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1.
《中国化学快报》2022,33(8):3705-3708
A kind of CdS/Cd-BiOCl immobilized films photocatalyst was prepared. The optical and physicochemical properties of the CdS/Cd-BiOCl photocatalysts were analysed, and the detailed characterization revealed CdS/Cd-BiOCl films photocatalyst with good charge carrier separation effect. The reusabilities and photocatalytic properties of the samples were studied. The 15%CdS/Cd-BiOCl photocatalyst exhibited superior performance in photocatalytic degradation of tetracycline (TC) and favorable stability under visible light irradiation. As for the photodegradation rate of TC, 15%CdS/Cd-BiOCl exhibited an excellent photodegradation activity, which is 4.06 and 9.53 times higher than that of CdS/Cd and BiOCl, respectively. The results showed that dominant active species are ?O2? and ?OH radicals during photodegradation. The charge transfer in Z-scheme CdS/Cd-BiOCl films photocatalyst could synchronously generate conduct band (CB) electrons in BiOCl and valence band (VB) holes in CdS, and metal Cd served as electron mediator. This work can be a reference for the design of film photocatalysts and new insight for photodegradating towards contaminants.  相似文献   

2.
通过溶剂散逸自组装法制备了聚苯乙烯(PS)有序多孔膜. 利用水珠在冷的PS溶液表面凝结形成有序阵列, 使PS以水珠阵列为模板形成有序多孔膜. 将有序多孔膜的上层剥离并附着在可收缩性高分子表面, 并进行离子溅射, 除掉有序多孔膜后在可收缩膜上留下了有序的金属圆盘阵列. 经过收缩, 有序阵列不仅光学性质发生了改变, 而且实现了导电的各向异性.  相似文献   

3.
采用有序介孔氧化硅为硬模板, 通过纳米浇筑法制备了由螺旋骨架构建的有序介孔硫化镉(CdS)光 催化材料. 该光催化材料具有约5 nm厚的超薄骨架和大的比表面积(238 m2/g), 能有效缩短光催化反应中 光生电荷迁移到表面进行反应的距离并同时提供更多的反应活性位点, 从而增强光催化性能. 通过原位化学沉积法将不同量的助催化剂硫化镍(NiS)沉积到有序介孔CdS表面, 得到了一系列超薄骨架有序介孔CdS/NiS复合光催化材料. 可见光照射下的光催化产氢活性测试结果表明, 负载适量NiS的有序介孔CdS具有显著增强的光催化产氢活性(3.84 mmol?h-1?g-1), 约为负载相同量NiS的普通商业化CdS材料(0.22 mmol?h-1?g-1)的17.5倍.  相似文献   

4.
The synthesis and characterization of cadmium sulphide (CdS) quantum dots, conjugated in a porous phosphate heterostructure functionalized with aminopropyl groups is described. The resulting material has fluorescence properties with maximum emission intensity at 575 nm. The fluorescent materials are not soluble in water and exhibit high stability in aqueous solution in the pH ranges from 2 to 9. Energy dispersive X-ray spectroscopy confirmed the qualitative elemental composition of the synthesized materials and X-ray photoelectron spectra showed a surface S/Cd atomic ratio of 1.09. SEM images show that the materials are amorphous, possessing porous with sizes of several tens nanometres, homogeneous and exhibit a layered morphology. The adsorption–desorption analysis by N2 at 77 K showed the accessibility of the CdS quantum dots onto the pores of the structure. The CdS quantum dots were stabilized by mercaptopropionic acid and bounded to the host materials by amine groups.  相似文献   

5.
In this Article, we addressed a facile method for the fabrication of porous polyimide film with an ordered surface based on the solvent-evaporation-assisted in situ self-assembly of polyamic acid (PAA, precursor of polyimide) and silica microspheres during vacuum-drying of PAA/silica colloid solution. Hydroxyl groups on the surface of silica microspheres have strong hydrogen-bonding with PAA chains, which improve the dispersion of silica microspheres in PAA/DMF solution and further help the self-assembly of PAA/silica colloid solution via solvent evaporation. The approach is simple, neither the preparation of special template nor complex preparation process and precise control over condition is necessary. Furthermore, the method could be employed for mass production of ordered porous polyimide films, and by changing the content and size of silica microspheres, the pore size and porous structure of the porous polyimide films could be tunable. The wettability behavior of the as-prepared porous polyimide films is also studied; the ordered surface topography of the porous polyimide films could change the wettability from hydrophilicity to hydrophobicity.  相似文献   

