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.     

WO3/ZnO复合光催化剂的制备及其光催化性能

采用沉淀-研磨法制备了一系列不同WO3含量的WO3/ZnO复合光催化剂,应用N2物理吸附、X射线衍射、扫描电镜、傅里叶变换红外光谱、紫外-可见光谱和光致发光谱等手段对催化剂进行了表征,并以λ=365nm的紫外光为光源,评价了该催化剂光催化降解酸性橙Ⅱ的活性,考察了WO3的复合对WO3/ZnO样品光催化性能的影响.结果表...     

WO_3纳米颗粒修饰ZnO纳米管的光催化性能（英文）

二甲四氯钠(MCPA-Na)是一种广泛用于牧场和果园的除草剂,但由于其生物降解性极低,已成为地下水和浅水中的主要污染物.研究发现,半导体可以有效地辅助降解转化危险化学品.ZnO纳米管因其中空结构和较大的比表面积,而在光催化降解有机物方面备受关注.但是,ZnO只能吸收紫外光,如果将其与窄带隙半导体进行复合,可以有效降低带隙,增强其在可见光区域的光吸收,表现出更好的光催化性能.WO_3是一种具有稳定物理化学性质及耐光腐蚀窄带隙半导体.采用WO_3修饰ZnO纳米管,能扩展ZnO吸收光的范围以及提高ZnO纳米管的耐光腐蚀性能.本文首先通过电化学合成的方法制备了ZnO纳米管,然后按照不同的W/Zn摩尔比将(NH4)6H2W12O40·XH2O滴加在纳米管表面,并在450°C下退火2 h制得ZnO-WO_3纳米管阵列.研究了不同WO_3含量的ZnO-WO_3纳米管光催化降解MCPA-Na性能,并且通过X射线光电子能谱(XPS)、傅里叶红外光谱仪(FTIR)、紫外可见光谱(UV-Vis)和光致发光光谱(PL)等手段研究了复合WO_3纳米颗粒后ZnO纳米管半导体光催化性能提高的原因.XPS结果表明,W元素在ZnO-WO_3纳米管阵列中以W6+的形式存在.FTIR结果表明,复合WO_3后的ZnO-WO_3复合半导体上比纯ZnO纳米管表面具有更多的-OH基团.由于-OH可以捕获光生空穴,并转化为具有反应活性的OH自由基,因此复合WO_3能在一定程度上提高ZnO纳米管的光催化活性.UV-Vis结果表明,WO_3的复合使得光谱发生明显红移,但随着WO_3含量的增加,ZnO-WO_3的吸光度明显增加.另外,PL结果表明,适当的复合WO_3可以抑制光生电子-空穴的复合.这是因为W6+和晶格氧的相互作用产生了较高不饱和键和表面缺陷,而表面缺陷可以作为光生载流子的陷阱,促进了光生电子和空穴的分离,因而光催化性能提高.在模拟太阳光下研究了不同WO_3含量的ZnO纳米管对光催化降解MCPA-Na溶液的性能.发现W/Zn摩尔比为3%的ZnO-WO_3样品表现出最好的光催化活性,200 min内其降解率为98.5%.与纯ZnO纳米管相比,其光催化循环性能也有所提高.利用Mott-Schottky测试方法并结合UV-vis结果,我们计算得到不同WO_3含量的ZnO-WO_3复合半导体导带价带位置.由于WO_3导带位置和价带位置都比ZnO的更高,WO_3上产生的光生电子会向ZnO的导带移动,而ZnO光生空穴向WO_3的价带移动,从而促使光生电子和空穴的分离,提高了光催化性能.但是如果WO_3复合的量太大,则在ZnO纳米管上分散性不好,反而成为光生空穴和电子复合中心,导致其光催化活性降低.     

均一形貌的ZnO纳米棒的制备及其光催化性能研究

ZnO nanorods were synthesized from high purity Zn granule by a vapor phase deposition in the Ar + O₂ gas. The products were characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). The ZnO nanorods were typically 1～2 μm in length and 20～30 nm in diameter with an aspect ratio as high as 20. The UV absorption properties were detected and the results show that the ZnO nanorods have an extremely strong absorption at 200～380 nm wavelength. The results were good when the ZnO nanorods were used as photocatalyst.     

