Cr~(2+):ZnS和Fe~(2+):ZnS光谱特性的比较研究

基于密度泛函理论和投影平面波方法,采用第一性原理对比分析了Cr2+:ZnS和Fe2+:ZnS的电子结构和光学性能。晶体中二价掺杂离子的态密度、能带结构和几何优化由广义梯度近似的PBE描述。Cr2+:ZnS和Fe2+:ZnS的近中红外光谱表明,特征吸收来自于局域激发的d和p-d杂化轨道之间的跃迁,Fe2+:ZnS的中心跃迁能量比Cr2+:ZnS的要低,红移0.34eV;分别制备了Cr2+:ZnS和Fe2+:ZnS晶体,并测得了Cr2+:ZnS和Fe2+:ZnS的吸收光谱,证实了Fe2+:ZnS的特征吸收峰较Cr2+:ZnS红移0.34eV。     

掺杂修饰与未修饰Fe_3O_4纳米粒子的光致聚合物全息性能

制备了未修饰以及用柠檬酸钠修饰的两种磁性Fe3O4纳米粒子,并研究了将其掺入到有机光致聚合物中的全息性能,阐述了形成光栅的双扩散原理及抗皱原因.研究表明:掺入这两种纳米粒子后,材料的全息性能均有所提高,但掺入修饰后纳米粒子的全息性能更为突出,衍射效率可达90%,空间折射率调制度达2.14×10-3,缩皱率降低至0.8%,说明经柠檬酸钠修饰后的Fe3O4纳米粒子更有利于提高光致聚合物的全息性能.     

Modelling self-sensing of a magnetostrictive actuator based on a terfenol-D rod

A simplified quasi-static computational model for self-sensing applications of magnetostrictive actuators based on terfenol-D rods is presented. Paths and angle changes in the magnetic moments rotation of Tb0.3Dy0.7Fe2 alloy are studied as functions of compressive stress and magnetic field, and then used to determine the magnetization in its actuation. Then sensing of magnetic induction picked from a driving coil in an actuator is derived. The model is quick and efficient to solve moments rotation and its magnetization. Sensing results of compressive stress and magnetostriction calculated by the model are in good agreement with experiments and will be helpful in the design and control of self-sensing applications in actuators.     

Optimization of the determination of chemical oxygen demand in wastewaters

Chemical oxygen demand (COD) is one of the most relevant chemical parameters for the management of wastewater treatment facilities including the control of the quality of an effluent. The adequacy of decisions based on COD values relies on the quality of the measurements. Cost effective management of the minor sources of uncertainty can be applied to the analytical procedure without affecting measurement quality. This work presents a detailed assessment of the determination of COD values in wastewaters, according to ISO6060:1989 standard, which can support reduction of both measurement uncertainty and cost of analysis. This assessment includes the definition of the measurement traceability chain and the validation of the measurement procedure supported on sound and objective criteria. Detailed models of the measurement performance, including uncertainty, developed from the Differential Approach, were successfully validated by proficiency tests. The assumption of the measurement function linearity of the uncertainty propagation law was tested through the comparison with the numerical Kragten method. The gathered information supported the definition of strategies for measurement uncertainty or cost reduction. The developed models are available as electronic supplementary material, in an MS-Excel file, to be updated with the user's data.     

蜂窝状CuO和Fe2O3纳米管协同光电还原CO2

采用阳极氧化法在Fe上原位生长直立有序的Fe2O3纳米管阵列,脉冲电沉积法将蜂窝状CuO组装到Fe2O3NTs上,得到CuO HCs/Fe2O3NTs催化剂.结果表明:Fe2O3NTs呈"火山状"规则生长,蜂窝状CuO均匀分布在Fe2O3NTs表面.修饰后,材料的能隙由原来的2.03 eV窄化为1.84 eV.同时发现该催化剂具有优良的光催化还原性能和电催化还原性能,光电催化还原CO2的主要生成产物为甲醇,甲醇在6 h时含量峰值为3.77 mmol/L.该研究对光电催化还原CO2有一定的指导和借鉴意义.     