6.
A series of surfactant-encapsulated polyoxometalates which have different compositions, shapes, and sizes, are able to self-assemble to the highly ordered honeycomb-structured macroporous films at the air/water interface without any extra moist airflow across the solution surface. The honeycomb film pores in the average diameter of 2-3 μm are obtained, which are independent of the polyoxometalates. It is speculated that the cooled micrometer water droplets act as the necessary templates for the formation of macropores, and the stability of these water droplets is crucial during the self-assembly. With increasing the concentration of surfactants, various morphologies from lowly ordered honeycomb films to highly ordered honeycomb films and then to disordered fragments can be modulated. The interfacial tension between chloroform solution and water droplets induces the changes of films. High-resolution TEM observations indicate a close-packed lamellar structure in the ordered honeycomb film walls. The self-assembly successfully performs the transfer of functional polyoxometalates from bulk solutions to interfacial films. Consequently, the produced honeycomb films present electronic activities, such as ferromagnetism and electrochemical properties. These detailed researches will enrich the studies based on materials obtained by encapsulations in cationic surfactants to construct newly nanostructures of polyoxometalates at interfaces, and promote the potential applications of the honeycomb films of surfactant-encapsulated polyoxometalates in advanced materials.  相似文献   

7.
表面修饰的Q态纳米CdS的荧光性能研究   总被引:6,自引:0,他引:6  
纪欣  章伟光  范军  钟昀  闫云辉 《化学学报》2004,62(16):1514-1518
以硫醇为表面修饰剂,通过控制硫醇与Cd2+的比例,得到性能稳定的Q-CdS,而后将Q-CdS与聚合物通过共混复合成膜.通过荧光光谱研究了硫醇和聚合物对Q-CdS的表面修饰作用,研究发现硫醇的长碳链有效阻止了CdS粒子间的团聚,碳链的增加导致Q-CdS稳定性的增强,Q-CdS的激子发射峰强度增大,且这种表面修饰效应随硫醇加入量的增大而增强,在一定硫醇加入量时的激子荧光发射强度达到最大.由于介电局域效应,聚合物的加入使Q-CdS的表面态荧光发光强度呈数量级增大.另一方面,随着聚合物加入量的增加又会导致Q-CdS的表面钝化,缺陷减小,表面态荧光发射峰相对减弱,而激子发射峰却增强.  相似文献   

8.
The influences of pH and NaCl concentration of dipping solutions and the pH and NaCl concentration of disintegration solutions on the disintegration behaviors of poly(4-vinylpyridiniomethanecarboxylate) (PVPMC)/poly(sodium 4-styrenesulfonate) (PSS) (PVPMC/PSS) multilayer films were investigated by ultraviolet-visible spectroscopy (UV-vis), Fourier transform infrared spectroscopy (FT-IR), quartz crystal microbalance (QCM) and atomic force microscopy (AFM). It was found that the disintegration rates and degrees of PVPMC/PSS multilayer films in neutral water could be well controlled by changing pH of dipping solutions and immersion time during the disintegration process. Furthermore, PVPMC/PSS multilayer films could be disintegrated completely and rapidly in pH 8 alkali solution or physiological condition (i.e., 0.15 M NaCl solution). The controllable disintegration of PVPMC/PSS multilayer films was then utilized to fabricate PEC/PSS free-standing multilayer films, in which PEC was a positively charged polyelectrolyte complex made from excessive poly(diallyldimethylammonium) (PDDA) and PSS. The experimental results indicated that the disintegration rates of PVPMC/PSS sacrificial sublayer strongly affected the integrity of the resultant PEC/PSS free-standing multilayer films. Only free-floating PEC/PSS was released from neutral water by disintegrating PVPMC/PSS multilayer sublayers. However, large size flat and tube-like PEC/PSS free-standing multilayer films with good mechanical properties were obtained facilely from pH 8 alkali solution and 0.15 M NaCl solution, respectively. The preparation of such free-standing films at physiological condition may be useful in the biological or medical application.  相似文献   

