A Facile Controllable Synthesis, Growth Mechanism, and Photocatalytic Properties of Nanoscale BiOCl

Nanoscale tetragonal BiOCl samples have been synthesized using Bi[SC12H25]3 and CHCl3 as bismuth and chlorine sources by solvothermal reactions. The structure, morphology, and formation process have been investigated by SEM, TEM, HRTEM, XRD, and EDX analyses. The layered crystal structure feature of BiOCl may induce the growth of nano plates, which can subsequently aggregate into 3D spherical or flower-like microstructures under the presence of ethanol. The reaction temperature and the identity of secondary solvent influence the morphology. The yield of BiOCl depends on the completeness of the reaction and the degree of a competition reduction of BiOCl to Bi by ethanol. The as-synthesized 3D quasi-spherical BiOCl sample has an optical band gap of 3.15 eV, and shows much better photocatalytic performance on the degradation of methyl orange than that of commercial P25.     

Controllable Synthesis of Inverse Opal TiO2‐x Photonic Crystals and Their Photoelectric Properties

In this study, inverse opal TiO_2‐x photonic crystals (IO‐TiO_2‐x) have been successfully synthesized by a two‐step calcination. The whole synthesis is safe and feasible. Additionly, the reduction degree and the structure of IO‐TiO_2‐x can be precisely controlled. A series of IO‐TiO_2‐x samples with different reduction degree were prepared and characterized. The TEM images show that the obtained samples possess a 3D‐ordered macroporous inverse opal structure. The reduced Ti atoms/oxygen vacancies were confirmed by Raman and XPS spectroscopy. All IO‐TiO_2‐x samples showed better photoelectric properties than those of common TiO₂ which indicates their great potential to be applied to photoelectric fields. The improvement of photoelectric properties is attributed to the efficient electron‐hole separation efficiency induced by moderately reduced Ti atoms/oxygen vacancies. Meanwhile, the 3D‐ordered macroporous inverse opal structure and the band gap are regulated to “capture” more solar energy. This new approach is proven to be a meaningful method to synthesize high‐performance TiO₂ materials.     

Controllable Photoelectric Properties of Carbon Dots and Their Application in Organic Solar Cells

Organic solar cells are a current research hotspot in the energy field because of their advantages of lightness,translucency,roll to roll printing and building integration.With the rapid development of small molecule acceptor materials with high-performance,the efficiency of organic solar cells has been greatly improved.Further improving the device efficiency and stability and reducing the cost of active layer materials will contribute to the industrial development of organic solar cells.As a novel type of carbon nanomaterials,carbon dots gradually show great application potential in the field of organic solar cells due to their advantages of low preparation cost,non-toxicity and excellent photoelectric performance.Firstly,the synthesis and classification of carbon dots are briefly introduced.Secondly,the photoelectric properties of carbon dots and their adjusting,including adjustable surface energy level structure,good film-forming performance and up/down conversion characteristics are summarized.Thirdly,based on these intrinsic properties,the feasibility and advantages of carbon dots used in organic solar cells are discussed.Fourthly,the application progress of carbon dots in the active layer,hole transport layer,electron transport layer,interface modification layer and down-conversion materials of organic solar cells is also reviewed.Finally,the application progress of carbon dots in organic solar cells is prospected.Several further research directions,including in-depth exploration of the controllable preparation of carbon dots and their application in the fields of interface layer and up/down conversion for improving efficiency and stability of device are pointed out.     

Divalent Europium Nanocrystals: Controllable Synthesis,Properties, and Applications

Magnetic and luminescent bifunctional divalent europium nanocrystals (Eu²⁺ NCs) are a promising class of novel advanced materials that have various applications in magneto‐optic devices, catalysis, bioimaging, and solar cells. In the past few decades, much work has been carried out to study the synthesis, properties, and applications of Eu²⁺ NCs. The aim of this Minireview is to present the progress in preparing Eu²⁺ NCs based on the reported research, by describing the advantages and disadvantages of the synthesis methods. The morphologies and size are controlled through adjusting the experimental conditions. Eu²⁺ NCs show superior magnetic and luminescence properties simultaneously. Self‐assembly and doping with other ions are important routes to improve their magnetic and luminescence properties. Their applications in magneto‐optic devices are discussed. Some difficulties and challenges in the fabrication of Eu²⁺ NCs are discussed, such as water‐soluble Eu²⁺ NCs and tunable luminescence in the whole visible region.     

