量子点修饰钛酸钠纳米管及其光电性能

以巯基乙酸为中间体,把CdSe量子点化学修饰在钛酸钠纳米管上,并对其光电性能进行了研究。结果表明：用CdSe量子点修饰以后钛酸钠纳米管在紫外。可见光区有很好的光伏响应,相对于没有进行修饰的钛酸钠纳米管,其光伏响应范围有一定程度的拓宽,并且响应强度也有很大增强。表面光电压谱的研究结果表明：在外部电场的作用下,没有经过修饰的钛酸钠纳米管的表面光电压信号随正电场的增强而增强,随负电场的增强而减弱;而用CdSe修饰过的钛酸钠纳米管的表面光电压响应与此不同,主要表现在其表面光电压信号强度先随正电场的增强而增强,当正电场的强度达到一定值时,部分波谱范围的表面光电压信号继续得到增强,而部分波谱范围的表面光电压信号反而减弱。我们利用漂移机制和扩散机制对这一现象作了解释。     

镶嵌铂的纳米管钛酸制备及其可见光光催化活性

通过在真空条件下将氯铂酸的乙醇溶液引入到钛酸纳米管内,再经过热处理制备了镶嵌铂的纳米管钛酸(简写为PNTA).X射线光电子能谱(XPS)表明氯铂酸大部分转变成Pt⁰和PtO,顺磁共振谱(ESR)表明在PNTA中生成了束缚单电子的氧空位,在紫外-可见扩散漫散射谱(DRS)谱上表现出对可见光有吸收能力.丙烯的可见光光催化氧化实验结果表明:在可见光激发下(λ>420nm),PNTA对丙烯的光催化去除反应具有活性.     

ZnO纳米管的光学性质及其对甲基橙降解的光催化活性

以十二烷基硫酸钠为模板剂采用水热法合成了ZnO纳米管,以尿素和ZnSO4为原料制备了ZnO纳米颗粒,并应用透射电镜、x射线衍射、光致发射光谱、拉曼光谱、比表面积测定、傅里叶红外光谱和紫外-可见漫反射光谱等技术对样品进行了表征.结果表明,ZnO纳米管的比表面积较大,在λ≈650nm的可见光波段ZnO纳米管开始出现吸收峰,而ZnO纳米颗粒在可见光波段几乎没有吸收.ZnO纳米管和纳米颗粒在紫外光照射下均对甲基橙有降解作用,其中ZnO纳米管的光催化活性较高.随着催化剂用量的增加和光照时间的延长,甲基橙降解率逐渐提高;甲基橙浓度的增大使甲基橙降解率降低.     

不同前驱体制备氮掺杂二氧化钛及其光催化性能比较

在氨气气氛中和不同温度下焙烧纳米管钛酸和商业Degussa-P25,得到两系列可见光响应型氮掺杂二氧化钛光催化剂.采用高分辨透射电子显微镜、紫外-可见漫反射光谱仪和X射线衍射仪对两系列样品的形貌、光谱吸收和晶体结构等物理化学性质进行了表征和比较.通过可见光光催化氧化丙烯评价系统对两系列样品的活性进行了评价.结果表明,600℃处理纳米管钛酸得到的催化剂可见光催化活性最好,是相同条件下处理Degussa-P25得到的催化剂(N-P25)活性的3.3倍.研究表明,纳米管钛酸是制备可见光响应型光催化剂较好的前驱体.     

静态法和EXAFS技术研究Eu(III)在钛酸纳米管上的吸附行为和微观机制

结合静态实验和X射线吸收精细结构谱学(EXAFS)技术研究了pH、时间、有机配体等环境因素对放射性核素Eu(III)在钛酸纳米管上的吸附行为和微观机制的影响.宏观实验结果表明:Eu(III)在钛酸纳米管上的吸附在pH<6.0条件下受离子强度影响,而在pH>6.0条件下不受离子强度影响;腐殖酸HA/FA在低pH条件下可以促进Eu(III)在钛酸纳米管上的吸附,而在高pH条件下抑制Eu(III)在钛酸纳米管上的吸附.EXAFS微观分析结果表明:在pH<6.0条件下,吸附属于外层吸附机理;在pH>6.0条件下,吸附属于内层吸附机理.pH<6.0时,中心原子Eu周围只有Eu-O一个配位层,其平均键长为2.40,配位数在9左右;随着pH逐渐升高,第一配位层的配位数下降,表明吸附Eu原子配位的对称性下降.当吸附时间延长或pH升高,吸附原子Eu周围出现了Eu-Eu和Eu-Ti第二配位层,其平均键长分别为3.60和4.40,配位数分别在2或1左右,表明形成了内层吸附产物或表面沉淀或表面多聚体.腐殖酸HA/FA的存在,可以改变Eu(III)在钛酸纳米管表面的吸附形态和微观原子结构,Eu(III)不仅可以与钛酸纳米管的表面羟基直接键合形成二元表面复合物(Eu-TNTs),还可以通过HA/FA的桥连作用形成三元表面复合物(HA/FA-Eu-TNTs).这些研究结果对于评估放射性核素Eu(III)与纳米材料在分子水平上的作用机理及分析Eu(III)在环境中的物理化学行为具有重要的意义.     

