单原子催化剂M1/FeOx(M=Pt,Fe)的理论研究:CO氧化反应

负载型纳米贵金属催化剂是用于多相催化反应的重要的催化剂之一,也是各国催化科学与技术研发的重点,其工业应用也越来越广泛.理论和实验的研究结果均表明,当载体表面的金属粒子尺寸减小至亚纳米级乃至更小的低配位、不饱和的原子团簇时,它们常常成为诱发催化反应的活性中心,呈现更高的催化活性和选择性.将负载的金属尺寸由纳米量级减小至分散的金属团簇甚至单原子而使每个原子成为反应的活性位点已成为研究的重点.最近,由张涛等首次合成的单原子催化剂(SAC)Pt1/FeOx引起了国内外催化及表面科学工作者的极大关注.单原子催化剂作为连接均相催化剂和多相催化剂的桥梁,不仅具有非均相催化剂的稳定、易于与反应体系分离、易表征等优点,而且具有均相催化剂活性中心结构均一、活性中心原子利用率百分之百等优点.一方面,单原子催化剂给多相催化领域注入了新的活力,另一方面也更有利于运用量子与计算化学的研究方法建立与实验相匹配的理论模型并从原子水平上进一步理解多相催化反应的微观作用机理.实验和理论的研究结果表明,其它单原子催化剂如Ir1/FeOx,Au1/FeOx和Ni1/FeOx催化CO氧化反应表现出不同的活性.然而,底物FeOx中的Fe同样是第VIII族中的3d过渡金属,却在低温下对CO氧化反应没有催化活性.我们围绕这一问题,重点研究了底物FeOx在负载单原子Pt1前后催化CO氧化的反应机理和活性,解释了单原子催化剂Pt1/FeOx相比于底物FeOx为何具有如此高的催化活性的原因.我们采用Vienna Ab-initio Simulation Package(VASP)从头算模拟软件和密度泛函理论(DFT)的广义梯度近似(GGA)进行了理论计算.其中,选择PBE泛函描述体系的交换关联相互作用,用投影缀加波(PAW)赝势基组方法描述体系中的电子和离子实之间的相互作用,对Fe原子采用了DFT+U方法进行d电子强相关校正,并使用Dimer计算方法搜寻反应过渡态.研究结果表明,底物FeOx中氧空位的再生伴随第二个CO2分子从催化剂表面脱附的过程需要较高的活化势垒(1.09 eV),这一过程是整个CO氧化反应的决速步.与此相比较,Pt1/FeOx催化剂中,由于Pt原子代替了表面Fe原子,导致电子结构及性质的显著变化,有利于CO的活化、氧化和CO2的脱附.我们从电子能量态密度(DOS)和Bader电荷分析及模型分子团簇的轨道相互作用的角度进一步分析了两种催化剂存在差异的本质;揭示了单原子催化剂Pt1/FeOx中Pt1和底物FeOx之间的相互作用的机理及催化剂表面Pt单原子在催化反应过程中的关键作用.     

酚醛树脂层压基板真空热裂解产物分析表征

利用程序升温的热解炉反应器对酚醛树脂层压基板进行真空热裂解,通过元素分析、傅里叶红外(FT-IR)分析和气相色谱-质谱(GC-MS)分析,对原料及产物油成分进行了表征。研究表明,热解油上层清液主要是一些较易溶于水的物质,如苯酚、甲酚、二甲酚、糖类、乙内酰脲类、吗啉类、吡喃酮类和吡啶类化合物等;而下层沉淀则主要为不溶或难溶于水的物质,如大取代基酚类(取代基碳原子数≥2)、磷酸三芳基酯类、脂肪酸酯类和腈类化合物等。其中,三聚氰胺在上层清液和下层沉淀中都有较高的含量。     

Influence of the substrate temperature on the structural,optical, and electrical properties of tin selenide thin films deposited by thermal evaporation method

Thin films of tin selenide (SnSe) were deposited on sodalime glass substrates, which were held at different temperatures in the range of 350‐550 K, from the pulverized compound material using thermal evaporation method. The effect of substrate temperature (T_s) on the structural, morphological, optical, and electrical properties of the films were investigated using x‐ray diffraction analysis (XRD), scanning electron microscopy (SEM), transmission measurements, and Hall‐effect characterization techniques. The temperature dependence of the resistance of the films was also studied in the temperature range of 80‐330 K. The XRD spectra and the SEM image analyses suggest that the polycrystalline thin films having uniform distribution of grains along the (111) diffraction plane was obtained at all T_s. With the increase of T_s the intensity of the diffraction peaks increased and well‐resolved peaks at 550 K, substrate temperature, were obtained. The analysis of the data of the optical transmission spectra suggests that the films had energy band gap in the range of 1.38‐1.18 eV. Hall‐effect measurements revealed the resistivity of films in the range 112‐20 Ω cm for films deposited at different T_s. The activation energy for films deposited at different T_s was in the range of 0.14 eV‐0.28 eV as derived from the analysis of the data of low‐temperature resistivity measurements. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