晶面可控BiOCl光催化剂的制备及其催化反应活性研究

以五水合硝酸铋和氯化钾为原料,通过水热法合成了BiOCl光催化剂,并对其结构进行表征,考察了前驱体的pH对催化剂结构和降解8-羟基喹啉活性的影响。结果表明,随前驱体pH的增加,催化剂[001]晶面暴露程度下降,带隙能减小,且催化反应活性降低,这可归因于低的带隙能和高的光生载流子复合效率。进一步考察降解体系pH对催化剂反应活性的影响,结果表明,降解体系pH影响8-羟基喹啉在催化剂表面的吸附行为,进而影响催化剂的反应活性。     

形貌可控卟啉材料的合成及光电性质

通过自组装方法制备了一种卟啉材料,并通过调节溶液pH值实现了对其形貌的可控。 当pH值较低时形成卟啉棒状结构;当pH值较高时形成卟啉叶片状结构。 利用紫外、红外和X衍射仪等多种表征方法对其结构和性质进行了表征。 结果表明,在无机酸的作用下,卟啉分子通过π-π、静电作用形成一维结构的J-聚集体;当pH值增加时,氢键的作用占主要作用形成二维片状结构。 将此卟啉棒状材料构筑微纳米器件,测试其光电性能,表明对可见光有很好的响应。 这种具有光电响应的卟啉材料有望成为微纳电子器件的光电元件。     

不同制备方法对BiOCl材料的形貌、结构与光催化性能的影响研究

对比采用溶剂热合成、传统固相合成与溶胶-凝胶合成技术,制备了四方相BiOC1和Nd3+掺杂BiOCl光催化材料.运用X射线粉末衍射(XRD)、扫描电子显微镜(SEM)及紫外-可见吸收光谱(UV-Vis),研究了不同合成方法所制备BiOCl材料的相结构、形貌和紫外-可见光吸收性能;并以甲基橙溶液为模拟废水,研究了不同方法所制备的BiOCl材料的光催化性能.结果表明:溶剂热合成的BiOCl是由纳米片组装成粒径小于1μm微球,紫外-可见吸收边为335 nm;固相合成所得BiOCl结晶度较高,其片状颗粒粒径约为6μm,紫外-可见吸收边为430n m;溶胶-凝胶合成法制得BiOCl片状颗粒粒径约为3～4 μm,紫外-可见吸收边为430 nm.进一步地对比研究了稀土离子Nd3+掺杂前后BiOCl样品的结构、紫外-可见光吸收特性,可以发现,Nd3+掺杂后样品的相结构及形貌均无变化,但吸收边均发生不同程度的红移,以溶胶-凝胶法制得的样品效果最为明显,并具有最优的光催化性能.     

共价接枝硅酞菁-多壁碳纳米管的合成及光电性能

采用酰胺反应把硅酞菁(SiPc)共价接枝到多壁碳纳米管(MWCNT)上,得到MWCNT-Pc,用紫外可见,红外光谱,拉曼光谱,X射线光电子能谱,热重分析等进行了表征,结果表明碳纳米管上每约457个碳原子接枝一个酞菁分子;为研究共价接枝的MWCNT-Pc体系中光激发的电子流动情况,探讨了Pc静电组装到MWCNT后的荧光淬灭的情况,结果显示SiPc的光激发电子向MWCNT转移;同时采用喷涂法构筑了ITO/MWCNT-Pc光电极,并在光伏电池中研究了其光电性能,在AM1.5光照条件下,光电流及光电压分别为0.434 V和0.158 mA·cm-2,在320 nm处的IPCE达19.8%。本研究目的在于制备碳纳米管衍生物并构筑基于碳管的复杂的功能纳米结构材料,为其应用奠定基础。     