共沉淀法制备稀土Ce掺杂的纳米ZnO及其光催化降解染料的性能

以六水合硝酸锌和六水合硝酸铈?髥为原料,通过共沉淀法制备了一系列稀土Ce掺杂的纳米ZnO,并采用X射线粉末衍射(XRD)、傅里叶红外光谱(IR)、扫描电镜(SEM)、X射线能谱分析(EDS)、紫外可见漫反射光谱对其进行了全面表征。部分样品还通过X射线光电子能谱(XPS)和光致荧光光谱(PL)进行了进一步分析。分别在日光和紫外光条件下,对这一系列Ce掺杂的ZnO进行了光催化降解亚甲基蓝的性能研究,得出当Ce的掺杂量为3%(n/n)时(ZnO-3%Ce),其光催化活性最佳,光催化降解亚甲基蓝的效率均超过98%。选取ZnO-3%Ce作为催化剂,分别进一步考察其在日光和紫外光下对罗丹明B和甲基橙的光催化降解性能。研究结果表明,ZnO-3%Ce在日光和紫外光下均表现出较好的光催化降解效果,体现出良好的光降解普适性。日光下光降解效率顺序为:亚甲基蓝>罗丹明B>甲基橙,而紫外光下降解效率顺序为:罗丹明B>亚甲基蓝>甲基橙。最后,我们研究了催化剂ZnO-3%Ce的循环利用及稳定性性能。实验结果表明:该催化剂循环使用3次之后,光催化效率仍然稳定在97%以上,并且其结构和组成保持不变,体现出优异的稳定性和应用前景。     

Fe_2O_3/TiO_2纳米管阵列的制备及其光催化性能

在钛基体上采用阳极氧化法制备了TiO2纳米管阵列,采用化学浴方法在TiO2纳米管阵列上修饰了Fe2O3纳米颗粒。利用扫描电镜、X射线衍射和紫外可见漫反射光谱等手段对材料进行了表征,同时测试了材料的光电化学性能及其光催化降解亚甲基蓝染料废水的性能。结果表明,Fe2O3纳米颗粒的修饰将TiO2纳米管阵列的光响应拓宽至可见光区域,提高了光电流,Fe2O3/TiO2纳米管阵列的光电流是未修饰的TiO2纳米管阵列的9倍。而在光催化反应中,亚甲基蓝最高降解率可达80%,比未修饰的TiO2纳米管阵列高出30%。     

Ti基ZnO纳米棒阵列的制备及其光催化性能研究

采用两电极体系中恒电流电沉积在Ti基底上制得较均一的ZnO纳米棒阵列,利用SEM和XRD观察表征样品,研究Zn(NO₃)₂浓度及电流密度对ZnO纳米棒阵列微观形貌的影响. 以甲基橙为目标降解物,考察该电极光催化性能. 结果表明,Zn(NO₃)₂浓度和电流密度对纳米棒阵列的形貌有显著影响;与ITO玻璃等其他基底相比,在Ti基底上也可沉积较好均一取向的ZnO纳米棒阵列;紫外灯照射下,ZnO/Ti电极对甲基橙（10 mg·L^-1）模拟印染废水降解2.5 h,降解率达到83.3%,光催化活性较佳;无光照时ZnO纳米棒的降解率仅7%.     

Fe2O3/TiO2纳米管阵列的制备及其光催化性能

在钛基体上采用阳极氧化法制备了TiO₂纳米管阵列,采用化学浴方法在TiO₂纳米管阵列上修饰了Fe₂O₃纳米颗粒.利用扫描电镜、X射线衍射和紫外可见漫反射光谱等手段对材料进行了表征,同时测试了材料的光电化学性能及其光催化降解亚甲基蓝染料废水的性能.结果表明,Fe₂O₃纳米颗粒的修饰将TiO₂纳米管阵列的光响应拓宽至可见光区域,提高了光电流,Fe₂O₃/TiO₂纳米管阵列的光电流是未修饰的TiO₂纳米管阵列的9倍.而在光催化反应中,亚甲基蓝最高降解率可达80%,比未修饰的TiO₂纳米管阵列高出30%.     

纳米ZnO/聚醋酸乙烯酯复合薄膜的光催化性能研究

采用溶胶-凝胶和浸渍-提拉而后煅烧的方法得到了在可见光作用下具有光催化性能的纳米ZnO/聚醋酸乙烯酯(PVAc)复合薄膜.通过正交设计实验,研究了PVAc的浓度、煅烧温度、煅烧时间、复合薄膜层数和附加ZnO膜层数等工艺因素对光催化性能的影响,并通过SEM,XRD和FT-IR对其进行了分析与表征.在室内普通照明用白炽灯作用下,以甲基橙溶液为催化对象,PVAc含量10%的、在250℃煅烧30min所得到的纳米ZnO/PVAe复合薄膜的光催化性能的实验结果表明,复合薄膜对甲基橙降解率达60%,而使用250℃煅烧30min所得到的纳米ZnO 4层薄膜或PVAc 4层薄膜催化的甲基橙溶液的浓度变化很小.     

