S/Cd物质的量比对微波水热制备CdS微晶的形貌影响及光学性能研究

采用微波水热法,以CdCl2·H2O和Na2S2O3·5H2O为镉源和硫源,在不同的S/Cd物质的量比条件下合成了CdS微晶。利用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、场发射扫描电子显微镜(FE-SEM)、EDS、透射电子显微镜(TEM)等对样品的物相、形貌和元素组分进行了分析。结果表明:随着S/Cd物质的量比的增大,产物CdS的形貌发生规律性变化,由四面体结构逐渐转变为准球形结构;准球形结构具有分级结构,是由更小的纳米晶组装而成;光致发光性质研究结果表明,所得的CdS微晶具有较好的蓝光发射性能。     

CdS形貌可控制备及其可见光分解水产氢性能

以还原型谷胱甘肽(GSH)作为硫源和结构导向剂水热法“一壶”制备系列硫化镉(CdS)光催化材料,采用透射电镜(HRTEM)、场发射扫描电镜(FESEM)、X射线衍射仪(XRD)、紫外可见漫反射(UV-Vis)、荧光光谱(PL)、比表面分析仪(BET)和光解水产氢反应等对催化材料的微观表面结构、光吸收性能以及光催化性能进行了研究。结果表明:通过调节反应物的nCd/nS比和水热温度等参数可控的制备出分散性好的CdS实心纳米球(s-CdS)、空心纳米球(h-CdS)以及纳米棒(r-CdS)等不同微观形貌的光催化材料。对比研究了不同形貌光催化剂的光解水产氢的宏观性能,发现s-CdS产氢活性最高,h-Cd次之,r-CdS最差。这一结果可归结于构成实心球表面亚微晶的粒径相比其它形貌的小,导致电子-空穴对快速迁移至表面并与溶液反应,抑制体相复合,导致生成的氢气量大大的提高。     

CdS形貌可控制备及其可见光分解水产氢性能

以还原型谷胱甘肽(GSH)作为硫源和结构导向剂水热法“一壶”制备系列硫化镉(CdS)光催化材料,采用透射电镜(HRTEM)、场发射扫描电镜(FESEM)、X射线衍射仪(XRD)、紫外可见漫反射(UV-Vis)、荧光光谱(PL)、比表面分析仪(BET)和光解水产氢反应等对催化材料的微观表面结构、光吸收性能以及光催化性能进行了研究。结果表明：通过调节反应物的nCd/nS比和水热温度等参数可控的制备出分散性好的CdS实心纳米球(s-CdS)、空心纳米球(h-CdS)以及纳米棒(r-CdS)等不同微观形貌的光催化材料。对比研究了不同形貌光催化剂的光解水产氢的宏观性能,发现s-CdS产氢活性最高,h-Cd次之,r-CdS最差。这一结果可归结于构成实心球表面亚微晶的粒径相比其它形貌的小,导致电子-空穴对快速迁移至表面并与溶液反应,抑制体相复合,导致生成的氢气量大大的提高。     