负载金的掺氮二氧化钛的制备及其可见光催化性能

以纳米管钛酸为前驱体,采用水热法先制备得到新型N掺杂二氧化钛,然后用沉积沉淀法在N掺杂二氧化钛表面负载微量贵金属Au,制备得到负载Au的掺N二氧化钛.利用TEM、XRD、XPS、ESR和DRS等手段研究了样品的形貌、晶体结构、元素化学态和光谱吸收性质.样品光催化活性通过可见光催化降解丙烯进行评价,结果表明,样品N-TiO₂和Au/N-TiO₂具有明显的可见光(λ≥420 nm)催化活性.ESR结果表明,掺氮过程中生成的束缚单电子的氧空位是样品具有可见光响应的原因.     

硫掺杂钛酸(盐)纳米管的表征与可见光光催化活性

以二硫化钛为钛源和硫源,通过与NaOH水热反应成功制备了硫掺杂钛酸(盐)纳米管。 采用X射线衍射、高分辨透射电子显微镜、扫描电子显微镜、扩展X射线吸收精细结构(EXAFS)和X光微区分析等手段对所制备的硫掺杂钛酸(盐)纳米管的结构、形貌、硫掺杂状态和掺杂量进行了表征,并以可见光光催化氧化乙醇反应为探针,采用原位气相色谱技术研究了硫掺杂钛酸纳米管的可见光光催化活性;结果表明,S原子以S2-形式取代了钛酸纳米管骨架中O原子的位置, 有效实现了硫掺杂;硫掺杂钛酸(盐)纳米管壁厚平均尺寸为2.9 nm,管径平均尺寸为9.7 nm。 可见光光催化氧化乙醇反应结果表明,掺硫钛酸纳米管在极低的掺硫量条件下,表现出比未掺杂的二氧化钛纳米管具有更高的可见光光催化活性。     

纳米管钛酸CO处理产物的结构及光催化活性

研究了在CO气流中,处理温度对纳米管钛酸(NTA)脱水产物TiO₂的结构及C₃H₆光催化氧化反应活性的影响.结果表明:NTA经CO高温处理后,样品未发生C掺杂,只有碳沉积发生;随着处理温度的升高,样品的比表面积大幅下降,与NTA在空气中焙烧处理相比,由锐钛矿向金红石TiO₂转变的温度提前;CO处理后产物对C₃H₆均未表现出可见光催化性能,但具有紫外光催化活性,随着在CO气氛中处理温度的升高,紫外光催化活性降低.     

水热法制备铂掺杂二氧化钛及其可见光催化性能

以纳米管钛酸为前驱体,采用水热法制备了Pt掺杂TiO2样品.水热反应过程中,纳米管钛酸表面羟基与氯铂酸发生酸碱中和反应,导致反应后pH值升高;在130°C开始纳米管钛酸晶体结构由正交晶系转变为锐钛矿相TiO2.表面化学组成分析表明,掺杂的Pt主要以+2价形式存在.以丙烯为模型污染物,评价样品的可见光(λ≥420nm)光催化活性.结果表明,Pt-TiO2具有明显的可见光光催化降解丙烯的活性,其中160°C水热处理制得的Pt-TiO2活性最高.最后讨论了低温水热法Pt掺杂的形成机理及Pt-TiO2具有可见光响应的原因.     