9.
吕功煊 《分子催化》2012,(3):265-275
用丙烯酸酯和环氧树脂将亲水性的-OH和芳香性的苯环修饰到Pt/ZnS-CdS/SiO2催化剂表面,在不同气氛下进行热处理,得到了表面修饰并热处理后的Pt/ZnS-CdS/SiO2光催化剂,考察催化剂的可见光催化分解水产氢活性.结果表明修饰并热处理后催化剂活性不同程度的下降.XRD结果表明,修饰前后ZnS和CdS的特征衍射峰没有改变,但空气热处理致使催化剂晶型由立方晶型的CdS和六方晶型的ZnS向六方晶型的CdS和α-ZnS的转变,氢气气氛热处理致使催化剂的晶型向六方结构的固溶体Zn0.5Cd0.5S转变,未修饰的催化剂在空气和氢气中热处理后晶型发生了同样的转变.HRTEM结果表明表面修饰后催化剂平均粒径由18 nm减小为6 nm,仍以ZnS为外层,CdS为内层的核壳结构形态存在.紫外可见漫反射(UV-Vis DRS)结果表明,经修饰和热处理后的光催化剂在450~800 nm区间的光吸收增加,在空气中773 K煅烧后的催化剂的吸收限由480 nm红移至520 nm,而在氢气中于773 K煅烧后吸收限则由480 nm蓝移至420 nm.修饰后催化剂的羟基吸收强度增大,出现了苯环的特征吸收峰,这些官能团经热处理后发生了显著变化.红外光谱(IR)结果表明空气热处理导致部分含氧官能团发生了脱离,羟基吸收增强;氢气热处理导致C—O和C—O—C的吸收峰增强,同时催化剂表面发生碳化.热重差热分析(TG-DTA)与红外结果均证实了这种变化.产氢活性下降可能归结为表面羟基减少导致的在反应体系中的分散性和光生电荷的分离效率降低;催化剂表面的含氧官能团占据了催化活性位并且降低了颗粒在水溶液中的分散性.  相似文献   

10.
Inverse opal films with unique optical properties have potential as photonic crystal materials and have stimulated wide interest in recent years. Herein, iridescent hybrid polystyrene/nanoparticle macroporous films have been prepared by using the breath‐figure method. The honeycomb‐patterned thin films were prepared by casting gold nanoparticle‐doped polystyrene solutions in chloroform at high relative humidity. Highly ordered hexagonal arrays of monodisperse pores with an average diameter of 880 nm are obtained. To account for the observed features, a microscopic phase separation of gold nanoparticles is proposed to occur in the breath‐figure formation. That is, individual gold nanoparticles adsorb at the solution/water interface and effectively stabilize condensed water droplets on the solution surface in a hexagonal array. Alternatively, at high nanoparticle concentrations the combination of breath‐figure formation and nanoparticle phase separation leads to hierarchical structures with spherical aggregates under a honeycomb monolayer. The films show large features in both the visible and NIR regions that are attributed to a combination of nanoparticle and ordered‐array absorptions. Organic ligand‐stabilized CdSe/CdS quantum dots or Fe3O4 nanoparticles may be loaded into the honeycomb structure to further modify the films. These results demonstrate new methods for the fabrication and functionalization of inverse opal films with potential applications in photonic and microelectronic materials.  相似文献   