一种环金属铱、铂双核配合物的合成及光电性能

设计合成了一种双核环金属铱,铂配合物二[N,N-2-(2,4-二氟苯基吡啶)C3,N1](吡啶甲酸)合铱(Ⅲ)-C₆-[苯基吡啶-C3,N1](吡啶甲酸)合铂(Ⅱ)(FIrPPyPt)。 通过核磁共振仪、元素分析仪、紫外-可见吸收光谱仪和光致发光光谱仪对其结构和性能进行了表征。 结果表明,配合物FIrPPyPt的紫外-可见吸收位于250~450 nm之间,荧光发射峰位于465和493 nm。 将配合物FIrPPyPt以质量分数1%~8%掺杂到主体材料聚乙烯基咔唑(PVK)+2-(联苯-4-芳基)-5-(4-叔丁基苯)-1,3,4-噁二唑(PBD)(30%)中制作了电致发光器件,在不同电压下电致发光光谱中,显现出铱配合物和铂配合物的特征峰,波峰位于400、500和530 nm蓝绿光区发射区。 该双核配合物用于单掺杂有机白光电致发光器件具有制作简单、色稳定性和重复性好等特点,为单掺杂白光发光器件提供了一种好的思路。     

Controllable Synthesis and Optical Properties of Connected Zinc Oxide Nanoparticles

Connected zinc oxide (ZnO) nanoparticles are successfully synthesized by a simple solution‐based chemical route that uses evaporation and concentration technology. The influences of processing parameters, especially the evaporation and concentration time on the size and morphology of the nanoparticles, have been investigated by transmission electron microscopy (TEM) and high‐resolution TEM (HRTEM). The structure and optical properties are systematically characterized by X‐ray diffraction (XRD), UV/Vis spectrophotometery, and fluorescence spectroscopy (FL). It is found that the average diameter and morphology are strongly affected by the evaporation and concentration time. Additionally, the formation mechanism of the nanoparticles is also discussed. The studies revealed that the evaporation and concentration are important aggregation or nucleation processes for ZnO growth, which leads to the macro‐differences in morphology. These results provide some insight into the growth mechanism of ZnO nanostructures. The synthetic strategy developed in this study may also be extended to the preparation of other nanomaterials and promising applications in various fields of nanotechnology.     

新型硒二唑衍生物荧光分子的合成及光电性能研究

为了增大前期工作开发中Hg²⁺荧光探针分子TBBA在近红外区间的吸收范围,降低分子的生物组织损耗,本研究在保持三苯胺为给电子单元不变的情况下,将苯并噻二唑分子换成吸电子能力更强的苯并硒二唑和吡啶硒二唑单元,并通过Suzuki偶联反应合成了两种新型荧光分子TBSeBA和TPSeBA。经过核磁共振氢谱、碳谱和ESI质谱确认了两种分子的结构,在DMSO溶液中TBSeBA和TPSeBA的吸收峰分别位于465.00 nm和520.00 nm。 TBSeBA的HOMO和LUMO能级分别为-5.00 eV和-2.82 eV; TPSeBA的HOMO和LUMO能级分别为-5.17 eV和-2.77 eV。硒原子的引入为荧光分子的光学性质和电化学性质调控提供了一种有效策略。     

有机溶剂热生长技术制备硫族化合物及其光学特性的研究

以有机溶剂热生长技术(solvothermaltechnique)制备了半导体硫族化合物(CdS、ZnS、MoS₂)等纳米颗粒,采用XRD、TEM等技术对其结构进行表征.以ITO导电玻璃以及导电聚合物(PANI、PPY)膜为基底,将纳米颗粒涂布其上并以PL法研究其光学特性,实验结果表明:经修饰后,材料的荧光发射位置发生显著的变化.     

