Eu~(3+)和Gd~(3+)共掺杂TiO_2粉体的制备及催化活性

采用溶胶-凝胶法制备纯TiO2和Gd3+/Eu3+共掺杂TiO2复合粉体,采用X射线衍射、漫反射光谱和扫描电镜等技术对样品进行表征,以亚甲基蓝(methyleneblue,MB)的光催化降解为目标反应评价其光催化活性,探讨Gd3+/Eu3+共掺杂对TiO2粉体光催化的影响机制。结果表明:Gd3+/Eu3+共掺杂可以显著提高TiO2粉体光催化活性。Gd3+/Eu3+共掺杂在TiO2粉体中产生协同作用,可以抑制TiO2由锐钛矿向金红石相转变,使TiO2的粒径减小。Gd3+/Eu3+共掺杂增大了TiO2粉体的晶格畸变,使TiO2粉体吸收带边蓝移。当Gd3+和Eu3+的质量掺量分别为0.05%和0.4%时,TiO2粉体光催化活性最高,降解率达到95.31%。     

Si掺杂TiO2光催化材料的制备、活性及其机理

采用两步溶胶-凝胶法制备了Si掺杂TiO2(Si:TiO2)粉体,通过X射线衍射、热重-差热分析和X射线光电子能谱表征了Si:TiO2粉体样品的晶相及表面结构,以甲基橙为目标物考察了Si掺杂TiO2的光催化活性.研究发现:Si:TiO2粉体在水中降解有机物时,比纯TiO2粉体具有更高的光催化活性;Si:TiO2粉体具有...     

S掺杂TiO_2/粉煤灰复合材料的制备及光催化性能的研究

以钛酸四丁酯为前驱体,粉煤灰为载体,采用溶胶凝胶法制备了掺杂不同质量分数S的TiO2/粉煤灰复合纳米材料。用红外光谱(IR)、X射线衍射(XRD)、扫描电镜(SEM)及能谱分析(EDS)等测试手段对其进行了表征,以甲基橙的降解为模型反应,评价了试样光催化活性。结果表明,掺杂TiO2/粉煤灰具备较高可见光催化活性,原因是掺杂的硫取代TiO2中的晶格氧形成Ti—S键,使TiO2的带隙能窄化引起对可见光的响应,增强催化剂对可见光的吸收,与未掺杂的TiO2/粉煤灰相比较,掺杂负载型二氧化钛催化剂能够获得更高的光催化活性。     

锌掺杂TiO2超微粉的溶胶-凝胶法制备及光催化性能研究

以钛酸四丁酯为原料,采用溶胶-凝胶法制备了锌掺杂纳米TiO2光催化剂,探讨了锌掺杂对TiO2光催化活性的影响.用X射线衍射仪(XRD)、扫描电子显微镜(SEM)表征了产品的微观结构和晶相组成,用综合热分析仪对前驱体凝胶进行了差热分析;以亚甲基蓝为降解对象,考察了锌掺杂、掺杂浓度对TiO2光催化活性的影响.结果表明:锌掺杂对TiO2晶由锐钛矿型向金红石型的相转变有抑制作用,并能够提高纳米TiO2的光催化活性;锌掺杂量具有一个相对最佳比例,当掺杂量3%、热处理温度550℃时,用溶胶-凝胶法可得到粒径分布均匀、锐钛矿晶型含量高、具有较高光催化活性的锌掺杂纳米TiO2.     

超声-S/TiO_2纳米颗粒可见光催化协同降解亚甲基蓝

采用共沉淀-浸渍法制备掺杂S的TiO2光催化剂,利用XRD,TEM,UV-Vis-DRs,XPS等方法对其结构、元素组成和光谱学特征进行研究,以亚甲基蓝(MB)的光催化降解反应为模型,探讨高效利用可见光降解亚甲基蓝的反应体系。实验结果表明,S掺杂最佳热处理温度为500℃。掺杂光催化剂晶型仍为锐钛矿型,其粒径变小,比表面积增大,热稳定性增加,对可见光的吸收增强。超声波对光催化降解反应有协同作用,S/TiO2在可见光下对亚甲基蓝的降解率明显高于纯TiO2。     

离子液体辅助Fe掺杂TiO2的制备及可见光活性

以钛酸四丁酯为钛源,FeC2O4·2H2O为铁源,离子液体([C4MIM] BF4)为模板剂采用溶胶凝胶法制备了具有大比表面积及可见光活性的Fe掺杂介孔TiO2光催化材料.采用X射线衍射仪、氮气吸附-脱附仪、透射电子显微镜、紫外可见吸收光谱对样品进行表征.结果表明所制备样品IL-Fe/TiO2中TiO2主要以锐钛矿相存在,Fe掺杂量对TiO2晶相影响不大,样品IL-0.1％ Fe/TiO2具有介孔结构和较大的比表面积,颗粒尺寸在30 nm左右.紫外可见光谱分析表明铁掺杂后TiO2的吸收带红移,带隙能降低.以亚甲基蓝为模拟污染物,在可见光(λ＞420 nm)下测定样品光催化活性,结果表明IL-0.1％ Fe/TiO2的可见光催化活性最高.     

