硫化镉反蛋白石光子晶体制备及光解水制氢

对硫化镉反蛋白石结构光子晶体薄膜进行了可控合成,用巯基乙酸修饰的纳米晶和P(St-MMA-SPMAP)高分子小球共组装,成功地构筑了反蛋白石结构并用于可见光光解水产氢。结果表明,在可见光(λ≥420 nm)照射下,Cd S-310反蛋白石结构薄膜的光解水产氢性能比硫化镉纳米颗粒提高了一倍。这主要是因为等级孔结构反蛋白石光子晶体特性对催化剂的光催化性能的提升:首先,反蛋白石的周期性结构增加了光子在材料中的传播,提高了催化剂对太阳光的利用率;同时,大孔孔壁是由纳米颗粒堆积而成的,在反应中提供了更多的反应活性位点;此外,孔结构有利于物质的传输和分子的吸附。     

Degradation of rhodamine B photocatalyzed by Eu-doped CdS nanowires illuminated by visible radiation

CdS nanowires doped with different contents of Eu dopant were synthesized by solvothermal method. XRD, SEM, TEM and Raman analyses certified that the as-synthesized samples were hexagonal CdS uniform nanowires. The pure CdS nanowires were 1–3 ?μm long and 80 ?nm diameter with the 1st and 2nd order longitudinal phonon modes at 298 and 594 ?cm^?1. The 3% Eu-doped CdS wires were 800 ?nm–2.5 ?μm long and 75 ?nm diameter with the 1st and 2nd order longitudinal phonon modes at 296 and 593 ?cm^?1. CdS nanowires grew along the [001] direction due to the surface energy effect. The photocatalytic properties of CdS and Eu-doped CdS nanowires were investigated for the degradation of rhodamine B (RhB) illuminated by visible radiation. In this research, Eu dopant played the role in promoting the photocatalytic kinetics because Eu³⁺ ions act as an electron acceptor to promote charge separation and photocatalytic activity. Both ^●OH and ^●O₂^? were the main active radicals used to transform RhB molecules into CO₂, H₂O and other intermediates.     

核壳结构CdS@C纳米复合材料的光催化性能研究

采用水热碳化法成功制备了不同碳含量的CdS@C纳米颗粒,同时对CdS@C的晶体结构、形貌、光学性能、光电化学和光催化性能进行了研究。实验结果表明本方法制备的碳包覆CdS纳米颗粒外壳为碳层,内核为六方纤锌矿结构CdS颗粒。CdS@C颗粒分散性良好,颗粒形貌主要为类球形,粒度均匀。X射线光电子能谱(XPS)证实CdS@C颗粒表面负载的碳主要以非晶碳形式存在。紫外-可见光光谱(UV-Vis)表明CdS@C纳米晶中表面碳的敏化作用提高了可见光响应范围,使得能隙变窄。光致发光光谱(PL)表明碳包覆CdS@C纳米颗粒的发光强度比纯CdS弱,有效抑制了光生载流子的复合。瞬态光电流响应和电化学阻抗谱(EIS)说明CdS@C纳米复合材料更有效促进电子-空穴对分离和提高转移效率。CdS@C纳米复合材料在可见光辐射下表现出良好的光催化活性和稳定性,其中·O₂^-和h⁺在光催化中起主要作用。     

Synthesis and characterization of ternary nanocomposites of TiO2/rGO/CdS as an efficient catalyst for photo-degradation of methyl orange

Novel ternary composite photocatalysts have been successfully prepared by TiO₂ nanofibers, reduced graphene oxide, and CdS nanoparticles (TiO₂/rGO/CdS) by using electrospinning technique with easy chemical methods. The structures and their properties are examined by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and field-emission scanning electron microscope (FESEM). The structural characterization of the composite reveals that pure TiO₂ NFs and CdS NPs crystalline very well and the reduced graphene oxide is tightly composed with TiO₂ NFs and CdS Nps. The photodegradation of methyl orange (MO) under UV light illumination is significantly enhanced compared with that of bare materials. This ternary composite degrades methyl orange within 75 min. The enhanced photocatalytic degradation performance resulted from effective separation of e–h pairs with rGO sheets and also contributed for high rate degradation efficiency. This novel ternary composite has a potential application of wastewater purification and utilization for energy conversions.     

