ZnO/CdS/Ag复合光催化剂的制备及其催化和抗菌性能

先用水热反应合成六方晶相CdS多层级花状微球并在其表面生长ZnO纳米棒形成均匀的ZnO/CdS复合结构,然后用光还原法将Ag纳米颗粒负载于ZnO纳米棒制备出ZnO/CdS/Ag三元半导体光催化剂,对其进行扫描电镜和透射电镜观察、光电性能测试、活性基团捕获实验以及光催化降解和抗菌性能测试,研究其对亚甲基蓝(MB)的降解和抗菌性能。结果表明：ZnO纳米棒均匀生长在CdS微球表面,CdS晶体没有明显裸露,Ag纳米粒子负载在ZnO纳米棒的表面;ZnO/CdS/Ag三元复合光催化剂有良好的可见光响应、较低的阻抗和较高的光电流密度;ZnO/CdS/Ag复合光催化剂能同时产生羟基和超氧自由基等活性氧基团;ZnO/CdS/Ag三元复合光催化剂对亚甲基蓝(MB)的30 min降解率高于90%;0.25 mg/mL的ZnO/CdS/Ag对革兰氏阴性菌(大肠杆菌)的灭菌率高于96%,对革兰氏阳性菌(金黄色葡萄球菌)能完全灭除。     

Effect of leavening agent on structural and photocatalytic properties of ZnO nanorods

In the present work, we have demonstrated a simple, facile, one-step, rapid and cost effective synthesis of ZnO nanorods through the thermal decomposition of zinc acetate and leavening agent (NaHCO₃). The silver nanoparticles (AgNPs) were deposited on the surface of ZnO nanorods by photocatalytic reduction of Ag (I) to Ag(0). As synthesized ZnO nanorods and Ag–ZnO nanocomposites were characterized by using X-ray Diffraction, field emission scanning electron microscope, high-resolution transmission electron microscope and diffuse reflectance spectroscopy. The photocatalytic activities of the ZnO nanorods and Ag–ZnO nanocomposites were evaluated for the photodegradation of Methyl Orange (MO) under UV and sunlight irradiation. The use of common leavening agent helps to prevent the aggregation of ZnO nanorods, further it hinders crystallite growth and narrowing the diameter of nanorods by the evolution of carbon dioxide during calcination. The ZnO nanorods and Ag–ZnO nanocomposite exhibited an enhanced photocatalytic activity and separation of photogenerated electron and hole pairs. Due to effect of leavening agent and AgNPs deposited on surface of ZnO nanorods finds best catalyst for the 99% degradation of MO within 30 min compared to ZnO.     

RGO/ZnO纳米棒复合材料的合成及光催化性能

采用水热合成法制备ZnO纳米棒及RGO/ZnO纳米棒复合材料。研究不同含量的RGO对RGO/ZnO纳米棒复合材料光催化活性的影响。采用X射线衍射仪(XRD)、场发射电子显微镜(FESEM)、光电子能谱仪(XPS)及漫反射紫外-可见吸收光谱(UV-Vis)检测手段对RGO/ZnO进行表征。结果显示:RGO与ZnO纳米棒成功复合。加入GO的含量不同,获得的RGO/ZnO样品在可见光区域的吸光度值不同。以甲基橙作为模拟污染物的光催化结果表明,RGO/ZnO复合材料具有高的紫外-可见光光降解效率,加入GO与ZnO的质量比为3%时,样品紫外-可见光光催化性能最佳,120min内甲基橙基本可以完全降解;且在波长大于400nm可见光照射下,RGO/ZnO具有一定的可见光活性,180min内其降解甲基橙效率最大可达26.2%。同时,RGO/ZnO具有较好的光稳定性。     

Preparation and photoluminescence properties of reverse type-I ZnO/PbS core/shell nanorods

ZnO/PbS one-dimensional core/shell nanorods have been fabricated by a two-step growth method. Photoluminescence properties of these samples with different shell thickness are studied in detail. The result reveals that the photoluminescence intensity of the ZnO/PbS core/shell nanorods changes with the increase of thickness of PbS shell. When the shell is very thin, the increase in photoluminescence intensity is attributed to the modification of surface defect state. When the shell becomes thicker, the formation of a reverse type-I band alignment between the core and shell is ascribed to be the factor resulting in the decrease in intensity of the photoluminescence properties.     