11.
Ligand exchange reactions at the surface of oleate- and trioctylphosphine oxide (TOPO)-capped CdS quantum dots have been studied with attenuated total reflection infrared (ATR-IR) spectroscopy, using thin films deposited from organic solvent suspensions. The oleate and trioctylphosphine capping ligands were found to form highly ordered and densely packed monolayers on the CdS surface. Adsorbed oleate is coordinated to CdS in a chelating bidentate manner through the carboxylate functional group, while adsorbed trioctylphosphine oxide is coordinated though the P=O functional group and appears to have numerous adsorption environments on the CdS surface. Exposure of such films to aqueous solution was found to cause partial delamination of the films from the ATR prism interface which was reversible upon redrying. Ligand exchange reactions on the oleate- and trioctylphosphine-capped CdS films were studied in situ at room temperature by allowing the films to be exposed to dilute aqueous solutions of thiol-containing ligands. Oleate and trioctylphosphine oxide are both strongly adsorbed to the CdS surface, and ligand exchange with monothiol-containing ligands has been found to be highly dependent upon experimental conditions, in particular pH, where exchange is only observed at solution pH where the exchanging ligand is uncharged. This is attributed to the inability of a charged ligand to penetrate the hydrophobic polymethylene layer on the CdS surface.  相似文献   

12.
Semiconducting films of CdS are produced by the cathodic deposition of Cd on inert electrodes in the presence of dissolved S8 in dimethylsulfoxide solution. Linear potential scans and potential pulse measurements show that the first layers are formed by underpotential deposits of Cd reacting with S8 from the solution. With increasing coverage of the surface the mechanism changes to a mixed reduction of Cd and a reduction of S8 to sulfide, which forms the deposit with Cd2+ from the solution. Photoeffects are observed with deposits greater than three or four equivalent monolayers of CdS, demonstrating the n-type character of the deposits. The photocurrent spectrum of films in the micrometer range differs considerably from that of single-crystal CdS. Films produced in this way need further treatment before they could be useful as low-cost electrodes for solar cells.  相似文献   

13.
如何提高光催化制氢量子产率是太阳能分解水制氢研究的重点和焦点. Zn-Cd-S固溶体因具有窄的带隙宽度及合适的导带和价带位置而显示了广阔的应用前景. 然而, 两方面的问题限制了其规模化应用: (1)往往需负载Pt, Pd, Ru和Rh等贵金属助催化剂才能获得可观的光催化性能; (2)传统合成技术通常采用硫代乙酰胺、硫脲及硫化钠等昂贵且有毒的化学试剂作硫源. 与上述硫源相比, 生物小分子L-胱氨酸分子中含有-COOH、-NH2及-SH基团, 这些基团易于与金属阳离子配位, 因此能够有效调控硫源释放S2-的速度, 硫化物的形貌、尺寸以及取向能够灵活地得到调控. 另外, 在强碱或强酸性介质中, L-胱氨酸具有良好的水溶性, 因此材料的合成可选择在水介质中, 这对光催化过程是非常关键的, 有利于改善材料在光催化反应过程中的稳定性. 基于此, 本文以经济环保的生物小分子作硫源, 制备了高效、稳定且有可见光响应的纳米硫化物光催化体系, 旨在发展环境友好、条件温和、成本低廉、操作简单和易于工业化生产的绿色制备技术, .以L-胱氨酸为硫源和结构导向剂, 采用水热合成技术在温和条件下制备了立方相结构的Zn-Cd-S固溶体光催化剂, 采用XRD, TEM, HRTEM, XPS, UV-vis及N2吸附等手段表征了其结构和形貌. 结果表明, 随Zn含量增加, 其带隙在2.11-3.19 eV间连续可调. 在可见光(λ > 420 nm)照射、无助催化剂和Na2S/Na2SO3水溶液为牺牲剂的条件下研究了其光催化制氢的性能. 其中Zn0.9Cd0.1S具有最佳的光催化活性, 其产氢速率约为4.4 mmol h -1g -1(无助催化剂, 远高于CdS), 且显示优良的稳定性及抗光腐蚀能力. 通过经验公式计算得出了其能带结构示意图, 结果表明, ZnxCd1-xS固溶体的导带和价带的位置随着Zn含量的增加而向更负的导带和更正的价带移动. 固溶体导带电位更负促进更有效的氢产生, 电位价带更正导致电荷更容易发生转移. Zn0.9Cd0.1S高的光催化活性可能归因于中等的导带边缘和最合适的带隙. 最后利用光电流及交流阻抗阐明了其光生电子-空穴对的分离及迁移机理. 与CdS相比, Zn-Cd-S固溶体的形成促进了光生载流子在界面间的传输, 抑制了其快速复合, 从而大幅度改善了光催化活性及稳定性. 该硫化物纳米晶的绿色制备技术期望可推广到其它硫化物可见光光催化体系.  相似文献   