New glass ceramics: an effective conjunction of wet chemistry synthesis and sintering

A glass with CdS nanoparticles was used simultaneously as a matrix for Ce-doped garnet and a yellow-red phosphor to prepare luminescent glass ceramics for the sources of white light. CdS nanoparticles compensate for the unbalanced Ce³⁺ emission spectrum of the composite material due to the addition of a red component. The synthesized composite material can be a tunable light converter due to altered luminescence spectra by changing the sintering conditions and excitation wavelength     

Photovoltammetric behavior and photoelectrochemical determination of p-phenylenediamine on CdS quantum dots and graphene hybrid film

A photoelectroactive film composed of CdS quantum dots and graphene sheets (GS) was coated on F-doped SnO₂ (FTO) conducting glass for studying the electrochemical response of p-phenylenediamine (PPD) under photoirradiation. The result indicated that the cyclic voltammogram of PPD on CdS–GS hybrid film became sigmoidal in shape after exposed under visible light, due to the photoelectrocatalytic reaction. Such a photovoltammetric response was used to rapidly optimize the photoelectrocatalytic activity of hybrid films composed of different ratios of CdS to GS toward PPD. The influences of scan rate and pH on the photovoltammetric behavior of PPD on CdS–GS film revealed that although the controlled step for electrochemical process was not changed under photoirradiation, more electrons than protons might participate the photoelectrocatalytic process. Furthermore, the photoelectroactive CdS–GS hybrid film was explored for PPD determination based on the photocurrent response of film toward PPD. Under optimal conditions, the photocurrent signal on CdS–GS film was linearly proportional to the concentration of PPD ranging from 1.0 × 10⁻⁷ to 3.0 × 10⁻⁶ mol L⁻¹, with a detection limit (3S/N) of 4.3 × 10⁻⁸ mol L⁻¹. Our work based on CdS–GS hybrid film not only demonstrated a new facile photovoltammetric way to study the photoinduced electron transfer process of PPD, but also developed a sensitive photoelectrochemical strategy for PPD determination.     

Temperature and Composition Dependent Optical Properties of CdSe/CdS Dot/Rod-Based Aerogel Networks

Employing nanocrystals (NCs) as building blocks of porous aerogel network structures allows the conversion of NC materials into macroscopic solid structures while conserving their unique nanoscopic properties. Understanding the interplay of the network formation and its influence on these properties like size-dependent emission is a key to apply techniques for the fabrication of novel nanocrystal aerogels. In this work, CdSe/CdS dot/rod NCs possessing two different CdSe core sizes were synthesized and converted into porous aerogel network structures. Temperature-dependent steady-state and time-resolved photoluminescence measurements were performed to expand the understanding of the optical and electronic properties of these network structures generated from these two different building blocks and correlate their optical with the structural properties. These investigations reveal the influence of network formation and aerogel production on the network-forming nanocrystals. Based on the two investigated NC building blocks and their aerogel networks, mixed network structures with various ratios of the two building blocks were produced and likewise optically characterized. Since the different building blocks show diverse optical response, this technique presents a straightforward way to color-tune the resulting networks simply by choosing the building block ratio in connection with their quantum yield.     