硫化物负载ZnO/ZnAl2O4复合空心球及其光催化还原CO2

采用一步水热法制备了ZnO/ZnAl₂O₄纳米复合物, 通过浸渍法负载CuS、CdS和Bi₂S₃对其进行修饰, 并在模拟太阳光照射下研究负载样品的光催化活性。用XRD、SEM、TEM、BET和FL等技术对所得样品进行表征, 以NaOH 和Na₂SO₃作为光催化还原二氧化碳过程的牺牲剂, 考察了硫化物种类及其负载量对ZnO/ZnAl₂O₄光催化还原活性的影响。结果表明, 负载CuS和CdS均可提高ZnO/ZnAl₂O₄光催化还原活性, 而负载Bi₂S₃却有所降低。当CuS负载量为1wt%时, 样品光催化还原活性最佳, 反应6 h后所得还原产物甲醇的生成量为8.21 mmol/g_cat, 在相同条件下较原样提高了约3.2倍。对CuS/ZnO/ZnAl₂O₄的光催化机理进行了初步探讨。     

ZnO nanorod/CdS nanocrystal core/shell-type heterostructures for solar cell applications

ZnO/CdS core/shell nanorod arrays were fabricated by a two-step method. Single-crystalline ZnO nanorod arrays were first electrochemically grown on SnO(2):F (FTO) glass substrates. Then, CdS nanocrystals were deposited onto the ZnO nanorods, using the successive ion layer adsorption and reaction (SILAR) technique, to form core/shell nanocable architectures. Structural, morphological and optical properties of the nanorod heterojunctions were investigated. The results indicate that CdS single-crystalline domains with a mean diameter of about 7 nm are uniformly and conformally covered on the surface of the single-crystalline ZnO nanorods. ZnO absorption with a bandgap energy value of 3.30 ± 0.02 eV is present in all optical transmittance spectra. Another absorption edge close to 500 nm corresponding to CdS with bandgap energy values between 2.43 and 2.59 eV is observed. The dispersion in this value may originate in quantum confinement inside the nanocrystalline material. The appearance of both edges corresponds with the separation of ZnO and CdS phases and reveals the absorption increase due to CdS sensitizer. The photovoltaic performance of the resulting ZnO/CdS core/shell nanorod arrays has been investigated as solar cell photoanodes in a photoelectrochemical cell under white illumination. In comparison with bare ZnO nanorod arrays, a 13-fold enhancement in photoactivity was observed using the ZnO/CdS coaxial heterostructures.     

Effect of Surface Coating on the Photocatalytic Function of Hybrid CdS–Au Nanorods

Hybrid semiconductor–metal nanoparticles are interesting materials for use as photocatalysts due to their tunable properties and chemical processibility. Their function in the evolution of hydrogen in photocatalytic water splitting is the subject of intense current investigation. Here, the effects of the surface coatings on the photocatalytic function are studied, with Au‐tipped CdS nanorods as a model hybrid nanoparticle system. Kinetic measurements of the hydrogen evolution rate following photocatalytic water reduction are performed on similar nanoparticles but with different surface coatings, including various types of thiolated alkyl ligands and different polymer coatings. The apparent hydrogen evolution quantum yields are found to strongly depend on the surface coating. The lowest yields are observed for thiolated alkyl ligands. Intermediate values are obtained with L‐glutathione and poly(styrene‐co‐maleic anhydride) polymer coatings. The highest efficiency is obtained for polyethylenimine (PEI) polymer coating. These pronounced differences in the photocatalytic efficiencies are correlated with ultrafast transient absorption spectroscopy measurements, which show a faster bleach recovery for the PEI‐coated hybrid nanoparticles, consistent with faster and more efficient charge separation. These differences are primarily attributed to the effects of surface passivation by the different coatings affecting the surface trapping of charge carriers that compete with effective charge separation required for the photocatalysis. Further support of this assignment is provided from steady‐state emission and time‐resolved spectral measurements, performed on related strongly fluorescing CdSe/CdS nanorods. The control and understanding of the effect of the surface coating of the hybrid nanosystems on the photocatalytic processes is of importance for the potential application of hybrid nanoparticles as photocatalysts.     