14.
We report for the first time the synthesis of free-standing mesoporous carbon films with highly ordered pore architecture by a simple coating-etching approach, which have an intact morphology with variable sizes as large as several square centimeters and a controllable thickness of 90 nm to ~3 μm. The mesoporous carbon films were first synthesized by coating a resol precursors/Pluronic copolymer solution on a preoxidized silicon wafer and forming highly ordered polymeric mesostructures based on organic-organic self-assembly, followed by carbonizing at 600 °C and finally etching of the native oxide layer between the carbon film and the silicon substrate. The mesostructure of this free-standing carbon film is confirmed to be an ordered face-centered orthorhombic Fmmm structure, distorted from the (110) oriented body-centered cubic Im3?m symmetry. The mesoporosity of the carbon films has been evaluated by nitrogen sorption, which shows a high specific BET surface area of 700 m(2)/g and large uniform mesopores of ~4.3 nm. Both mesostructures and pore sizes can be tuned by changing the block copolymer templates or the ratio of resol to template. These free-standing mesoporous carbon films with cracking-free uniform morphology can be transferred or bent on different surfaces, especially with the aid of the soft polymer layer transfer technique, thus allowing for a variety of potential applications in electrochemistry and biomolecule separation. As a proof of concept, an electrochemical supercapacitor device directly made by the mesoporous carbon thin films shows a capacitance of 136 F/g at 0.5 A/g. Moreover, a nanofilter based on the carbon films has shown an excellent size-selective filtration of cytochrome c and bovine serum albumin.  相似文献   

15.
A nanoarchitectural approach based on in situ formation of quantum dots (QDs) within/outside clay nanotubes was developed. Efficient and stable photocatalysts active under visible light were achieved with ruthenium-doped cadmium sulfide QDs templated on the surface of azine-modified halloysite nanotubes. The catalytic activity was tested in the hydrogen evolution reaction in aqueous electrolyte solutions under visible light. Ru doping enhanced the photocatalytic activity of CdS QDs thanks to better light absorption and electron–hole pair separation due to formation of a metal/semiconductor heterojunction. The S/Cd ratio was the major factor for the formation of stable nanoparticles on the surface of the azine-modified clay. A quantum yield of 9.3 % was reached by using Ru/CdS/halloysite containing 5.2 wt % of Cd doped with 0.1 wt % of Ru and an S/Cd ratio of unity. In vivo and in vitro studies on the CdS/halloysite hybrid demonstrated the absence of toxic effects in eukaryotic cells and nematodes in short-term tests, and thus they are promising photosensitive materials for multiple applications.  相似文献   

16.
A simple method of microwave assisted chemical bath deposition (MA-CBD) was adopted to fabricate cadmium sulfide (CdS) thin films. The superhydrophobic surface with a water contact angle (CA) of 151 degrees was obtained. Via a scanning electron microscopy (SEM) observation, the film was proved having a porous micro/nano-binary structure which can change the property of the surface and highly enhance the hydrophobicity of the film. A possible mechanism was suggested to describe the growth of the porous structure, in which the microwave heating takes an important role in the formation of two distinct characteristic dimensions of CdS precipitates, the growth of CdS sheets in micro-scale and sphere particles in nano-scale. The superhydrophobic films may provide novel platforms for photovoltaic, sensor, microfluidic and other device applications.  相似文献   

17.
This paper reports a rapid and facile method of preparing free-standing colloidal crystals from monodisperse charged polystyrene (PS) microspheres. Mixed solvents (ethanol/water) were used as the dispersion medium in the self-assembly process of colloidal crystals. By a simple "floating self-assembly" method, PS microspheres floated on the surface of liquid and self-assembled into large area of three-dimensional (3D) ordered colloidal crystals within 15 min. Then epichlorohydrin was added in as a cross-linking agent to strengthen the colloidal-crystal film. After cross-linking reactions between the microspheres, the obtained colloidal-crystal film was free-standing and could be easily transferred to other substrates. Using tetrabutyl titanate as a titania precursor, 3D porous TiO(2) materials with rodlike skeletal structure were fabricated from the prepared free-standing colloidal crystal. This work provides a facile method to fabricate free-standing colloidal-crystal film, which can be used as an ideal template for the preparation of porous materials.  相似文献   