一锅水热法制备柳枝状MoS2/CdS异质结材料及其可见光催化产氢性能

自从1972年Fujishima和Honda发现TiO_2光电催化分解水产氢以来,半导体光催化分解水产氢技术被认为是解决能源危机和环境污染问题最有效的策略之一.然而,由于TiO_2的可见光吸收能力差、活性低、价格高等问题限制了其实际应用,因此寻求和发展高效的可见光催化剂具有重要意义.CdS半导体材料具有合适的带隙及导带位置,可以有效吸收可见光产生电子并将H~+还原生成H_2,是目前公认的较好的可见光催化产氢材料之一.然而光催化过程中Cd S材料较快的电子-空穴复合速度极大降低了其效率,如何促进光催化过程中电子-空穴对的分离成为研究重点.研究表明,采用负载助催化剂、构筑异质结、表面修饰、金属/非金属元素掺杂等技术可明显提高Cd S的光催化产氢性能,其中发展非贵金属助催化剂引起了广泛兴趣.近年有文献报道过渡金属硫化合物Mo S2用于光催化助催化剂,可以明显提高光催化性能.目前已制备出具有不同形貌的MoS_2/Cd S异质材料如纳米球、纳米棒、纳米纤维等,但多数Mo S2/CdS异质材料的制备采用两步法或多步法,制备工艺复杂,易引入杂质,阻碍了其实际应用.因此,发展简单温和的一步法制备具有新颖形貌的MoS_2/Cd S异质材料具有重要意义.本文采用简单的一步水热法制备了一种新颖的柳枝状MoS_2/Cd S异质材料.采用X射线衍射、场发射扫描电子显微镜、透射电子显微镜、X射线光电子能谱、紫外-可见漫反射吸收光谱和氮气吸附-脱附测试对所得样品进行了表征.结果表明,制备的柳枝状MoS_2/CdS异质材料具有核壳结构,两者之间形成紧密的异质结.光催化性能测试表明,制备的MoS_2/Cd S异质材料相比纯相Cd S产氢性能明显提高,优化后的MoS_2/Cd S异质材料(MoS_2/CdS摩尔比为5:100)的产氢性能是纯Cd S的28倍.通过紫外-可见漫反射光谱、荧光光谱分析、光电流、EIS阻抗谱及莫特肖特基曲线测试发现, CdS与MoS_2之间致密的异质核壳结构有助于光生载流子的迁移与分离,从而明显提高光催化活性.     

新型CdS/TiO2纳米复合材料的制备及其可见光催化性能研究

采用浸渍法和水热法相结合制备了新型的CdS/TiO₂纳米复合材料,并采用X射线衍射(XRD)、透射电子显微镜(TEM)、UV-Vis吸收光谱(UV-VIS)、电子自旋共振谱(ESR)等对样品进行了表征,XRD、TEM表明所制备的新型CdS/TiO₂粒径小、分散均匀,TiO₂以锐钛矿型存在,CdS以高分散的立方相和六方相存在,对比直接法制备的CdS/TiO₂,新型的CdS/TiO₂对活性艳红X-3B具有明显提高的可见光催化活性;大量的束缚单电子氧空位及电子之间强相互作用是新型CdS/TiO₂可见光催化活性提高的主要原因.     

NaOH溶液中CdS纳米棒的水热合成

在NaOH溶液中水热合成了CdS纳米棒, 并探讨了NaOH溶液浓度和反应时间对CdS纳米棒形貌及晶体结构的影响及其可能的生长机理和母液循环可行性. 用粉末X射线衍射(XRD)、 扫描电子显微镜(SEM)、 透射电子显微镜(TEM)、 高分辨透射电子显微镜(HRTEM)和选区电子衍射(SAED)对CdS纳米棒进行了表征, 并考察了其在可见光照射下光催化降解亚甲基蓝的活性. 结果表明, NaOH溶液是形成棒状形貌的关键因素. 在最优实验条件下, 可获得六方纤锌矿结构CdS纳米棒, 直径约200 nm, 长度可达4 μm. 该纳米棒具有良好的可见光光催化活性.     

CoFe2O4/CdS纳米复合物的制备、表征及其声催化降解有机染料污染物

在低温(200℃)下采用一步水热分解CoFe2O4纳米粒子表面的镉二硫代氨基甲酸酯配合物制备了磁性CoFe2O4/CdS纳米复合物,运用X射线衍射、红外光谱、扫描电镜、X射线能量散射谱、紫外-可见光谱、透射电镜(TEM)、N2吸附-脱附、X射线光电子能谱和振动样品磁强计对所制样品进行了表征.TEM结果表明,CoFe2O4/CdS纳米复合物由几乎均一的约20nm球形纳米粒子组成.光吸收谱显示该样品的带隙为2.24 eV,很适合用于声/光催化降解有机污染物.在紫外光照射下评价了CoFe2O4/CdS纳米复合物的声催化H2O2辅助降解甲基蓝、罗丹明B和甲基橙反应活性.结果表明,该纳米复合物对这3种染料均表现出很好的声催化活性(5-9 min内完全降解).另外,比较实验结果表明,CoFe2O4/CdS纳米复合物是一个比纯CdS更高效的声催化剂.因此,纳米复合是一种非常好的提高CdS声催化活性的手段.该CoFe2O4/CdS纳米复合物表现出的磁性使其很容易从反应混合物中分离出来而重复使用.     