Enhanced ferromagnetic and photocatalytic properties in Mn or Fe doped p-CuO/n-ZnO nanocomposites

Mn doped CuO/ZnO heterostructure exhibited significant room temperature ferromagnetism and visible light photocatalytic properties. Phase analysis for the pure, Mn and Fe doped CuO/ZnO nanocomposites evidently confirmed the formation of CuO and ZnO phases in each composite without any impurities. Based on Rietveld refinement analysis, the inclusion of Mn ions into CuO/ZnO nanocomposite decreased the unit cell volume of both oxides while Fe ions lead to lattice expansion. Mn ions induced the formation of ZnO hexagonal nanorods in CuO/ZnO nanocomposite. Nano-flakes and spherical nanoparticles shapes were seen for Fe doped CuO/ZnO nanocomposites. The characteristics IR absorption bands of CuO and ZnO overlapped together in their nanocomposites structure. From Kubelka-Munk plots, the incorporation of Mn ions enabled the ZnO band gap to absorb in the visible light region. Pure CuO/ZnO nanocomposite exhibited room temperature ferromagnetism with saturation magnetization (M_s) of 0.042 emu/g and coercivity (H_c) of 547 Oe. The ferromagnetic properties of the pure CuO/ZnO nanocomposite were greatly improved by Mn and Fe doping and the saturation magnetization extremely jumped to 0.86 and 0.85 emu/g, respectively. High photocatalytic activity, 98%, with good reusability for methyl orange (MO) degradation under visible light irradiation was achieved by 4 wt% Mn doped CuO/ZnO nanocomposite. A relation between the crystallinity, band gap and photocatalytic activity with dopant type (Mn or Fe) incorporated into CuO/ZnO nanocomposites was noticed. In contrary to Fe dopant, Mn as dopant played successful roles in improving the crystallinity, band gap and photocatalytic properties of CuO/ZnO nanocomposite. Multifunctional properties can be realized by combining different oxides in heterostructure form and using doping technique.     

纳米ZnO可见光催化活性的改善及其降解性能

由于半导体ZnO禁带宽度较宽,因而其可见光催化活性较差。本文分别采用N掺杂、碳包覆、贵金属修饰以及半导体复合等方式来改善纳米ZnO的可见光催化活性,并以罗丹明B为降解污染物,对比了不同材料可见光催化降解有机污染物的效率。研究结果显示以氨水为氮源,通过水热法制备的氮掺杂N-ZnO光催化剂,相比于纯ZnO,对可见光吸收增强。采用葡萄糖水热碳化法所制备的C@N-ZnO样品则对有机污染物具有强的吸附能力,贵金属沉积所获得的样品Au/C@N-ZnO与半导体复合所制备的复合结构CdS/Au/C@N-ZnO在可见光区域具有更强的吸收能力。稳态和瞬态荧光光谱显示氧缺陷、贵金属沉积以及半导体复合形成异质结可有效提高光生载流子的分离效率,从而提高催化剂的光降解效率,并对催化机理进行了初步探讨。可见光催化降解罗丹明B结果显示CdS/Au/C@N-ZnO样品的反应速率是纯ZnO的6.7倍。     

In-situ synthesis of CdS/g-C<Subscript>3</Subscript>N<Subscript>4</Subscript> hybrid nanocomposites with enhanced visible photocatalytic activity

A novel and simple in situ synthetic strategy was used to fabricate CdS/g-C₃N₄ hybrid nanocomposite catalysts with visible-light-driven photocatalytic activity from cadmium-containing carbon nitride compounds. X-ray diffraction measurements, high-resolution transmission electron microscopy images, and Fourier transform infrared spectra showed heterojunctions with a close interface between the g-C₃N₄ and the CdS nanoparticles and nanorods in the composite. Ultraviolet visible diffuse reflectance spectra exhibited a red shift that further presented the CdS in the polymer g-C₃N₄ skeleton, which allowed the efficient utilization of the solar spectrum for creating photogenerated electrons and holes. The photoluminescence spectra of the nanocomposites suggested charge transfer from g-C₃N₄ to CdS. The photocurrent intensity of hybrid nanocomposites was 2.3 times than that of pure g-C₃N₄ sample, and photocatalytic activity for the photodegradation of methyl orange was 2.5 times, and hydrogen evolution reaction was 2.8 times. Enhanced photocatalytic activity and photocurrent for the CdS/g-C₃N₄ hybrid nanocomposites were achieved.     