18.
A facile gas phase polymerization method has been proposed in this work to fabricate porous free-standing polypyrrole (PPy) films. In the presence of pyrrole vapor, the films are obtained in the gas/water interface spontaneously through the interface polymerization with the oxidant of FeCl(3) in the water. Both the thickness of the film and the size of the pores could be controlled by adjusting the concentrations of the oxidant and the reaction time. The as-prepared PPy films exhibited a superhydrophilic behavior due to its composition and porous structures. We have demonstrated a possible formation mechanism for the porous free-standing PPy films. This gas phase polymerization is shown to be readily scalable to prepare large area of PPy films.  相似文献   

19.
CdS nanoparticles, prepared in reverse micellar system, were immobilized onto thiol-modified aluminosilicate particles (ASSH) by a simple operation: addition of ASSH in the micellar solution and mild stirring. The resulting CdS nanoparticles-aluminosilicate composites (ASCdS) were used as photocatalysts for H2 generation from 2-propanol aqueous solution. The chemical properties of the aluminosilicate, such as affinity for water and other reactants, were found to affect the photocatalytic property of the CdS nanoparticles immobilized. Zeolite particles, having affinity for water and 2-propanol, gave a good ASCdS photocatalyst with respect to H2 generation.  相似文献   

20.
Carbon dioxide (CO2) is one of the main greenhouse gases in the atmosphere. The conversion of CO2 into solar fuels (CO, HCOOH, CH4, CH3OH, etc.) using artificial photosynthetic systems is an ideal way to utilize CO2 as a resource and reduce CO2 emissions. A typical artificial photosynthetic system is composed of three key components: a photosensitizer (PS) to harvest visible light, a catalyst (C) to catalyze CO2 or protons into carbon-based fuels or H2, respectively, and a sacrificial electron donor (SED) to consume the holes generated in the PS. In most cases, the PS and catalyst are two different components of a system. However, some components that possess both light harvesting and redox catalysis functionalities, e.g., nano-semiconductors, are referred to as photocatalysts. During photocatalysis, the PS is typically excited by photons to generate excited electrons. The excited electrons in the PS are transferred to the catalyst to generate a reduced catalyst. The reduced catalyst is used as an active intermediate to perform CO2 binding and transformation. The PS can be recovered through a reaction with the SED. Nano-semiconductors have been used as photosensitizers and/or photocatalysts in photocatalytic CO2 reduction systems owing to their excellent photophysical and photochemical properties and photostability. CdS and CdSe nano-semiconductors, such as quantum dots, nanorods, and nanosheets, have been widely used in the construction of photocatalytic CO2 reduction systems. Systems based on CdS or CdSe nano-semiconductors can be classified into three categories. The first category is systems based on CdS or CdSe photocatalysts. In these systems, CdS or CdSe nano-semiconductors function as photocatalysts to catalyze CO2 reduction without a co-catalyst under visible-light irradiation. The CO2 reduction reaction occurs at the surface of the CdS or CdSe nano-semiconductors. The second category is systems based on CdS or CdSe composite photocatalysts. CdS or CdSe nano-semiconductors are combined with functional materials, such as reduced graphene oxide or TiO2, to prepare composite photocatalysts. These composite photocatalysts are expected to improve the lifetime of the charge separation state and inhibit the photocorrosion of the nano-semiconductors during photocatalysis. The third category is hybrid systems containing a CdS nano-semiconductor and molecular catalysts, such as nickel and cobalt complexes and iron porphyrin. In these hybrid systems, CdS functions as a photosensitizer and the CO2 reduction reaction occurs at the molecular catalyst. This review article introduces the construction of artificial photosynthetic systems and the photocatalytic mechanism of nano-semiconductors, and summarizes the representative works in the three aforementioned categories of systems. Finally, the challenges of nano-semiconductors for photocatalytic CO2 reduction are discussed.  相似文献   

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