Nano-Ag on vanadium dioxide. I. Localized spectrum tailoring

We report on the utilization of localized surface plasmon resonance (LSPR) of Ag nanoparticles to tailor the optical properties Of VO2 thin film. Interaction of nano-Ag with incident light yields a salient absorption band in the visible-near IR region and modifies the spectrum Of VO2 locally. The wavelength of modification occurs in a limited spectral region rather than affects the full spectrum. The wavelength of modification shows a strong dependence on the metal nanoparticle size and shifts toward the red as the particle size or the mass thickness of nano-Ag increases. Also, we found that the wavelength can be shifted into the IR further by introducing a thin layer of TiO2 onto the nano-Ag. Interestingly, with the help of LSPR effects the VO2 film exhibits an anomalous thermochromic behavior in the modification wavelength region, which may be useful in optical switching applications.

Nano-Ag on vanadium dioxide. II. Thermal tuning of surface plasmon resonance

Thermal tuning of the localized surface plasmon resonance (LSPR) of Ag nanoparticles on a thermochromic thin film of VO2 was studied experimentally. The tuning is strongly temperature dependent and thermally reversible. The LSPR wavelength lambda(SPR) shifts to the blue with increasing temperature from 30 to 80 degrees C, and shifts back to the red as temperature decreases. A smart tuning is achievable on condition that the temperature is controlled in a stepwise manner. The tunable wavelength range depends on the particle size or the mass thickness of the metal nanoparticle film. Further, the tunability was found to be enhanced significantly when a layer of TiO2 was introduced to overcoat the Ag nanoparticles, yielding a marked sensitivity factor Delta lambda(SPR)/Delta n, of as large as 480 nm per refractive index unit (n) at the semiconductor phase of VO2.

激光衍射法与吸管法对东北黑土区土壤粒径分布测定的差异性研究

目前激光衍射法(laser diffraction method,LD)逐步被用于土壤颗粒粒径分布(particle size distribution, PSD)的分析,为了对比LD法和吸管法测定东北黑土区土壤PSD的差异性,采用LD法和吸管法分别对东北黑土区宾州河流域36个土壤剖面不同层次178个土壤样品的PSD值进行了测定与分析。结果表明,同吸管法相比,LD法低估了土壤的黏粒含量,平均低估幅度19.69%,而高估了土壤的粉粒和砂粒含量,平均高估幅度分别为14.66%和5.13%。LD法所得PSD结果依据美国土壤质地分类制判定的土壤质地,相对于吸管法总体由粉黏质偏向粉砂质方向。建立了LD法与吸管法测定PSD结果的转换模型,将LD法测定的PSD结果利用转换模型校正后,其测定的各土壤粒级同吸管法相比,准确度达96.97%～98.71%,判定土壤质地的准确率也达83.15%。

土壤砂砾覆盖对入渗和蒸发影响研究进展

砂砾覆盖能防止土壤表面受到雨滴侵蚀,切断土壤的毛细管作用,从而对土壤入渗和蒸发规律产生影响。介绍了国内外砂砾覆盖对入渗和蒸发规律影响的研究成果,现有研究结果表明,降雨入渗与砾石覆盖度之间既有正相关关系,又有负相关关系,入渗不仅与砂砾粒径有关,还与砂砾在土壤表面所处的位置有关;砂砾覆盖能够抑制蒸发,抑制效果与砂砾粒径大小、颜色和厚度等有关。另外,一些国外学者通过定量化模型描述了砂砾覆盖条件下入渗和蒸发规律,但这些定量化模型还是最基本的简化模型,主要偏重于理论说明,直接应用于实践还存在一些问题。