Growth and photocatalytic properties of one-dimensional ZnO nanostructures prepared by thermal evaporation

Aligned ZnO nanorods and nanotubes were grown on the silicon substrates by thermal evaporation of high pure zinc powders without any other metal catalyst. The morphology evolution of ZnO nanostructures with prolonged growth time suggested that the growth of the ZnO nanorods and nanotubes follows the vapor–liquid–solid mechanism. ZnO nanoneedle and nanoparticle films were also synthesized by the same way, and their photocatalytic performances were tested for the degradation of organic dye methylene blue. The ZnO nanoneedle films exhibited very high photocatalytic activities. The decomposition kinetics of the organic pollutant was discussed. Moreover, it is found that the ZnO nanoneedle films showed very stable photocatalytic activity.     

Enhanced performance of Al2O3 coated ZnO nanorods in CdS/CdSe quantum dot-sensitized solar cell

CdS/CdSe quantum dot-sensitized solar cells (QDSCs) based on ZnO nanorods, 4.55 μm in length, were studied. Many studies have shown that the performance of QDSCs is limited by a recombination process. Therefore, the interface layer was fabricated on the surface of the ZnO nanorods to retard recombination at the interface between the semiconductor and electrolyte. Overall, the performance of the QDSCs was improved by a surface coating of aluminum isopropoxide (Al₂O₃) on the ZnO nanorod, which facilitates a decrease in electron recombination and increased adsorption of CdS/CdSe QDs on the ZnO nanorods.     

Size-induced variations in lattice dimension, photoluminescence, and photocatalytic activity of ZnO nanorods

Highly crystalline ZnO nanorods with diameters ranging from 5 to 57 nm were prepared by a seed-mediated solution method. With a diameter reduction, the lattice volume of ZnO nanorods increased and c/a ratio decreased, in apparent contradiction to what was observed in spherical ZnO nanocrystals. All ZnO nanorods showed a strong yellow emission without the UV or green emissions that had been observed for ZnO nanostructures prepared by other methods. For larger diameters, the yellow emission exhibited an abnormal red shift, which was associated with the lattice variations in the nanoscale structure and the resulting band modifications. The size-induced band modifications were also confirmed by the photocatalytic activity of ZnO nanorods, which have an optimum diameter (approximately 30 nm) for the photodegradation of Rhodamine B dye solution.     

Photocatalytic paper using zinc oxide nanorods

Zinc oxide (ZnO) nanorods were grown on a paper support prepared from soft wood pulp. The photocatalytic activity of a sheet of paper with ZnO nanorods embedded in its porous matrix has been studied. ZnO nanorods were firmly attached to cellulose fibers and the photocatalytic paper samples were reused several times with nominal decrease in efficiency. Photodegradation of up to 93% was observed for methylene blue in the presence of paper filled with ZnO nanorods upon irradiation with visible light at 963 Wm^–2 for 120 min. Under similar conditions, photodegradation of approximately 35% was observed for methyl orange. Antibacterial tests revealed that the photocatalytic paper inhibits the growth of Escherichia coli under room lighting conditions.     

Synthesis and characterization of ultra small PbS nanorods in sucrose ester microemulsion

In the present study, we report for the first time the synthesis of ultra small PbS nanorods in a non-ionic sugar based water-in-oil (w/o) microemulsion system using food grade sucrose ester as surfactant. PbS was formed by mixing lead nitrate and thioacetamide in the water core of the microemulsion system. The as-prepared PbS nanorods were characterized by X-ray diffractometry (XRD), uv–visible absorption spectroscopy (UV–VIS), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The diameter of the PbS nanorods were found to be extremely small, which is in the range of 2.64 nm to 2.91 nm depending on reaction aging time. Spherical PbS nanoparticles were formed after 12 h and PbS nanorods were formed after more than 1 day of reaction aging time.     