负载金的纳米管钛酸光催化氧化一氧化碳

 用化学方法制备了负载金的纳米管钛酸(Au/H2Ti2O4(OH)2)光催化剂,并用TEM,XPS,XRD和DRS等技术对催化剂进行了表征. 结果表明,经573 K处理后,纳米管钛酸表面及管内均有零价的金颗粒存在. 与纳米管钛酸(H2Ti2O4(OH)2)相比,Au/H2Ti2O4(OH)2具有明显的CO光催化氧化活性,但在暗态时无活性. 经分析认为,暗态时Au与纳米管相互接触的周界处不活泼,故催化剂无CO催化氧化活性; 紫外光照射下,纳米管激发产生e--h+对,e-从纳米管转移到Au0上, 使纳米管和Au-在接触周界处产生相互作用,形成活性位,导致CO催化氧化反应发生.     

Effects of photodegradation on the physical and antioxidant properties of melanosomes isolated from retinal pigment epithelium

Melanosomes of the retinal pigment epithelium (RPE) are relatively long-lived organelles that are theoretically susceptible to changes induced by exposure to visible light. Here melanosomes were isolated from porcine RPE cells and subjected to high intensity visible light to determine the effects of illumination on melanosome structure and on the content and antioxidant properties of melanin. As compared to untreated melanosomes, illuminated granules showed morphologic changes consistent with photodegradation, which included variable reductions in electron density demonstrated by transmission electron microscopy (TEM), and particle fragmentation and surface disruption revealed by scanning electron microscopy (SEM) and atomic force microscopy. Illuminated melanosomes had lower melanin content, indicated by measures of absorbance and electron spin resonance (ESR) signal intensity, and reduced ability to bind iron, shown by chemical and ESR analyses. Compared to untreated melanosomes, ESR-spin trapping analyses further indicated that illuminated melanosomes show increased photogeneration of superoxide anion and reduced ability to inhibit the iron ion-catalyzed free radical decomposition of hydrogen peroxide. It appears therefore that visible light irradiation can disrupt the structure of RPE melanosomes and reduce the amount and antioxidant properties of melanin. Some of these changes occur in human RPE melanosomes with aging and the results obtained here suggest that visible light irradiation is at least partly responsible. The consequence of light-induced changes in RPE melanosomes may be a diminished capacity of melanin to help protect aged cells from oxidative damage, perhaps increasing the risk of diseases with an oxidative stress component such as age-related macular degeneration.     

Mechanistic studies of the photocatalytic oxidation of trichloroethylene with visible-light-driven N-doped TiO2 photocatalysts

Visible-light-driven TiO2 photocatalysts doped with nitrogen have been prepared as powders and thin films in a cylindrical tubular furnace under a stream of ammonia gas. The photocatalysts thus obtained were found to have a band-gap energy of 2.95 eV. Electron spin resonance (ESR) under irradiation with visible light (lambda > or = 430 nm) afforded the increase in intensity in the visible-light region. The concentration of trapped holes was about fourfold higher than that of trapped electrons. Nitrogen-doped TiO2 has been used to investigate mechanistically the photocatalytic oxidation of trichloroethylene (TCE) under irradiation with visible light (lambda > or = 420 nm). Cl and O radicals, which contribute significantly to the generation of dichloroacetyl chloride (DCAC) in the photocatalytic oxidation of TCE under UV irradiation, were found to be deactivated under irradiation with visible light. As the main by-product, only phosgene was detected in the photocatalytic oxidation of TCE under irradiation with visible light. Thus, the reaction mechanism of TCE photooxidation under irradiation with visible light clearly differs markedly from that under UV irradiation. Based on the results of the present study, we propose a new reaction mechanism and adsorbed species for the photocatalytic oxidation of TCE under irradiation with visible light. The energy band for TiO2 by doping with nitrogen may involve an isolated band above the valence band.     

An electron spin resonance study of dry vegetables before and after irradiation

The ESR signals were successfully observed for the first time in dry vegetables (DVs) that are prominently used in oriental cuisines. We analyzed ESR signals of DV before and after irradiation. Before irradiation, the ESR signal of DV consisted of the three components: a singlet at g=2.0030, the sextet signals from Mn(2+) ion, and a singlet from Fe(3+). The first originated from a carbon centered organic free radical. The second is attributable to the sextet signal with hyperfine interactions of Mn(2+) ion centered at g=2.0020. The third is a singlet at g=4.0030 due to Fe(3+). After the gamma-ray irradiation, a new pair of signals, or twin peaks, appeared in the ESR spectrum of DV. The intensity of the organic free radical at g=2.0030 of the irradiated DV increased lineally with radiation doses. Progressive saturation behavior of the DV indicates a unique saturation and the signals obeyed various relaxation processes.     