具有三维阵列结构的树枝晶CdS的制备及生长机理研究

采用电沉积和溶剂热相结合的方法,以树枝状金属Cd颗粒为模板和前驱体,在乙二胺溶剂中以六亚甲基四胺(HMTA)为表面修饰剂,制备出具有三维阵列结构的树枝晶CdS。利用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)结合X射线能谱仪(EDS)等对样品的物相、形貌、元素组分和结构进行了分析。结果表明:在溶剂热反应过程中,当不加入HMTA时,得到的产物是无序的CdS纳米线;而在HMTA的作用下,则生成的是具有三维阵列结构的树枝晶CdS;通过分析溶剂热反应过程中的化学反应,并结合产物形貌演变规律,提出了具有三维阵列结构的树枝晶CdS的形成机理。光催化性能测试表明具有三维树枝晶CdS纳米阵列在可见光照射下表现出良好的光催化活性。     

CdS/BiVO4复合半导体制备及其光催化性能

采用水热法以BiVO_4纳米片为基体原位生长CdS晶体,得到CdS/BiVO_4复合光催化剂,利用XRD、SEM、UV-Vis DRS等方法对材料进行了表征,通过降解亚甲基蓝对样品的光催化性能进行评价。结果表明,BiVO_4为方形片状颗粒,其表面附着棒状CdS纳米颗粒,分散较好。CdS/BiVO_4复合光催化剂表现出较高的光催化活性,在可见光照射下,利用CdS/BiVO_4光催化降解亚甲基蓝,60 min后的降解率达94.79%,相比于纯相BiVO_4和CdS有显著提高,且对多种有机染料均有良好的降解效果,重复使用性较好。机理研究发现,超氧自由基(·O_2~-)是CdS/BiVO_4光催化降解亚甲基蓝的主要活性物种。     

0D/1D碳点修饰硫化镉纳米线异质结增强可见光光催化性能（英文）

硫化镉(CdS)作为一种对可见光响应的窄带隙半导体(带隙宽度约为2.4 eV),具有合适的能带位置,近年来受到越来越多的重视.然而在光催化过程中,光生电子与空穴的快速复合极大地限制了CdS的实际应用,如何提高光生电子-空穴对的分离效率成为研究重点.一维CdS纳米棒(1D CdS NWs)具有较大的长径比,能快速有效地转移光生载流子.零维碳点(0D C-dots)是一种粒径在10 nm以下的新型纳米碳材料,其作为助催化剂能够加快光生载流子传递速率,可提高材料光催化性能.因此,通过C-dots对CdS NWs进行修饰并形成异质结,利用C-dots助催化剂的作用以提升CdS NWs的光催化性能,具有一定的可行性.本文成功构建了一种0D/1D碳点修饰CdS NWs异质结(C-dots/CdS NWs),并考察其光催化性能.通过X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)和紫外-可见(UV-Vis)吸收光谱等技术对系列C-dots/CdS NWs样品进行表征.研究发现,C-dots成功负载在CdS NWs的表面并形成异质结.通过测试系列样品在可见光照射下光催化降解罗丹明B(RhB)以及光催化产氢性能发现,C-dots的修饰能够有效增强CdS NWs的光催化性能,其中0.4%C-dots/CdS NWs表现出最佳的光催化降解RhB活性,其经可见光照射60 min即可实现对RhB的完全降解(相同条件下CdS NWs需要180 min).同时自由基捕获实验表明,·O_2~–是降解罗丹明B过程中的主要活性基团.在光催化产氢性能测试中,0.4%C-dots/CdS NWs样品表现出最高的光催化产氢能力,产氢速率可达1633.9μmol g~(-1) h~(-1),比纯CdS的(196.9μmol g~(-1) h~(-1))提高了8.3倍,并且C-dots/CdS NWs具有良好的稳定性.研究发现,在可见光照射下,C-dots/CdS NWs能够产生较强的光生电流,且形成的0D/1D C-dots/CdS NWs异质结具有良好的电子传输能力,实现了C-dots/CdS NWs光生电子与空穴的有效分离,从而增强了光催化性能.     

