量子点PbS修饰纳米结构TiO2复合膜的光电化学研究

用光电流作用谱、光电流-电势图等光电化学方法研究了ITO(铟锡氧化物导电玻璃)/TiO₂ /Q-PbS(量子点PbS)膜电极的光电转换性质。结果表明，由于量子尺寸的效应，在膜电极制备中，随着ITO/TiO₂电极在饱和Pb(CH₃COO)₂溶液中浸泡时间的不同，所制备的Q-PbS颗粒大小不同，禁带宽度随着浸泡时间的增大而减小，浸泡时间为40 s、在80 ℃烘干下制备的Q-PbS的禁带宽度为1.68 eV，其价带位置为-5.072 eV。Q-PbS修饰ITO/TiO₂电极可使光电流发生明显的红移，从而提高宽禁带半导体的光电转换效率。     

Synthesis and Characterization of Lead Sulfide Nanoparticles in Zirconia-Silica-Urethane Thin Films Prepared by the Sol-Gel Process

PbS nanocrystals (NCs) ranging between 4–8 nm were incorporated into Zirconium-Silica-Urethane (ZSUR) matrix obtained by the sol-gel method. The sizes of the particles were controlled by temperature treatment and by concentration of PbS in ZSUR matrix. The sizes of PbS NCs were determined by TEM measurements. The quantum size effect could also be extracted from optical absorption and photoluminescence spectra. The new matrix allows incorporation of up to 40% PbS forming a characteristic structure of dendrite by reacting lead acetate with ammonium thiocyanate in sol-gel matrix. The sol precursors of the matrix for Zirconium-Silica-Urethane contained zirconium oxide (ZrO₂) matrix solution, tetramethoxysilane (TMOS), 3-glycid oxypropyl trimethoxysilane (GLYMO) and polyethylene urethane silane (PEUS) synthesized separately. The ZrO₂ matrix solution was obtained from zirconium n-tetrapropoxide in propanol and acetic acid was used as a chelating agent to stabilize the zirconium oxide precursor.     

含铅聚合物微凝胶与硫化氢反应前后在良溶剂中的分子扩散行为

用溶液聚合法制备出轻度交联的含铅微凝胶,用光子相关光谱技术测定其在良溶剂中与H2S反应前、后的扩散行为,由外推法得到在浓度无限稀时的分子扩散系数,给出微凝胶的流体力学半径。结果表明:相同量的含铅微凝胶在不同的初始浓度下与H2S反应,生成含PbS纳米微粒的凝胶；但其体积增大不同,这说明H2S与含铅微凝胶的反应既可以在分子内也可以在分子间进行,分子间的反应使含硫化铅微凝胶扩散系数随浓度的变化曲线的线性范围变小。     

液相合成方形PbS纳米晶的光学特性

采用一种简单、温和的液相合成方法制备了PbS纳米晶，利用透射电镜和高分辨透射电镜对PbS纳米晶的形貌与晶型结构进行了表征．研究了PbS纳米晶的光学吸收和光致发光特性，并比较分析了包覆剂聚乙烯吡咯烷酮(PVP)和回流时间对产物光学特性的影响．结果表明：PVP分子链中的O原子与纳米晶表面吸附的游离态Pb原子形成Pb-O配位键，使产物的激子吸收大为减弱，同时引起了表面浅束缚态能量的升高，最终导致了荧光淬灭现象．     

Effect of Al incorporation on the structural,morphological, optoelectronic and transport properties of PbS thin films

Doping of PbS thin films with different metal atoms produce considerable changes in structural and material properties that make them useful in the technology of thin film devices. The goal of this work is to study the effects of doping on the structural, morphological, optoelectronic and transport properties of PbS thin films as a function of Al³⁺ concentration. Thin films of pure and Al doped PbS nanoparticles are prepared on soda lime glass substrates by chemical bath deposition technique. The Al content in aqueous solution is varied from 0 to 20 mg. XRD analysis of the films revealed significant enhancement in crystallinity and crystallite size up to an optimum concentration of doping. Films are polycrystalline with crystallite size 19–32 nm, having face centered cubic structure. The optical band gap energy exhibits a decreasing trend and is shifted from 2.41 to 1.34 eV with increasing Al content. The room temperature conductivity of the as-deposited PbS films is in the range of 0.78×10⁻⁸ to 0.67×10⁻⁶(Ω cm)⁻¹ with a maximum for optimum Al content. The Al doped PbS thin film, which we synthesize with optimum Al concentration of 15 mg is found to be a most suitable material for solar control coating applications.     