吸附在溴化银颗粒表面上的增感染料的ESR波谱研究

本文用电子顺磁共振技术研究了光照条件下三十八种增感染料与溴化银之间发生的电子转移过程。增感染料和溴化银无论在黑暗处还是在光照下,均不产生ESR信号。当增感染料吸附在溴化银颗粒表面上时,如不加光照,仍看不到ESR信号。只有在光照条件下,才有可能观察到ESR信号,这主要取决于增感染料分子的最高占有能级与溴化银价带的相对位置。若染料分子的最高占有能级比溴化银价带顶部高0.7 eV,就可以观察到ESR信号,反之则观察不到。顺磁性中心是由染料正空穴Dye^©形成的。根据ESR信号的强度可以判断增感染料是否有较强的减感作用。     

Photochromically-controlled, reversibly-activated MRI and optical contrast agent

The contrast agent which tethers a spiropyran group to a Gd-DO3A moiety has higher relaxivity and fluorescence intensity in the dark; the relaxivity and fluorescence intensity decrease after irradiation with visible light.     

内敏乳剂的ESR研究

本文制备了具有化学结构缺陷以及具有物理晶格缺陷的两种内敏核壳乳剂,并研究了它们的电子自旋共振波谱。随着化学增感时间的增加,ESR信号强度增强,达到一最大值后又下降。ESR信号强度随核壳比的下降而下降;随灰化程度的上升而下降。不同减感染料由于其减感机理的不同,对内部感光性能和ESR信号强度的影响也不同。上述结果可以用空穴在颗粒内部的行为来解释。     

竹红菌甲素半醌自由基的变化特点

通过研究竹红菌甲素半醌负离子自由基衰减的动力学,建立了甲素半醌自由基在624nm的可见吸收强度和ESR信号强度的平行关系.在624nm的可见吸收属于甲素半醌自由基的吸收.这个研究结果对研究甲素的半醌自由基具有实用意义.讨论了还原型谷胱甘肽存在下光诱导所产生的甲素 半醒自由基的衰变特点.     

The effect of processing treatments on the radiation-induced ESR signal in the cuticle of irradiated Norwat lobster (Nephrops norvegicus).

Cooked, frozen or chilled whole tails of Norway lobster were either not irradiated or given doses of 1, 2, 3, 4 or 5 kGy using a cobalt 60 source. The cuticle was removed, freeze-dried and ground before determination of the free radical concentration using electron spin resonance (ESR) spectroscopy. The ESR signal strength increased linearly with increasing irradiation dose. In comparison to the chilled samples, cooking before irradiation significantly increased (69%) signal intensity whereas cooking after irradiation decreased (27%) signal strength. Irradiating the samples in the frozen state did not significantly alter the free radical concentration in the cuticle.     

Hypocrellin A与二苄胺和N-甲基苄胺的光化学反应

In order to discuss the free radicals formation mechanism of Hypocrellin A（HA）with amino derivatives,the electron-spin resonance（ ESR） spectroscopy was adopted to study the photochemistry on HA with dibenzyl amine（DBA）and N-methyl benzyl amine（NMBA）,respectively. When HA with DBA or NMBA in chloroform solution was illuminated with visible light,singlet oxygen,semiquinone radical and oxynitride radical were formed depending on the condition of the solvent system containing the amino-substituted and solved oxygen. The signal intensity of oxynitride radical decreased with increasing the illumination time,and the signal intensity of semiquinone radical increased with increasing the illumination time. The oxynitride radical content was in inverse ratio with the semiquinone radical generated by being irradiated. In the aerobic system of chloroform solution containing DBA/HA,smiquinone radical was the main radical irradiated. The results indicated that HA induced amino derivatives into HA semiquinone radical.     

ZnO-B2O3∶Tb3+长余辉玻璃的发光性质

通过还原方法制备了Tb³⁺离子掺杂的硼酸锌玻璃，并观察到在254 nm紫外光激发后有明亮的绿色长余辉发光现象，余辉时间达6 h。通过激发与发射光谱、余辉光谱、余辉衰减曲线、热释光谱、热释光释出速率衰减曲线等得到的信息，研究了Tb³⁺离子掺杂的硼酸锌玻璃的发光性质。