Physicochemcial characteristic of CdS-anchored porous WS2 hybrid in the photocatalytic degradation of crystal violet under UV and visible light irradiation

In this work, we report the synthesis of CdS-incorporated porous WS₂ by a simple hydrothermal method. The structural, morphological, and optical properties of the samples were examined by X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), Fourier transform infrared spectroscopy (FTIR), high resolution X-ray photoelectron spectroscopy (XPS) and UV–visible spectrometry. The photocatalytic activities were established for degradation of crystal violet (CV) under UV and visible light irradiation. The CdS-incorporated porous WS₂ hybrid demonstrated high photocatalytic activity for degradation of CV pollutant compared to pure CdS nanoparticles and porous WS₂ sheets. This result implies that the CdS-incorporated porous WS₂ promoted more electron-hole pair transformation under UV and visible light irradiation. This significant enhancement of photocatalytic efficiency of CdS-incorporated porous WS₂ photocatalyst under visible light can be ascribed to the presence of CdS nanospheres on the meshed-like WS₂ sheets which potentially improves absorption in the visible range enabled by surface plasmon resonance effect of CdS nanospheres. The photostability and reusability of the CdS-porous WS₂ were examined through recycling experiments.     

A new 2D cadmium coordination polymer based on hydroxyl-substituted benzenedicarboxylic acid as an effective heterogeneous catalyst for Knoevenagel condensation

A self-assembled new 2D cadmium network, [Cd (BDC-OH)(DMF)₂·DMF]_n (Cd-BDC-OH), was synthesized based on 2-hydroxyterephthalic acid (BDC-OH) ligand and utilized as a heterogeneous catalyst for Knoevenagel condensation. The structure was fully elucidated by single-crystal X-ray diffraction, Hirshfeld surface analysis, powder X-ray diffraction, field emission-scanning electron microscopy, Fourier transform-infrared spectroscopy and thermogravimetric analysis. The fabricated coordination polymer exhibited high catalytic activity under ambient conditions, and was used without significant drop in product yield in further cycles.     

ZnO-rich CdS-ZIF-8 catalyst for enhanced visible-light photocatalytic degradation of methylene blue

CdS-ZIF-8 photocatalyst was prepared by introducing a ZnO-rich zeolitic imidazolate framework-8 (ZIF-8) during synthesis of CdS by a facile solvothermal method, using ZnO-rich ZIF-8 and cadmium acetate [Cd(Ac)₂] as support and CdS precursor, respectively. The introduction of ZnO-rich ZIF-8 and the photodegradation performance of the catalyst for methylene blue (MB) organic dye were systemically investigated. The CdS-ZIF-8 catalysts were also characterized using X-ray diffraction analysis, transmission electron microscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy, N₂ adsorption–desorption measurements, Fourier-transform infrared (FT-IR) spectroscopy, ultraviolet–visible (UV–Vis) diffuse reflectance spectroscopy (DRS), and photoluminescence spectroscopy. The results indicated that CdS-ZIF-8 contained ZIF-8, CdS, and ZnO phases. The CdS in CdS-ZIF-8 catalysts exhibited smaller particle size compared with pure CdS. Furthermore, compared with pure CdS, CdS-ZIF-8-30 with introduction of ZnO-rich ZIF-8 exhibited higher surface area (77.3 m²/g) and pore volume (0.103 cm³/g). EDX and FT-IR results suggested that a CdS/ZnO heterostructure was formed, which effectively reduced recombination of photogenerated electron–hole pairs. Radical trapping experimental data and band edge position analysis revealed that Z-scheme behavior also played a role in the system. Relying on the combined effect of their structure, the photodegradation efficiency of all the CdS-ZIF-8 catalysts was obviously superior to that of pure CdS for degradation of MB under visible-light irradiation. Photodegradation results illustrated that CdS-ZIF-8 with introduction of 30 mg ZnO-rich ZIF-8 (denoted as CdS-ZIF-8-30) exhibited optimal photodegradation activity.     