铁和镧共掺杂二氧化钛的光催化活性

采用溶胶-凝胶法制备了纯的和铁镧共掺杂的TiO2纳米粒子,对样品进行了X射线和紫外-可见吸收光谱分析。结果表明,500℃煅烧的未掺杂和共掺杂TiO2均呈锐钛矿结构,铁镧共掺杂抑制了TiO2粒径的长大,使TiO2的吸收带边红移且在可见光区的光吸收增强;光催化降解甲基橙表明,未掺杂的TiO2光催化活性高于P25,而适量铁镧共掺杂TiO2光催化活性进一步得到提高,最佳掺杂比是0.05%的Fe和0.5%的La。     

N、Mo共掺杂TiO_2光催化剂的制备及对亚甲基蓝降解性能研究

以硫脲、钼酸铵和钛酸四丁酯为原料,利用溶胶-凝胶法制备了未掺杂的和N、Mo共掺杂的TiO2光催化剂。用紫外-可见吸收光谱对制备的催化剂样品进行了表征,考察了不同条件下光催化剂对亚甲基蓝溶液的光催化活性。试验结果表明,N、Mo共掺杂使TiO2催化剂的吸收带边位置发生了红移;在可见光条件下,0.125 gN、Mo共掺杂TiO2(n(N)∶n(Mo)=2∶1)、pH值为6.20、温度为30℃的体系对质量浓度为20 mg/L的亚甲基蓝溶液的脱色效果最好。     

煅烧温度及气氛对GdBr3掺杂TiO2粉体可见光光催化活性的影响

采用醇盐水解法制备了掺杂GdBr3改性的纳米TiO2光催化复合材料,采用x射线衍射、透射电子显微镜、表面及孔隙度分析仪等测试技术分析和研究了改性TiO2粉体的晶相组成、形貌、比表面积及可见光光催化活性.结果表明,改性TiO2粉体在N2环境中经550℃煅烧2h后,粉体分散较好,TiO2仍为锐钛矿相,GdBr3/TiO2(摩尔比)为0.05的改性粉体在波长为420nm,照度为1200μw/cm2的可见光下照射12h后,对甲基橙的降解率可达70%,呈现出较好的可见光光催化活性.     

可见光活性负载型Fe2O3/TiO2光催化剂的制备

以FeCl3·6H2O和TiOSO4为原料,尿素为沉淀剂,采用均匀共沉淀法制备了Fe3 掺杂的纳米TiO2粉体,并通过X射线衍射、透射电镜分析及观察粉体的相结构、形貌和粒径.以甲基橙溶液为降解对象,考察了掺杂后的粉体在紫外和可见光作用下的光催化性能并对其机理进行了探讨.结果表明:Fe3 部分固溶于TiO2的晶格;当Fe3 掺杂量＜0.8%(摩尔分数,下同)时,随铁离子掺入量的增加,TiO2的光催化性能提高;当Fe3 掺杂量为0.8%时,复合粉体的光催化性能提高15%以上;当Fe3 掺杂量＞0.8%时,随铁离子掺入量的增加,TiO2的光催化性能降低,而当Fe3 掺杂量＞1.2%时,粉体的光催化性能受到抑制,低于纯TiO2粉体.     

Insect antifeedant properties of anthranoids from the genusVismia

Vismiones and ferruginins, representatives of a new class of lypophilic anthranoids from the genusVismia were found to inhibit feeding in larvae of species ofSpodoptera, Heliothis, and inLocusta migratoria.     

Direct observation of freeze-thaw instability of latex coatings via high pressure freezing and cryogenic SEM

Despite its industrial importance, the subject of freeze-thaw (F/T) stability of latex coatings has not been studied extensively. There is also a lack of fundamental understanding about the process and the mechanisms through which a coating becomes destabilized. High pressure (2100 bar) freezing fixes the state of water-suspended particles of polymer binder and inorganic pigments without the growth of ice crystals during freezing that produce artifacts in direct imaging scanning electron microscopy (SEM) of fracture surfaces of frozen coatings. We show that by incorporating copolymerizable functional monomers, it is possible to achieve F/T stability in polymer latexes and in low-VOC paints, as judged by the microstructures revealed by the cryogenic SEM technique. Particle coalescence as well as pigment segregation in F/T unstable systems are visualized. In order to achieve F/T stability in paints, latex particles must not flocculate and should provide protection to inorganic pigment and extender particles. Because of the unique capabilities of the cryogenic SEM, we are able to separate the effects of freezing and thawing, and study the influence of the rate of freezing and thawing on F/T stability. Destabilization can be caused by either freezing or thawing. A slow freezing process is more detrimental to F/T stability than a fast freezing process; the latter actually preserves suspension stability during freezing. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 27–29, 2004 in Chicago, IL. Tied for first place in The John A. Gordon Best Paper Competition.     