两种土壤水分特征曲线间接推求方法对黄土的适应性评价

土壤水分特征曲线(SWCC)是模拟土壤水分运动和溶质运移的一个重要参数,利用土壤的基本物理性质来间接推求SWCC的方法已经成为当今土壤物理学领域的研究热点。为了比较两种SWCC间接推求方法——Arya-Paris物理经验方法(简称AP方法)和Tyler-Wheatcraft分形几何方法(简称TW方法)对黄土的适应性,该文分析了黄土高原296组土壤颗粒分布、容重和水分特征曲线等资料,利用简化的Fredlund(Fred3P)模型模拟得到连续的土壤颗粒分布曲线,然后应用AP和TW方法预测出相应吸力下的土壤含水量。研究结果表明,对于黄土性土壤,AP和TW两种方法的预测结果均达到了一定的精度,相比较而言AP方法的预测效果明显优于TW方法,且受质地影响小。

黄土丘陵区不同恢复年限草地土壤微团粒分形特征

运用分形理论研究黄土丘陵区不同恢复年限草地土壤微团粒的粒径组成、分形维数特征及与土壤理化性质关系,使分形学在土壤微团粒性状与土壤肥力特征研究中得到进一步应用,并为评价草地生态系统土壤特征及生态恢复提供新方法。结果表明:表土层分形维数随植被恢复年限的增加而减少;剖面土壤沙粒含量越高,微团粒分形维数越低,粘粒规律相反,而粉粒与分形维数相关性不显著;土壤质地由粗到细使得分形维数由小到大变化;分形维数也可有效地表征不同植被恢复年限的草地土壤结构和养分的变化趋势;分形维数与土壤容重、非活性孔度、全磷、速效钾及氨态氮之间存在正相关性,与土壤活性孔度、孔隙比、有机质、全氮、碱解氮及硝态氮表现出负相关。

Absorption and luminescence of the surface states in ZnS nanoparticles

A broad absorption band around 500 nm is observed in ZnS nanoparticles. The absorption becomes more intensive and shifts to the blue as the particle size is decreased. The absorption energy is lower than the band gap of the particles and is considered to be caused by the surface states. This assignment is supported by the results of the fluorescence and of the thermoluminescence of the surface states. Both the absorption and the fluorescence reveal that the surface states are size dependent. The glow peak of the semiconductor particles is not varied as much upon decreasing size, indicating the trap depth of the surface states is not sensitive to the particle size. Considering these results, a new model on the size dependence of the surface states is proposed, which may explain our observations reasonably. (C) 1997 American Institute of Physics.

Thermoluminescence of ZnS nanoparticles

The thermoluminescence (TL) of ZnS nanoparticles is reported. The TL intensity increases as the particle size is decreased. The consistency of the size dependence of the TL with that of the surface fluorescence indicates that the TL may be related to the surface states. TL may be caused by the recombination of carriers released from the surface states or defect sites by heating. Smaller particles have higher surface/volume ratio and more surface states, therefore contain more accessible carriers for TL. Besides, the carrier recombination rate increases upon decreasing size due to the increase of the overlap between the electron and hole wave functions. These two effects may make the TL increase upon decreasing size of the particles. The appearance of TL prior to any radiation reveals that trapped carriers have pre-existed. The investigation of TL may provide some useful information about the surface states that may explain the size dependence of the surface fluorescence. (C) 1997 American Institute of Physics.

Behavior of Pentacene Initial Nucleation on Various Dielectrics and Its Effect on Carrier Transport in Organic Field-Effect Transistor

The influence of dielectric surface energy on the initial nucleation and the growth of pentacene films as well as the electrical properties of the pentacene-based field-effect transistors are investigated. We have examined a range of organic and inorganic dielectrics with different surface energies, such as polycarbonate/SiO2, polystyrene/SiO2, and PMMA/SiO2 bi-layered dielectrics and also the bare SiO2 dielectric. Atomic force microscopy measurements of sub-monolayer and thick pentacene films indicated that the growth of pentacene film was in Stranski-Kranstanow growth mode on all the dielectrics. However, the initial nucleation density and the size of the first-layered pentacene islands deposited on different dielectrics are drastically influenced by the dielectric surface energy. With the increasing of the surface energy, the nucleation density increased and thus the average size of pentacene islands for the first mono-layer deposition decreased. The performance of fabricated pentacene-based thin film transistors was found to be highly related to nucleation density and the island size of deposited Pentacene film, and it had no relationship to the final particle size of the thick pentacene film. The field effect mobility of the thin film transistor could be achieved as high as 1.38 cm(2)/Vs with on/off ratio over 3 x 10(7) on the PS/SiO2 where the lowest surface energy existed among all the dielectrics. For comparison, the values of mobility and on/off ratio were 0.42 cm(2)/Vs and 1 x 10(6) for thin film transistor deposited directly on bare SiO2 having the highest surface energy.