磷酸修饰对纳米Fe2O3热稳定性及光催化性能的影响

通过溶液浸渍蒸干过程实现了磷酸对Fe₂O₃纳米粒子的表面修饰, 研究了磷酸修饰对纳米Fe₂O₃的热稳定性及光催化活性的影响. 结果表明, 磷酸修饰显著提高了Fe₂O₃的热稳定性, 主要归因于磷酸修饰在样品表面抑制了粒子之间的团聚生长. 同时, 在光催化降解气相乙醛和液相苯酚的测试中, 磷酸修饰后热处理温度为600 ℃的样品表现出了最佳的可见光催化性能, 这主要归因于该样品具有高晶化度、 小粒子尺寸及大比表面积, 并且适量的修饰有利于其光催化性能的提高.     

A highly sensitive non-enzymatic glucose sensor based on a simple two-step electrodeposition of cupric oxide (CuO) nanoparticles onto multi-walled carbon nanotube arrays

A novel, stable and highly sensitive non-enzymatic glucose (Glc) sensor was developed using vertically well-aligned multi-walled carbon nanotubes array (MWCNTs) incorporated with cupric oxide (CuO) nanoparticles. The MWCNTs array was prepared by catalytic chemical vapor deposition on a tantalum (Ta) substrate, while a simple and rapid two-step electrodeposition technique was used to prepare the CuO-MWCNTs nanocomposite. First, Cu nanoparticles were deposited onto MWCNTs at constant potential and then they were oxidized into CuO by potential cycling. The electrocatalytic activity of CuO-MWCNTs array was investigated for Glc under alkaline conditions using cyclic voltammetry and chronoamperometry. The sensor exhibited a linear response up to 3 mM of Glc and sensitivity of 2190 μA mM⁻¹ cm⁻², which is two to three orders of magnitude higher than that of most non-enzymatic Glc sensors reported in the literature. The sensor response time is less than 2 s and detection limit is 800 nM (at signal/noise = 3). When tested with human blood serum samples, the sensor exhibited high electrocatalytic activity, stability, fast response and good selectivity against common interfering species, suggesting its potential to be developed as a non-enzymatic Glc sensor.     

Biosynthesis of zinc oxide nanoparticles using Euphorbia milii leaf constituents: Characterization and improved photocatalytic degradation of methylene blue dye under natural sunlight

A facile biosynthesis route was followed to prepare zinc oxide nanoparticles (ZnO NPs) using Euphorbia milii (E. milii) leaf constituents. The SEM images exhibited presence of spherical ZnO NPs and the corresponding TEM images disclosed monodisperse nature of the ZnO NPs with diameter ranges between 12 and 20 nm. The Brunauer–Emmett–Teller (BET) analysis revealed that the ZnO NPs have specific surface area of 20.46 m²/g with pore diameter of 2 nm–10 nm and pore volume of 0.908 cm³/g. The EDAX spectrum exemplified the existence of Zn and O elements and non-appearance of impurities that confirmed pristine nature of the ZnO NPs. The XRD pattern indicated crystalline peaks corresponding to hexagonal wurtzite structured ZnO with an average crystallite size of 16.11 nm. The FTIR spectrum displayed strong absorption bands at 512 and 534 cm^?1 related to ZnO. The photocatalytic action of ZnO NPs exhibited noteworthy degradation of methylene blue dye under natural sunlight illumination. The maximum degradation efficiency achieved was 98.17% at an illumination period of 50 min. The reusability study proved considerable photostability of the ZnO NPs during photocatalytic experiments. These findings suggest that the E. milii leaf constituents can be utilized as suitable biological source to synthesis ZnO NPs for photocatalytic applications.     

纳米氧化锌光催化降解有机染料性能的研究

用自制的纳米ZnO在室外阴天、太阳光照射、室内紫外灯照射等条件下对不同有机染料的降解性能作了系统的研究。结果表明纳米ZnO在太阳光照射条件下对弱碱性有机染料溶液的降解效果较好。本文还比较了自制纳米ZnO与纳米TiO2对有机染料的降解性能，结果表明ZnO的降解效果优于TiO2。     