高活性硫化铅电极的制备及在量子点敏化太阳能电池中的应用

为了提高量子点敏化纳晶薄膜太阳能电池的光电转换效率,我们通过连续在酸和多硫溶液中处理铅片制备了对多硫电解液具有高电催化活性的硫化铅电极.通过电化学阻抗谱测试评价所制备硫化铅电极的催化活性,从而确定制备高效硫化铅电极的最佳条件.以在最佳条件下制备的硫化铅为对电极、CdSe量子点敏化TiO2纳晶薄膜为工作电极和多硫电解液组装成量子点敏化太阳能电池.光电性能测试结果表明所制备的电极具有良好的催化活性和光电转换性能.与已报导的方法相比,新方法大幅度地减少制备过程所需的时间,但却提高了所制备的硫化铅对电极的催化活性.通过X射线衍射和扫描电镜测试表征了硫化铅的生成过程,探讨了催化活性提高的原因.     

Natural Soft/Rigid Superlattices as Anodes for High-Performance Lithium-Ion Batteries

Volume expansion and poor conductivity are two major obstacles that hinder the pursuit of the lithium-ion batteries with long cycling life and high power density. Herein, we highlight a misfit compound PbNbS₃ with a soft/rigid superlattice structure, confirmed by scanning tunneling microscopy and electrochemical characterization, as a promising anode material for high performance lithium-ion batteries with optimized capacity, stability, and conductivity. The soft PbS sublayers primarily react with lithium, endowing capacity and preventing decomposition of the superlattice structure, while the rigid NbS₂ sublayers support the skeleton and enhance the migration of electrons and lithium ions, as a result leading to a specific capacity of 710 mAh g⁻¹ at 100 mA g⁻¹, which is 1.6 times of NbS₂ and 3.9 times of PbS. Our finding reveals the competitive strategy of soft/rigid structure in lithium-ion batteries and broadens the horizons of single-phase anode material design.     

Fabrication of PbS nanocrystal-sensitized ultrafine TiO2 nanotubes for efficient and unusual broadband-light-driven hydrogen production

It is highly desired to maximize the use of solar light by developing broadband-light-responsive H₂ production system in the field of photocatalysis. Herein, a novel PbS/(Pt–TiO₂) nanocomposite with efficient and unusual broadband-light-driven H₂ production feature is constructed by using infrared-bandgap PbS nanocrystals as sensitizer of Pt-loaded ultrafine anatase TiO₂ nanotubes (Pt–TiO₂). After optimizing the component ratio, the resultant PbS/(Pt–TiO₂) nanocomposite delivers a H₂ production activity of 813 and 186 μmol h^?1 under ultraviolet (UV)-visible (Vis)-near-infrared (NIR) and Vis-NIR light irradiation, respectively. Moreover, an apparent quantum yield of 38.6%, 26.2%, 2.43%, 3.21%, 2.17%, 0.36%, 0.11% and 0.01% can be attained from the PbS/(Pt–TiO₂) nanocomposite illuminated at 350, 420, 550, 700, 760, 850, 950 and 1064 nm monochromatic light, respectively. The intimate interfacial contacts in the PbS nanocrystals decorated ultrafine TiO₂ nanotubes, which serve as the support and electron acceptor of PbS nanocrystals, can effectively promote the photoexcited hot electrons transferring from PbS nanocrystals to TiO₂ nanotubes before the thermalization losses, and thus causing the efficient Vis-NIR-light-responsive H₂ production activity of the PbS/(Pt–TiO₂) nanocomposite. These results provide an intriguing application of infrared-bandgap materials to exploit the low-energy photons of the solar light for constructing efficient and unusual broadband-responsive H₂ production system.     

Harmonic Mode-Locked Er-Doped Fiber Laser Based on a Microfiber-Based PbS Nanoparticle Saturable Absorber

Lead sulfide (PbS) is a nanomaterial with excellent optical and chemical properties, such as a narrow bandgap (0.37 eV), high thermal damage threshold, and high stability. Obviously, it is appropriate as a saturable absorber (SA) device for ultrafast photonics. However, PbS nanoparticles (NPs) as the SA of ultrashort harmonic mode-locked pulse still haven't been demonstrated at present. In this paper, the PbS NPs are made into an SA-device-based microfiber by optical deposition method and connected in an integrated Erbium-doped fiber laser. And both characteristics and nonlinear optical properties of PbS NPs have been systemically investigated. A fundamental frequency mode-locked pulsed laser is proposed, whose central wavelength is 1560 nm, and the pulse width is 1 ps. In addition, high repetition rate operations are achieved, with a maximum repetition rate of 833 MHz. This is the first time that PbS NPs are used to generate 96th-order harmonic mode-locking, and the corresponding pulse duration is 987 fs. It is demonstrated that PbS NPs are a kind of SA photonic material with excellent performance. It can improve the communication capacity by applying fiber communication, and it has potential application value even in material processing and optical comb.