradation of phenol in river water

As the disappearance of phenols from river water principally occurs by bacteriological degradation, the effect of varying several parameters, which can influence bacteriological activity and thus the degradation kinetics of phenol, was studied.In order to have an idea about what happens to phenol and its degradation products, we examined the degradation of ¹⁴C phenol.     

Fenton溶液预处理对TiO2纳米管催化活性的影响

采用Fenton溶液对TiO2纳米管电极进行预处理,研究其对TiO2纳米管催化活性的影响,考察了Fenton溶液的浓度、配比和处理时间等影响因素,研究了Fenton预处理过程中溶液中二价铁和总铁的含量变化,运用X射线光电子能谱仪(XPS)和场发射扫描电子显微镜(FESEM)对TiO2纳米管电极进行了表征,初步探讨了经处理后TiO2纳米管催化活性再生或增强的机理.结果表明,经Fenton溶液处理后的TiO2纳米管催化活性有明显地提高,Fenton溶液浓度越高,TCs降解率越大(相应于TiO2纳米管催化活性的增强);在一定浓度范围内,H2O2的配比高低对TCs降解率影响较大,其所占比例高,则降解率高,而Fe2+配比高低对TCs降解率影响相对较小.在Fenton溶液处理过程中,溶液中剩余的Fe2+含量较为恒定,总铁的含量呈下降趋势.XPS分析表明,经Fenton溶液处理后,TiO2纳米管电极表面C1s含量降低,O1s、Fe2p含量增大;部分含碳官能团含量明显降低,O1s的电子结合能向高能端位移.     

Enhancement of photocatalytic performance in sonochemical synthesized ZnO–rGO nanocomposites owing to effective interfacial interaction

Nanocomposites composed of two or more components with desirable performance have attracted tremendous attention, mainly due to the synergic effect between the components. The effective combination of ZnO and reduced graphene oxide would lead to ameliorate the photocatalytic performance. To enhance applicability of semiconductor photocatalytic, the composites used should be good interfacial contact governed by suitable particle size distribution. Herein we aim to fabricate the different crystallize size of ZnO nanoparticles (NPs) in ZnO–reduced graphene oxide (ZnO–rGO) nanocomposites by sonochemical synthesis and subsequent facile drying treatment method. The Zn precursor, Zn(Ac)₂, with a plenty of functional groups, was used as a starting source for both reduction of graphene oxide and formation of ZnO on rGO sheets through chemical bonds without the addition of hazardous reducing agents. LiOH was chosen as an assistive reagent to enhance the complete reaction between Zn(Ac)₂ and GO in the formation of ZnO–rGO nanocomposites. More remarkably, drying condition has the great influence on the crystallize size of ZnO NPs in as-prepared ZnO–rGO nanocomposites. It is found that ZnO–rGO nanocomposites dried at ?50 °C (freeze drying) show the highest photocatalytic efficiency in the degradation of rhodamine B (RhB) as compared to ZnO–rGO nanocomposites by other drying conditions under visible-light irradiation. Correlating the crystallize size obtained by different drying temperatures with the photocatalytic activity, it is probed that the smaller crystallize size in ZnO–rGO nanocomposites enhances the interfacial contact and a chemical bonding between rGO and ZnO NPs leading to the effective separation of electrons and holes. In addition, the O ₂ ^·? anion was determined to be the main active oxidant by free radicals trapping experiment and a photodegradation mechanism of ZnO–rGO nanocomposites over rhodamine B (RhB) was proposed based on our observations.     

Photocatalytic degradation of methyl orange using ZnO nanorods

Nanosized ZnO rods were synthesized using a microwave-assisted aqueous method. High molecular weight polyvinyl alcohol was used as a stabilizing agent. Size, surface morphology, and structure were investigated using transmission electron microscopy (TEM), scanning electron microscopy (SEM), and X-ray diffraction (XRD). SEM and TEM images show that ZnO nanorods have diameters of about 50?nm and lengths of a few micrometers. The XRD pattern reveals that ZnO nanorods are of hexagonal wurtzite structure. The average crystallite size calculated from Scherrer's relation was found to be 40?nm. The effects of catalyst loading, pH value, and initial concentration of methyl orange on the photocatalytic degradation efficiency using ZnO nanorods as photocatalyst were discussed. The results revealed that ZnO nanorods with a diameter of 50?nm showed the highest photocatalytic activity at a surface density of 0.2?g?dm^?3.     

CuO-ZnO催化剂的XRD和EXAFS研究

用XRD和EXAFS方法研究了CuO-ZnO(50:50)CO_2加氢合成甲醇催化剂的结构.XRD研究发现,在催化剂还原前后,分别存在CuO,ZnO和Cu-ZnO晶相.EXAFS研究发现,在CuO-ZnO中,Cu—O,Cu—Cu键长及Cu的氧配位数、Cu的Cu配位数与纯CuO的十分接近,在Cu-ZnO中,Cu—Wu键长、Cu的Cu配位数与纯Cu的十分接近,说明催化剂在还原前后,CU的近邻结构分别与CuO与Cu的十分接近.纯Cu的活性、选择性很低,而Cu-ZnO的活性、选择性较纯Cu的有很大提高,说明催化剂的性能与催化剂中Cu的近邻结构无关.