Synthesis and Characterization of CdS Nanoparticles via Cyclic Microwave from Cadmium Oxalate

The present study reports synthesis and characterization of CdS nanoparticles prepared by cyclic microwave route with the use of [Cd(C₂O₄)·3H₂O] powder as a precursor. The products, with an average size ~15 nm, were characterized by X-ray diffraction, scanning electron microscopy, energy dispersive X-ray microanalysis, thermogravimetric analysis, transmission electron microscopy and Fourier transform infrared spectroscopy. Optical property of obtained product was investigated by photoluminescence spectroscopy. The prepared nanostructures displayed a very strong luminescence at 528 nm (2.34 eV) at room temperature.     

Hydrothermal synthesis, characterization and its photoactivity of CdS/Rectorite nanocomposites

CdS/Rectorite nanocomposites were prepared through hydrothermal method by using Cd[NH₂CSNH₂]₂Ac₂ complex as precursor of CdS which was derived from cadmium acetate and thiourea. The obtained nanocomposites were characterized by X-ray diffraction (XRD), Fourier transfer infrared spectra (FTIR), diffusion reflection spectra (DRS), transmission electron microscopy (TEM) and the selected area electron diffraction (SAED) patterns. Experimental results indicate that CdS exist in at least three forms: CdS adsorbed at surface, CdS pillared in montmorillonite-like layers of Rectorite and CdS pillared in the new layered structure formed during the hydrothermal process. Those CdS crystals are hexagonal symmetry. The photoactivity and photostability of the obtained CdS/Rectorite nanocomposites are improved significantly compared to that of the reference Rectorite and pure CdS.     

具有分级多孔结构和光催化性质的核-壳纳米球(HP-Fe2O3@TiO2)

通过溶剂热和溶胶-凝胶涂层法, 设计并制备了具有分级多孔结构和光催化性质的核-壳纳米球(HP-Fe₂O₃@TiO₂). 透射电子显微镜(TEM)照片证明所得HP-Fe₂O₃@TiO₂样品具备分级多孔结构, 这是因为HP-Fe₂O₃@TiO₂的内核-Fe₂O₃具有大孔空隙, 同时外壳-TiO₂具有介孔空隙. 此外, 通过X射线衍射(XRD)、扫描电子显微镜(SEM)、高分辨透射电子显微镜(HRTEM)、X射线光电子能谱(XPS)以及氮气吸附-脱附曲线深入研究了HP-Fe₂O₃@TiO₂的结构及其性质. 分别在可见及紫外光照下, 研究了样品在H₂O₂体系下的光催化降解亚甲基蓝(MB)的性质. 所观察到的HP-Fe₂O₃@TiO₂纳米球的光催化性能, 可归因于核-壳结构的协同作用, 这进一步表明, TiO₂外壳对α-Fe₂O₃的光催化活性有重要影响作用. 在可见光照射下, HP-Fe₂O₃@TiO₂ (1 mL Ti(OC₄H₉)₄ (TBT))具有较优异的光催化活性. 同时, HP-Fe₂O₃@TiO₂ (4mL TBT)具备优异的单分散形貌, 并在紫外光照射下, 表现出最优的光催化活性.     