在光催化还原CO2中具有高催化效率的八面体Cu2O修饰的TiO2纳米管

光催化还原CO2生成烃类燃料是一种可同时解决全球变暖和能源危机问题的最有效途径之一。尽管这方面的研究已经取得了一定的进展,但是整体的光催化转换效率还非常低。因此,需要发展更加高效的催化剂。由于半导体材料禁带宽度与太阳光谱相匹配,人们已经对其进行了广泛研究。其中TiO2因具有无毒、强氧化性以及良好的光学和电学性质等而成为最主要的研究对象。但是对于光催化还原CO2反应来说, TiO2仍存在很多不足,如只能吸收太阳光谱中的紫外光,光生载流子会快速结合,以及光生空穴的强氧化能力等,这些都限制了其光催化还原CO2的效率。采用窄禁带宽度半导体修饰TiO2是解决上述不足的有效途径之一。本文采用简单的电化学方法成功制备了一种由窄禁带半导体Cu2O修饰的TiO2纳米管(TNTs)的复合物,并运用扫描电子显微镜(SEM)、X射线衍射(XRD)以及X射线光电子能谱(XPS)表征了所制备复合物的形貌、化学组成和结晶度。表征结果显示,所制备的TiO2为整齐排列的纳米管阵列结构;复合物中的纳米颗粒为Cu2O;当电化学沉积Cu2O的时间为5 min时,得到的Cu2O纳米颗粒初步呈类八面体结构。随着沉积时间的增加, Cu2O颗粒尺寸增加,具有八面体结构。 XRD和XPS结果表明, TiO2纳米管为锐钛矿,八面体Cu2O纳米颗粒的主要暴露晶面为(111)面。我们还进一步研究了不同量Cu2O纳米颗粒修饰的TiO2纳米管复合物在可见光以及模拟太阳光下光催化还原CO2的能力。在可见光下,由于自身的禁带宽度,纯净的TiO2纳米管没有任何光催化还原CO2的能力;经过Cu2O纳米颗粒的修饰,复合物显现出明显的光催化还原CO2的能力,其中经过30 min Cu2O沉积的TNTs具有最高的光催化效率。在模拟太阳光下,经过15 min Cu2O沉积的TNTs具有最高的光催化效率。在所有光催化还原CO2过程中,主要碳氢产物为甲烷。为了深入地理解该复合体系在还原CO2中的高催化效率,我们对催化剂进行了进一步的表征。紫外-可见漫反射光谱表明, Cu2O八面体纳米颗粒的沉积将TNTs的吸收光谱拓展到了可见光区域,提高了复合物对太阳光的吸收能力。此外,我们还通过测试所制样品的光电流反应、荧光发射光谱以及电化学阻抗谱,研究了催化剂中光生电子和空穴的分离和迁移能力。结果表明,适量的Cu2O沉积提高了复合物对光的吸收能力,增加了光生载流子的数量,从而使更多的光生载流子参与光催化反应。综上,本文首次报道了八面体Cu2O纳米颗粒修饰TNTs复合物的光催化还原CO2的能力。在一定量的Cu2O纳米颗粒修饰下,该复合物在光催化还原CO2生成烃类反应中表现出高效性。经过一系列详细的表征和讨论,我们认为其高效性主要源于三个方面：(1) TNTs的管状结构为反应物的吸附提供了大量的活性位点,同时一维的管状结构更有利于光生载流子的运载,从而提高了电子和空穴的分离;(2) Cu2O纳米颗粒的修饰提高了催化剂对光的吸收,促进催化剂最大程度地利用太阳光;(3) TiO2和Cu2O之间导带以及价带位置的匹配,在减少光生载流子复合的同时也降低了TiO2价带上空穴的氧化能力,从而抑制了CO2还原产物的再氧化过程。     

Synthesis and field emission properties of carbon nanotube films modified with amorphous carbon nanoparticles by a simple electrodeposition method

Amorphous carbon nanoparticles （a-CNPs） on a multi-walled carbon nanotube （MWCNT） film, deposited on a silicon substrate, were synthesized using an electrodeposition combination from a methanol suspension of polydiallyldimethylammonium chloride-modified MWCNTs. A low-voltage electropho- retic deposition of the MWCNTs and a high-voltage electrochemical deposition of the a-CNPs were carried out to yield homogenously attached a-CNPs on the surfaces of the MWCNTs, and form a composite film with good adhesion to the substrate. This scalable technology can produce a large area of a-CNP/MWCNT film. And the field emission investigations show that the a-CNP/MWCNT film has turn- on electric field of 3.17 V μm- 1 （at 10 μA cm-2） and threshold field of 4.62 V μm-1 （at 1 mA cm-2）, which are lower than those of the MWCNT film. The a-CNP/MWCNT film can be deposited simply with large areas and may be a promising cathode material applied in field emission displays.     