长期施肥对土壤矿物粒级中碳水化合物分布特征的影响

土壤碳水化合物作为活性碳库的一部分，与土壤有机质转化所包含的复杂的微生物学、化学和物理学过程密切相关。本文采集公主岭市长期定位监测基地和沈阳农业大学田间试验地不同施肥处理的黑土和棕壤，通过超声分散方法得到细黏粒 (<0.2µm)，粗黏粒 (0.2-2µm)，粉粒 (2-50µm)，细砂粒 (50-250µm) 和粗砂粒 (250-2000µm)五个颗粒级别，研究化肥、有机肥的长期施用对两种土壤不同粒级中有机碳、氮和土壤碳水化合物 (中性糖和氨基糖) 的积累、分布特性的影响，并根据六碳糖与五碳糖的比值区分碳水化合物的植物或微生物的贡献，利用氨基葡萄糖/氨基半乳糖的比值进一步明确真菌和细菌对碳水化合物转化和富集的贡献。结果表明： 对于有机质水平较高的黑土来说，化肥和有机肥合理配施不仅显著增加了黑土有机碳、氮和碳水化合物含量，而且有利于它们在各粒级中的重新分布，如小粒级中土壤有机质明显损失，而大粒级中土壤有机质显著富集。在土壤原始有机质水平较低的土壤 (棕壤) 中，只有较高的有机肥用量才可以引起小粒级有机碳、氮向大粒级中的转移。暗示出长期施肥对土壤碳、氮以及碳水化合物的影响程度取决于土壤原有有机质水平，土壤有机碳在各粒级中的积累符合层级理论。粗砂粒级中土壤有机碳含量高和富集程度大是土壤质量较高的表征。 有机肥的施用引起了两种土壤各粒级，特别是大粒级中 (Gal+Man):(Ara+Xyl)比值的显著降低，表明植物源碳水化合物在有机质积累过程中的贡献要大于微生物源糖，说明有机肥中的植物源有机碳组分并不被土壤微生物全部矿化利用，而其中的一部分作为可利用的碳源或能源储藏在大粒级中，特别是粗砂粒级中。无论何种施肥处理，在有机质水平较高的黑土中，各粒级有机质中中性糖相对含量不变；但在有机质水平相对低的棕壤中，黏粒级有机质中中性糖相对含量都减小，粉粒和砂粒级有机质中中性糖相对含量增大。 在黑土处理中，施用有机肥有利于真菌源氨基糖相对积累，化肥则引起细菌源氨基糖所占比重的略微增加。有机肥和化肥配施在短期内会引起细菌活性的增强，可是从长期角度考虑，仍然是真菌源氨基糖的积累得到了加强。在有机质水平较低的棕壤中，几乎在所有的处理中，砂粒级均表现出细菌源氨基糖所占比重增加，而黏粒和粉粒级中真菌源氨基糖所占比重表现出一定程度的增加。