Simple and low temperature preparation and characterization of CdS nanoparticles as a highly efficient photocatalyst in presence of a low-cost ionic liquid

A simple and low temperature method is proposed for preparation of CdS nanoparticles in presence of 1-ethyl-3-methylimidazolium ethyl sulfate, [EMIM] [EtSO₄], a room-temperature ionic liquid (RTIL). The powder X-ray diffraction (XRD) studies display that the products are excellently crystallized in the form of cubic structure and size of the nanparticles prepared in presence of the RTIL is smaller than that prepared in water. Energy dispersive X-ray spectroscopy (EDX) investigations reveal that the products are very pure and nearly stoichiometric. The results obtained by scanning electron microscopy (SEM) demonstrate that the CdS nanoparticles prepared in presence of the RTIL have lower tendency for aggregation relative to the prepared sample in water. Diffuse reflectance spectra (DRS) of the product prepared in the neat RTIL, shows 1.52 eV blue shift relative to bulk CdS, which can be attributed to quantum confinement effect of the CdS nanoparticles. A possible formation mechanism for CdS nanoparticles in presence of the RTIL is presented. Photocatalytic activity of the CdS nanoparticles towards photodegradation of methylene blue (MB) using UV and visible lights was performed. The results demonstrate that observed firstorder rate constant for photodegradation of MB on CdS nanoparticles prepared in the neat RTIL are about 20 and 6 times greater than the prepared sample in water using visible and UV lights, respectively.     

Graphene oxide‐bound electron‐deficient tin(IV) porphyrin: a highly efficient and selective catalyst for trimethylsilylation of alcohols and phenols with hexamethyldisilazane

The catalytic activity of graphene oxide‐bound tetrakis(p ‐aminophenyl)porphyrinatotin(IV) trifluoromethanesulfonate, [Sn^IV(TNH₂PP)(OTf)₂], in the trimethylsilylation of alcohols and phenols with hexamethyldisilazane (HMDS) is reported. The prepared catalyst was characterized using inductively coupled plasma analysis, scanning electron microscopy, transmission electron microscopy, and Fourier transform infrared and diffuse reflectance UV–visible spectroscopies. This heterogeneous catalyst was used for selective trimethylsilylation of various alcohols and phenols with HMDS in short reaction times and high yields. Also, the catalyst is of high reusability and stability, in that it was recovered several times without loss of its initial activity. The chemoselectivity of this catalytic system in the silylation of primary alcohols in the presence of secondary and tertiary alcohols and also phenols was investigated.     

Synthesis of CdS/SiO2/polymer tri-layer fluorescent nanospheres with functional polymer shells

Tri-layer CdS/SiO₂/polymer hybrid nanospheres were synthesized by distillation precipitation polymerization of either ethyleneglycol dimethacrylate（EGDMA） or EGDMA together with comonomers having different functional groups, such as methacrylic acid,4-vinylpyridine and 2-hydroxyethylmethacrylate,in the presence of 3-（methacryloxy）propyl trimefhoxysilane（MPS）-modified CdS/SiO₂ nanoparticles as seeds in acetonitrile with 2,2’-azobisisobutyronitrile（AIBN） as initiator.In this approach,MPS-modified inorganic seeds were prepared by the modification of CdS/SiO₂ nanoparticles via the self-condensation reaction between the hydroxyl groups of sinaols,in which the CdS/SiO-2 nanoparticles were afforded by a reverse microemulsion technique for the synthesis of CdS core nanoparticles with the subsequent coating of silica layer. The polymer shell-layers encapsulated over the MPS-modified CdS/SiO₂ inorganic seeds via the efficient capture of the monomers and oligomers from the solution with the aid of the vinyl groups incorporated by the MPS modification,in which the polymer shell-thickness and functional groups including carboxyl,pyridyl and hydroxyl,were facilely controlled by the feed of EGDMA as well as the types of comonomers used for the polymerization.These nanospheres were characterized by transmission electron microscopy（TEM）,Fourier-transform infrared spectroscopy（FT-IR）,thermogravimetric analysis （TGA）,fluorescence spectroscopy and zeta potential.