Simultaneous photoelectrochemical detection of dual microRNAs by capturing CdS quantum dots and methylene blue based on target-initiated strand displaced amplification

Herein,we propose a novel photoelectrochemical(PEC) biosensor for dual microRNAs(miRNAs) highly sensitive and simultaneous biosensing based on strand displaced amplification(SDA) reaction.The recognition of H_(miR-21) and H_(let-7 a) by microRNA-21 and let-7 a leads to their change in hairpin structures,subsequently initiating the immobilization of abundant CdS quantum dots(CdS QD s) and methylene blue(MB) based on SDA reaction.The immobilized CdS QDs and MB produce both high PEC currents under430 nm light and 627 nm light illumination,respectively,and the generated PEC currents are closely relied on target miRNAs amounts.Thus,highly sensitive and simultaneous detection of microRNA-21 and let-7 a was readily achieved with detection limit at 6.6 fmol/L and 15.4 fmol/L based on 3σ,respectively.Further,this PEC biosensor was applied in simultaneous analysis of miRNA-21 and let-7 a in breast cancer patient's serum with acceptable results.We expect this biosensor will find more useful application in diagnosis of miRNA-related diseases.     

利用地球上丰富的炭黑和NiS_2双助催化剂修饰提高CdS纳米片体系的可见光产氢活性(英文)

光催化产氢技术是目前解决能源和环境问题的最有潜力的方法之一,因此制备安全高效的光催化剂已成为目前的研究热点.在目前研究的各种光催化剂中,CdS光催化剂因为具有较窄的带隙(2.4 eV)和合适的导带位置,所以在可见光催化产氢领域受到广泛关注.然而,光生电子/空穴对易复合和光腐蚀作用极大地限制了CdS光催化剂的放大应用.因此,人们采用众多改性策略以提高CdS光催化剂的可见光产氢活性,其中构建CdS纳米结构和负载助催化剂被认为是最有效的方式.构建CdS纳米结构既可以缩短载流子的迁移路径,也可以减少CdS晶体中的缺陷.很多不同纳米结构的CdS光催化剂已经被开发,例如纳米线、纳米颗粒和纳米棒等.因为制备过程极为复杂繁琐,所以CdS纳米片的研究鲜见报道.本文采用乙酸鎘和硫脲为原材料,通过简单的溶剂热法合成了CdS纳米片.在CdS的各类助催化剂中,由于常用的Pt,Ag和Au等贵金属的高成本和低储量等问题严重限制了它们的实际应用,所以近年来众多非贵金属助催化剂(例如MoS_2,WS2,NiS,NiO和WC等)得到了广泛关注.由于非贵金属助催化剂存在弱电导率和低功函数等问题,影响了对光生电子的收集和利用.纳米碳材料具有极高的电导率、强可见光吸收、有效的载流子分离和较多的反应位点等优点,因此组合纳米碳材料和非贵金属助催化剂被认为是一种有效的解决方案.本文首次采用炭黑和NiS_2作为双助催化剂改性CdS纳米片,通过简单的溶剂热/沉淀两步法成功合成了廉价高效的CdS/CB/NiS_2三元光催化体系.光催化产氢性能测试表明,CdS-0.5%CB-1%NiS_2展现出最高的光催化效率(166.7μmol h~(-1)),分别是CdS NSs和CdS-1.0%NiS_2的5.16和1.87倍.X射线衍射、高分辨电子显微镜和X射线光电子能谱结果证实了CdS催化剂的片状结构,且炭黑和NiS_2成功负载在CdS纳米片表面.紫外-可见漫反射结果表明,随着炭黑和NiS_2的负载,复合催化剂的吸收边缘产生明显的红移,且对可见光的吸收增强.荧光光谱、阻抗和瞬态光电流曲线测试结果证明,炭黑和NiS_2的加入可以有效地促进光生电子/空穴对分离.极化曲线结果表明,加入炭黑和NiS_2可以降低CdS的产氢过电势,因此加速表面产氢动力学.总之,炭黑和NiS_2之间显著的协同效应极大地提高了可见光吸收,促进光生电子/空穴对分离,加速表面产氢动力学,最终得到了三元光催化体系极高的光催化产氢活性.