Meso-四(对甲基-苯基)卟啉锌的合成及其光电性能

采用改进“Alder法”制得meso-四(对甲基 苯基)卟啉（TMPP）; TMPP络合锌离子合成了meso-四(对甲基-苯基)卟啉锌（TMPP-Zn）,收率21.22%,其结构和性能经FL, UV-Vis, ¹H NMR, IR和HR-MS(ESI)表征。溶剂化效应研究结果表明：TMPP-Zn在非质子非极性溶剂甲苯中有较强的发光性,强度为186.5561,在极性溶剂乙腈中发光性较弱,强度仅136.9312。聚集发光性能测试结果表明：水含量增加,发光性先增强后减弱,水含量90% 时发光性最好。循环伏安测试及单线态氧测试结果表明：TMPP-Zn能级差为1.98,能隙较高,10 min发光强度达2.8×10⁶。     

基于氟代喹喔啉D-A型共轭聚合物的合成及其光电性能

分别以噻吩、联二噻吩和三联噻吩为给体单元,氟代噻吩基喹喔啉为受体单元,通过Stille反应合成了三种新型的聚合物太阳电池材料（PT-TFQ, PTT-TFQ和PTTT-TFQ）,其结构经¹H NMR表征。研究了不同给电子能力的结构单元对其UV-Vis谱光谱、电化学性质以及光伏性能的影响。结果表明,PT-TFQ, PTT-TFQ和PTTT-TFQ氯仿溶液的最大吸收峰分别位于545 nm, 578 nm和649 nm,而薄膜的最大吸收峰相对于溶液的吸收峰分别红移了81 nm, 97 nm和44 nm; PT-TFQ, PTT-TFQ和PTTT-TFQ的开路电压依次降低,分别为0.86 V, 0.60 V和0.50 V;基于三者的器件效率分别为3.19%, 3.10%和2.63%。     

4,7-二噻吩-[2,1,3]苯并硒二唑的合成及其光电性能

苯并硫二唑经溴代,还原和闭环反应制得4,7-二溴[2,1,3]苯并硒二唑(3);以Pd(PPh3)2Cl2为催化剂,3与2-三丁基锡噻吩(4)经斯蒂尔偶联反应合成了4,7-二噻吩-[2,1,3]苯并硒二唑(5)。5为新化合物,其结构和性能经1H NMR,13C NMR,UV-Vis,荧光光谱法和循环伏安法表征。结果表明:5具有应用于光伏材料的带隙(12.2 e V);有较宽的吸收波长(260 nm~487 nm),在红光区域发射较强的荧光(620 nm);有可逆的氧化还原曲线,电化学性质稳定。     

含咔唑基团的新颖Re(Ⅰ)配合物的合成、表征和光电性质的研究

合成了一种含咔唑基团的新颖配合物Re(CO)_3CLL[L=1-乙基-2-(N-乙基－咔唑 并-4-)咪唑并[4.5-f]1,10-邻菲咯啉],通过元素分析、红外光谱、紫外光谱、~1H NMR、荧光光谱和循环伏安学对其进行了表征，制备了基于真空沉积膜的双层电致 发光器件：ITO/TPD (30 nm)/Re(Co)_3CLL (10 nm)/Mg_(0.9)Ag_(0.1) (110 nm) /Ag(60 nm)该器件启动电压为5V，在电压为9V时达到最大亮度113cd/m~2，发出桔 红色的光。     