纳米Fe3O4含量对微生物燃料电池性能的影响

以不锈钢网为集流体,采用辊压工艺制备了Fe3O4质量分数分别为0%、2.5%、5.0%和7.5%的不锈钢网、活性炭粉和Fe3O4构成的复合阳极AcM、AcFeM1、AcFeM2和AcFeM3,研究了Fe3O4含量对单室无膜空气阴极微生物燃料电池(MFC)产电性能的影响,并通过塔菲尔曲线和阳极充电-放电测试研究了不同Fe3O4含量的阳极的电化学行为。结果表明,阳极Fe3O4质量分数由0%增加至2.5%、5.0%时,MFCs的最大输出功率和净电容电荷由AcM阳极的664 mW/m2和293.9 C分别上升至AcFeM1、AcFeM2电极的731 mW/m2和300.4 C、809 mW/m2和388.5 C,当Fe3O4含量继续增加至7.5%时,MFCs的产电效率和净电容电荷均减小,Fe3O4质量分数在5.0%时,MFCs性能最佳;电化学测试进一步说明Fe3O4质量分数在5.0%时,MFCs阳极的动力学活性最好。     

Electrocatalytic conversion of CO2 to liquid fuels using nanocarbon-based electrodes

Recent advances on the use of nanocarbon-based electrodes for the electrocatalytic conversion of gaseous streams of CO₂ to liquid fuels are discussed in this perspective paper. A novel gas-phase electrocatalytic cell, different from the typical electrochemical systems working in liquid phase, was developed. There are several advantages to work in gas phase, e.g. no need to recover the products from a liquid phase and no problems of CO₂ solubility, etc. Operating under these conditions and using electrodes based on metal nanoparticles supported over carbon nanotube (CNT) type materials, long C-chain products (in particular isopropanol under optimized conditions, but also hydrocarbons up to C8–C9) were obtained from the reduction of CO₂. Pt-CNT are more stable and give in some cases a higher productivity, but Fe-CNT, particular using N-doped carbon nanotubes, give excellent properties and are preferable to noble-metal-based electrocatalysts for the lower cost. The control of the localization of metal particles at the inner or outer surface of CNT is an importact factor for the product distribution. The nature of the nanocarbon substrate also plays a relevant role in enhancing the productivity and tuning the selectivity towards long C-chain products. The electrodes for the electrocatalytic conversion of CO₂ are part of a photoelectrocatalytic (PEC) solar cell concept, aimed to develop knowledge for the new generation artificial leaf-type solar cells which can use sunlight and water to convert CO₂ to fuels and chemicals. The CO₂ reduction to liquid fuels by solar energy is a good attempt to introduce renewables into the existing energy and chemical infrastructures, having a higher energy density and easier transport/storage than other competing solutions (i.e. H₂).     

Fe改性对Ru/Al_2O_3催化剂的马来酸二甲酯加氢性能影响

以Al2O3为载体,采用吸附-沉淀法制备一系列Ru-Fe/Al2O3催化剂,并进行了H2-TPR、XRD及XPS表征。以马来酸二甲酯(DMM)催化加氢合成丁二酸二甲酯(DMS)为探针反应,考察了Fe的加入对Ru/Al2O3催化性能的影响。评价结果表明,当Fe/Ru原子比小于2时,催化剂活性变化不大;但Fe/Ru原子比大于或等于2时,催化剂活性明显增加;与Ru/Al2O3催化剂相比,Fe的加入改善了催化剂的高温氧化还原处理稳定性。以甲醇为溶剂,在70℃、1.0 MPa压力、600 r/min转速下,Ru-Fe/Al2O3催化DMM的转化率与生成DMS的选择性均接近100%。XPS和H2-TPR表征结果表明,Ru-Fe/Al2O3中Fe与Ru产生较强的相互作用,促进Ru的分散且调变了Ru的电子特性。     

不同金属外掺杂富勒烯C20M（M=Li,Ti,Fe）的储氢性能

使用密度泛函理论(DFT)中的广义梯度近似(GGA)对经碱金属原子Li、过渡金属原子Ti和Fe修饰的富勒烯C20M(M=Li,Ti,Fe)的储氢性能进行研究.结果表明,C20Li(C20Ti和C20Fe)能够吸附H2的最大数目为6,6和4,与18电子规则相吻合;C20M(M=Li,Ti,Fe)对H2的平均吸附能在0.25~0.80 eV范围内,介于物理吸附和化学吸附之间(0.1~0.8 eV),因此可以实现常温下对氢的可逆吸附.C20Li主要通过正负电荷形成的偶极矩作用进行储氢,而C20Ti和C20Fe主要通过Dewar-Kubas作用进行储氢.     

Magnetization of Fe‐oxide based nanocomposite tuned by surface charging

Aiming at a voltage‐control of magnetism, the magnetization of a porous γ‐Fe₂O₃–Pt nanocomposite is studied under the influence of charging the surfaces of the porous structure in an electrolyte. Reversible variations of the magnetization of up to 10.4% could be achieved upon charging in the regime where electrochemical adsorption and desorption occurs. The observed variation of the magnetization with electrochemical charging is assigned to the γ‐Fe₂O₃ nanoparticles whereas the conductive network of Pt nanoparticles is necessary for charging. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)