Structural,optical and photocatalytic activity of cerium doped zinc aluminate

Zinc aluminate and cerium-doped zinc aluminate nanoparticles are synthesised by co-precipitation method. Ammonium hydroxide is used as a precipitating agent. The synthesised compounds are characterised by powder X-ray diffraction (XRD), Fourier transform Infrared spectroscopy (FT-IR), Ultraviolet diffuse reflectance spectroscopy (UV-DRS), Thermogravimetric analysis (TGA), Scanning electron microscopy (SEM) and Surface area measurements. The photocatalytic activity of zinc aluminate and cerium doped zinc aluminate nanoparticles are studied under the UV light and visible light taking methylene blue as a model pollutant. The amount of catalyst, concentration of dye solution and time are optimised under UV-light. Degradation of methylene blue under the UV-light is found to be 99% in 20 min with 10 mg of cerium doped catalyst. Compared to visible light degradation, the degradation of dye under UV-light is higher. Cerium doping in zinc aluminate (ZnAl₂O₄:Ce³⁺) increased the photocatalytic activity of zinc aluminate.     

Antibacterial study of Eucalyptus grandis fabricated zinc oxide and magnesium doped zinc oxide nanoparticles and its characterization

Mg-doped zinc oxide and zinc oxide nanoparticles were prepared by using methanolic seed extract from the Eucalyptus grandis plant via a green approach. Phytoconstituents present in seed extract act as capping and stabilizing agents for the biosynthesis of nanoparticles. Doping of Mg to zinc oxide nanoparticles increases the bandgap energy, thus enhancing its chemical, physical and optical properties. Further, it was characterized by various techniques such as scanning electron microscopy giving morphological information about the wurtzite hexagonal structure of bio-synthesized nanoparticles. X-ray diffraction technique tells about the crystalline nature of particles and the average crystallite size for zinc oxide and doped zinc oxide nanoparticles. Mg as a dopant enhances the properties of nanoparticles, thus making it more efficiently applicable as an antibacterial agent against Escherichia coli, gram-negative bacteria.     

Ti基TiO_2纳米管阵列的改性及其光催化降解有机污染物

对近年发展的Ti基TiO2纳米管阵列改性的方法及其在光催化降解有机污染物方面应用的研究进展进行了全面的综述,分析了当前存在的问题,并对TiO2纳米管阵列材料研究的发展趋势进行了展望.     

Photocatalytic,antibacterial and anticancer activity of silver-doped zinc oxide nanoparticles

Silver-doped zinc oxide nanoparticles (Ag-ZnO NPs) were successfully synthesized by the Sol-gel method coated with polyethylene glycol as a stabilizing and capping agent. The UV–Vis spectrophotometer analysis was done to analyze the optical property of the nanoparticles. XRD pattern showed the hexagonal structure of ZnO nanoparticles and the reduction in the intensity of the peaks of Ag-ZnO NPs indicates the incorporation of Ag⁺ ions in the ZnO lattices. The surface structural properties of the NPs were confirmed by Field Emission Scanning Electron Microscope (FE-SEM), High Resolution Transmission Electron Microscopy (HRTEM) and Selected Area Electron Diffraction (SAED). The elemental composition of nanoparticles was confirmed by EDAX and XRF-Spectroscopy. The functional group of ZnO and Ag nanoparticles were determined by FT-IR spectroscopy. The photocatalytic activity of Ag-ZnO NPs was studied against ponceau and the maximum degradation percentage was observed to be 89% at 140 min. Further, Ag-ZnO NPs unveiled high potent antibacterial activity against the selected bacterial pathogens and it also rendered significant anticancer activity in UVB-induced HaCaT cells. Consequently, the fluorescent microscopic analysis confirmed the increasing Reactive Oxygen Species (ROS) generation and Mitochondrial Membrane Potential (MMP) loss in the HaCaT cells that leads to the apoptosis induction. Hence, the selected combination of nanoparticles has proven to exhibit higher photocatalytic, antibacterial and anticancer activity. In the near future, it could be an efficient tool for eradicating the dye pollution from wastewater and also preferably be utilized in the cosmetics and pharmaceutical industries to prevent skin cancer.     

Enhancing photocatalytic activity of zinc oxide by coating with some natural pigments

An attempt has been made to enhance the photocatalytic activity of zinc oxide semiconductor by coating it with extracts of natural pigments, chlorophyll and anthocyanin. Coated photocatalyst has been used for the photobleaching of rose bengal dye. Progress of the reaction has been monitored spectrophotometrically by measuring absorbance of the reaction mixture at definite time intervals. The effect of variation of different parameters such as pH, concentration of dye, amount of semiconductor and light intensity on the rate of photobleaching was also observed. A tentative mechanism for the reaction has been proposed.