桥连氧化钨纳米线的可控合成及气敏性质

The rapid development of industrialization has resulted in severe environmental problems. A comprehensive assessment of air quality is urgently required all around the world. Among various technologies used in gas molecule detection, including Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy, mass spectroscopy (MS), electrochemical sensors, and metal oxide semiconductor (MOS) gas sensors, MOS gas sensors possess the advantages of small dimension, low power consumption, high sensitivity, low production cost, and excellent silicon chip compatibility. MOS sensors hold great promise for future Internet of Things (IoT) sensors, which will have a profound impact on indoor and outdoor air quality monitoring. The development of nanotechnology has significantly enhanced the development of MOS gas sensors. Among various nanostructures like nanoparticles, nanosheets and nanowires, the emergence of quasi-one-dimensional (q1D) nanowires/nanorods/nanofibers, with unique q1D geometry (facilitating fast carrier transport) and large surface-to-volume ratio, potentially act as ideal sensing channels for MOS sensors with extremely small dimension, and good stability and sensitivity. These structures have thus been the focus of extensive research. Among the various MOS nanomaterials available, tungsten oxide (WO_3-x, 0 ≤ x < 1) nanowires feature the characteristic properties (multiple oxidation states, rich substoichiometric oxides with distinct properties, photo/electrochromism, (photo)catalytic properties, etc.), and unique q1D geometry (single-crystalline pathway for fast carrier transport, large surface-to-volume ratio, etc.). WO_3-x nanowires have broad applications in smart windows, energy conversation & storage, and gas sensing devices, and have thus become a focus of attention. In this paper, the fundamental properties of tungsten oxide, synthesis methods and growth mechanism of tungsten oxide nanowires are reviewed. Among various (vapor-liquid-solid (VLS), vapor-solid (VS) and thermal oxidation) growth methods, the thermal oxidation method enables an in situ integration of WO_3-x nanowires on predefined electrodes (so-called bridged nanowire devices) via the oxidation of lithographically patterned W film at relatively low growth temperature (~500 ℃) because of interfacial strain, defects and oxygen on the surface of the W film. The novel bridged nanowire-based sensor devices outperform traditional lateral nanowire devices in terms of larger exposure area, low power consumption via self-heating, and greater convenience in device processing. Recent progress in bridged WO_3-x nanowire devices and sensitive NO_x molecule detection under low power consumption have also been reviewed. Power consumption of as low as a few milliwatts was achieved, and the detection limit of NO₂ was reduced to 0.3 ppb (1 ppb = 1 × 10^-9, volume fraction). In situ formed bridged WO_3-x nanowire devices potentially satisfy the strict requirements of IoT sensors (small dimension, low power consumption, high integration, low cost, high sensitivity, and selectivity), and hold great promises for future IoT sensors.     

Controllable Electrochemical Synthesis of Silver Dendritic Nanostructures and Their SERS Properties

Ag dendritic nanostructures were synthesized on fluorine-doped tin oxide covered glass sub-strates by the electrodeposition method. Results demonstrate that the size, diameter, crys-tallinity, and branch density of the Ag dendrites can be controlled by the applied potential,the surfactants and the concentration of AgNO₃. Three kinds of typical silver dendrites were applied as substrates of the surface enhanced Raman scattering (SERS) and one of them was able to clearly detect rhodamine 6G concentrations up to 0.1 nmol/L. The differences of the SERS spectra at these Ag dendrites confirmed that the shapes and interparticle spacings have great effect on Raman enhancement, especially the interparticle spacings.     

基于吩噻嗪供体的敏化染料的合成及其光电性质

以吩噻嗪为供体,设计并合成了具有D-A-π-A或D-π-A结构的有机敏化染料2-氰基-3-{5-[7-(10-己基吩噻嗪-3-基)-苯并[1,2,5]噻二唑-4-基]-2-噻吩基}-丙烯酸(CVBTP)和2-氰基-3-{5-[7-(10-己基吩噻嗪-3-基)-2-噻吩基}-丙烯酸(CVTP)。在结构表征的基础上,研究了结构变化对敏化染料的光物理性质、电化学性质和光伏性能的影响。结果表明,在染料CVTP的D-π-A结构链上插入受体苯并噻二唑单元,得到的具有D-A-π-A结构的染料CVBTP的带隙变小,共轭体系变大,光吸收性能得到明显提升。CVBTP、CVTP的HOMO能级分别为-4.83、-4.82eV,LUMO能级分别为-2.85、-2.28eV,均与常见电解质I-/I-3(-4.60eVvs vacuum)和TiO2导带能级(-4.40eVvs vacuum)相匹配,都可用作DSSCs的敏化染料,但与CVBTP相比,CVTP具有更适合的LUMO能级和较好的光伏性能。