Many Drugs of Abuse May Be Acutely Transformed to Dopamine,Norepinephrine and Epinephrine In Vivo

It is well established that a wide range of drugs of abuse acutely boost the signaling of the sympathetic nervous system and the hypothalamic–pituitary–adrenal (HPA) axis, where norepinephrine and epinephrine are major output molecules. This stimulatory effect is accompanied by such symptoms as elevated heart rate and blood pressure, more rapid breathing, increased body temperature and sweating, and pupillary dilation, as well as the intoxicating or euphoric subjective properties of the drug. While many drugs of abuse are thought to achieve their intoxicating effects by modulating the monoaminergic neurotransmitter systems (i.e., serotonin, norepinephrine, dopamine) by binding to these receptors or otherwise affecting their synaptic signaling, this paper puts forth the hypothesis that many of these drugs are actually acutely converted to catecholamines (dopamine, norepinephrine, epinephrine) in vivo, in addition to transformation to their known metabolites. In this manner, a range of stimulants, opioids, and psychedelics (as well as alcohol) may partially achieve their intoxicating properties, as well as side effects, due to this putative transformation to catecholamines. If this hypothesis is correct, it would alter our understanding of the basic biosynthetic pathways for generating these important signaling molecules, while also modifying our view of the neural substrates underlying substance abuse and dependence, including psychological stress-induced relapse. Importantly, there is a direct way to test the overarching hypothesis: administer (either centrally or peripherally) stable isotope versions of these drugs to model organisms such as rodents (or even to humans) and then use liquid chromatography-mass spectrometry to determine if the labeled drug is converted to labeled catecholamines in brain, blood plasma, or urine samples.     

Ethanol and (−)-α-Pinene: Attractant Kairomones for Bark and Ambrosia Beetles in the Southeastern US

In 2002–2004, we examined the flight responses of 49 species of native and exotic bark and ambrosia beetles (Coleoptera: Scolytidae and Platypodidae) to traps baited with ethanol and/or (−)-α-pinene in the southeastern US. Eight field trials were conducted in mature pine stands in Alabama, Florida, Georgia, North Carolina, and South Carolina. Funnel traps baited with ethanol lures (release rate, about 0.6 g/day at 25–28°C) were attractive to ten species of ambrosia beetles (Ambrosiodmus tachygraphus, Anisandrus sayi, Dryoxylon onoharaensum, Monarthrum mali, Xyleborinus saxesenii, Xyleborus affinis, Xyleborus ferrugineus, Xylosandrus compactus, Xylosandrus crassiusculus, and Xylosandrus germanus) and two species of bark beetles (Cryptocarenus heveae and Hypothenemus sp.). Traps baited with (−)-α-pinene lures (release rate, 2–6 g/day at 25–28°C) were attractive to five bark beetle species (Dendroctonus terebrans, Hylastes porculus, Hylastes salebrosus, Hylastes tenuis, and Ips grandicollis) and one platypodid ambrosia beetle species (Myoplatypus flavicornis). Ethanol enhanced responses of some species (Xyleborus pubescens, H. porculus, H. salebrosus, H. tenuis, and Pityophthorus cariniceps) to traps baited with (−)-α-pinene in some locations. (−)-α-Pinene interrupted the response of some ambrosia beetle species to traps baited with ethanol, but only the response of D. onoharaensum was interrupted consistently at most locations. Of 23 species of ambrosia beetles captured in our field trials, nine were exotic and accounted for 70–97% of total catches of ambrosia beetles. Our results provide support for the continued use of separate traps baited with ethanol alone and ethanol with (−)-α-pinene to detect and monitor common bark and ambrosia beetles from the southeastern region of the US.     

Novel polyurethane coating technology through glycidyl carbamate chemistry

Glycidyl carbamate chemistry combines the excellent properties of polyurethanes with the crosslinking chemistry of epoxy resins. Glycidyl carbamate functional oligomers were synthesized by the reaction of polyfunctional isocyanate oligomers and glycidol. The oligomers were formulated into coatings with several amine functional crosslinkers at varying stoichiometric ratios and cured at different temperatures. Properties such as solvent resistance, hardness, and impact resistance were dependent on the composition and cure conditions. Most coatings had an excellent combination of properties. Studies were carried out to determine the kinetics of the curing reaction of the glycidyl carbamate functional oligomers with multifunctional and model amines. Detailed kinetic analysis of the curing reactions was also undertaken. The results indicated that the glycidyl carbamate functional group is more reactive than a glycidyl ether group. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, on October 27–29, 2004, in Chicago, IL.