ZnO:Cd纳米棒的制备及其光催化降解性能研究

采用水热法制备了ZnO和不同Cd掺杂浓度的ZnO:Cd纳米棒。通过x射线衍射仪、扫描电子显微镜、紫外-可见-近红外分光光度计和拉曼光谱对ZnO:Cd纳米棒的结构和光学特性进行了系统研究。结果显示,样品为一维纳米棒结构,Cd的掺杂可以减小ZnO纳米棒的晶粒尺寸和光学带隙。利用分光光度计检测ZnO:Cd纳米棒对偶氮结构染料(甲基橙溶液)的光催化降解效率,结果表明Cd掺杂可以改善ZnO的光催化性能,掺杂浓度为16%时ZnO:Cd纳米棒对甲基橙溶液的光催化降解效率最高。     

Facile preparation of Ag/ZnO nanoparticles via photoreduction

Ag/ZnO nanoparticles can be obtained via photocatalytic reduction of silver nitrate at ZnO nanorods when a solution of AgNO₃ and nanorods ZnO suspended in ethyleneglycol is exposed to daylight. The mean size of the deposited sphere like Ag particles is about 5 nm. However, some of the particles can be as large as 20 nm. The ZnO nanorods were pre-prepared by basic precipitation from zinc acetate di-hydrate in the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide. They are about 50–300 nm in length and 10–50 nm in width. Transmission electron microscopy (TEM), energy-dispersive X-ray analysis (EDS), X-ray powder diffraction (XRD), UV–Vis spectroscopy, X-ray photoelectron spectroscopy (XPS), and photoluminescence (PL) were used to characterize the resulting Ag/ZnO nanocomposites.     

Photocatalytic paper using zinc oxide nanorods

Abstract

Zinc oxide (ZnO) nanorods were grown on a paper support prepared from soft wood pulp. The photocatalytic activity of a sheet of paper with ZnO nanorods embedded in its porous matrix has been studied. ZnO nanorods were firmly attached to cellulose fibers and the photocatalytic paper samples were reused several times with nominal decrease in efficiency. Photodegradation of up to 93% was observed for methylene blue in the presence of paper filled with ZnO nanorods upon irradiation with visible light at 963 Wm^–2 for 120 min. Under similar conditions, photodegradation of approximately 35% was observed for methyl orange. Antibacterial tests revealed that the photocatalytic paper inhibits the growth of Escherichia coli under room lighting conditions.     

Well-defined Au/ZnO nanoparticle composites exhibiting enhanced photocatalytic activities

Well-defined Au/ZnO nanoparticle composites were prepared by modifying ZnO with preformed Au nanoparticles protected with bifunctional glutathione ligand. In this approach, the Au nanoparticles were highly monodisperse and their loading on ZnO surface could be precisely controlled by the anchoring conditions. Steady-state and time-resolved photoluminescence of the composites revealed the ability of the Au nanoparticles to efficiently extract conduction band electrons from the photoexcited ZnO. The composites exhibited strongly enhanced photocatalytic activity without requiring thermal activation process in degrading organic substrates in both oxidative and reductive pathways. A clear correlation between the photocatalytic activity and the Au loading was found for both oxidative and reductive photocatalytic reactions. These results demonstrate that thiolate-protected AuNPs can significantly enhance the charge separation by extracting electrons from the photoexcited ZnO and consequently improve the photocatalytic activity of the composites.     

水热法制备纤维素基CdS纳米复合材料及其光催化性能研究

以棉花为纤维素基质,CdCl_2·21/2H_2O和L-半胱氨酸为原料,采用水热法制备了纤维素基CdS纳米复合材料。以亚甲基蓝(MB)为目标降解物,研究了反应时间和反应温度对该复合材料光催化性能的影响,通过XRD、SEM、FT-IR和UV-VisDRS对不同温度下制得的复合材料进行了结构表征。结果表明,反应温度为影响纤维素基CdS样品光催化活性的关键因素,且对样品中CdS的微观结构有显著影响。当反应温度为120℃时,样品的光催化活性最佳,反应50min对MB溶液的光降解率达到94.78%。经过3次循环其光降解率基本保持不变,表明纤维素基CdS是一种稳定有效的光催化剂。光催化增强机理分析表明,CdS光生电子迁移至纤维素表面,实现了与光生空穴的有效分离,从而增强了材料的光催化性能。