应用负载型纳米铁去除饮用水中砷的研究

砷是毒性最强的元素之一，水体中砷的污染己经引起人们广泛的关注。我国的新疆、内蒙、山西和台湾等省和地区地下水砷含量严重超标。全球共有5,000多万人遭受高砷饮用水的威胁，其中中国有1,500多万，是饮用水砷污染最严重的国家之一。WHO推荐饮用水砷的最高允许浓度从原来的50 µg•L-1已降至10 µg•L-1。更为严格的砷卫生标准的颁布，对作为饮用水源的地下水中的砷去除工艺提出了更高的要求。吸附法除砷比膜法、混凝法和离子交换法更安全、简便，是砷去除工艺中最有效的方法之一。 首先，本研究通过优化制备条件（包括炭种类的选择、炭的粒径大小、还原剂的浓度及滴定速率、反应温度、铁盐的种类及浓度、分散剂的比例及浓度），制备了负载型纳米铁。考虑到砷的去除效率、工程应用的可行性以及经济性，最优的制备条件如下：选用粒径为20~40目煤质炭，在室温、一定的分散剂比例及浓度，0.2 M KBH4滴速为20 d•min-1时所制备的Fe/炭为82.0 mg•g-1；纳米铁在活性炭孔内呈针状，其直径为30~500 nm，长度为1,000~2,000 nm。绝大多数的铁都负载到活性炭内部，这在处理水时铁不流失很重要。 其次，利用制备的负载型纳米铁作吸附载体，进行了饮用水中As(Ⅴ)的吸附去除实验。研究了该吸附剂对As(Ⅴ)的吸附等温线、动力学以及影响动力学的各种因素（包括As(Ⅴ)的不同初始浓度、吸附剂用量、pH值、共存离子和不同温度）、pH值、共存离子等环境条件对As(Ⅴ)去除的影响；以及吸附剂的再生及再生后的吸附效率等。研究发现在前12 h内吸附较快，72 h时达到了平衡。用Langmuir 吸附等温式估算出As(Ⅴ)的吸附量为12.0 mg•g-1。该吸附剂在pH 6.5， (25±2)℃， As(Ⅴ)初始浓度为2 mg•L-1，吸附剂用量为1.0 g•L-1时，As(Ⅴ)的去除率为75.2%；当把吸附剂的用量增加到1.5 g•L-1时，As(Ⅴ)的去除率可达99.9%以上。吸附剂可以用0.1M的NaOH浸泡12 h后即可再生，再生效率较高。常见的阴离子中PO43-、SiO32-对As(Ⅲ)的去除抑制较大，而SO42-、CO32-、C2O42-等离子对砷的去除影响较小。Fe2+对As(Ⅲ)的吸附抑制作用较大而其它阳离子影响不大。吸附剂可用0.1 M NaOH 有效再生，并且具有良好的机械性能。实验室初步实验数据表明，该吸附剂对饮用水除砷具有较好的应用前景。 第三，利用实验室制备的负载型纳米铁对饮用水中As(Ⅲ)的吸附去除也进行了研究。考察了吸附等温线、动力学以及影响动力学的各种因素、pH值、共存离子等环境条件对As(Ⅲ)去除的影响；以及吸附剂的再生及再生后的吸附效率等。研究发现，该吸附剂在pH 6.5， (25±2)℃， As(Ⅲ)初始浓度为2 mg•L-1，吸附剂用量为1.0 g•L-1时， 对As(Ⅲ)的去除率为99.8%；其吸附容量为1.996mg•g-1。吸附过程中部分As(Ⅲ)被氧化。与As(Ⅴ)的吸附相比，该吸附剂对As(Ⅲ)的效率比较高-而常见的其它除砷吸附剂如载铁纤维棉等，对As(Ⅴ)的效率比As(Ⅲ)高，为有效去除As(Ⅲ)，常常需要专门加上氧化这一过程。 最后，利用负载型纳米铁对饮用水中As(Ⅲ) 的氧化性能进行考察，发现该吸附剂不但能够有效吸附去除饮用水中的砷，而且还能把As(Ⅲ)有效地氧化为As(Ⅴ)。经过对吸附剂的构成组分分析发现，活性炭表面因富含多种官能团而对三价砷的氧化作用最大；其次是纳米铁也能把As(Ⅲ)氧化为As(Ⅴ)。