状态转变增强拉曼光谱

表面增强拉曼散射(SERS)是公认的超灵敏的光谱工具.和传统的优化SERS基底材料或构筑完美的结构策略相比,我们提出了一种极其简单和灵敏的方法,该方法被命名为状态转变增强拉曼光谱(STERS).这种STERS检测方法可广泛的应用于毒品安全检测、食品安全和环境保护等方面.如果我们把这种方法和便携式拉曼光谱仪结合,这种应用...     

193 nm氟化物增透膜的特性

 为了研制低损耗、高性能的193 nm氟化物增透膜,研究了基底和不同氟化物材料组合对氟化物增透膜的影响。在熔石英基底上,将挡板法和预镀层技术相结合,采用热舟蒸发方式制备了不同氟化物材料组合增透膜,对增透膜的剩余反射率和光学损耗等光学特性,以及表面粗糙度和应力等特性进行了测量和比较。在分析比较和优化的基础上,设计制备的3层1/4波长规整膜系AlF3/LaF3增透膜在193 nm的剩余反射率低于0.14%,单面镀膜增透膜的透射率为93.85%,增透膜表面均方根粗糙度为0.979 nm,总的损耗约为6％。要得到高性能的193 nm增透膜,应选用超级抛光基底。     

超光滑基片表面散射的数值研究

以一阶微分散射理论为基础,从理论和模拟两个方面对超光滑基片表面的散射电磁场进行了数值研究.分析了s偏振光和p偏振光的微分散射随入射角和散射角的分布情况.研究发现,当入射角较大时,p偏振光在某个散射方向的微分散射为0,而无论入射角和散射角如何变化,s偏振光的微分散射均大于0.当用光散射法对超光滑基片进行表面测试时,相对于...     

Synthesis surface effects on the stress and deformation of film/substrate system

The closed-form solutions of bending curvature and stress distribution in film/substrate system with the synthesis surface effect are proposed by minimizing the total potential energy. Effects of the roughness and the residual surface stress on stress in film are addressed. Results reveal that, at a given thickness of the substrate, effects of roughness and residual surface stress on the bending curvature become significant with decreasing the film thickness. The roughing surface will enlarge the magnitudes of bending curvature and film stress. The direction change of residual surface stresses can lead to a reversed bending of film/substrate system.     

Swiss-Roll燃烧器催化剂结构的实验研究

实验研究了装有Pt覆盖的多孔陶瓷的Swiss-Roll燃烧器的燃烧特性,分别得到了3种不同长度的催化剂基底的熄火极限,并测量3种情况下催化剂壁面及催化剂后部空间的温度。实验结果表明,3种情况中,催化剂基底长4.5mm的燃烧器可燃范围最大,所以此长度较适合此Swiss-Roll燃烧器。从温度数据可以看出来,催化剂后部空间存在反应,且受上游催化剂表面反应强度的影响。     

Finite element buckling analysis of multi-layered graphene sheets on elastic substrate based on nonlocal elasticity theory

Graphene-polymer nano-composites are one of the most applicable engineering nanostructures with superior mechanical properties. In the present study, a finite element (FE) approach based on the size dependent nonlocal elasticity theory is developed for buckling analysis of nano-scaled multi-layered graphene sheets (MLGSs) embedded in polymer matrix. The van der Waals (vdW) interactions between the graphene layers and graphene-polymer are simulated as a set of linear springs using the Lennard-Jones potential model. The governing stability equations for nonlocal classical orthotropic plates together with the weighted residual formulation are employed to explicitly obtain stiffness and buckling matrices for a multi-layered super element of MLGS. The accuracy of the current finite element analysis (FEA) is approved through a comparison with molecular dynamics (MD) and analytical solutions available in the literature. Effects of nonlocal parameter, dimensions, vdW interactions, elastic foundation, mode numbers and boundary conditions on critical in-plane loads are investigated for different types of MLGS. It is found that buckling loads of MLGS are generally of two types namely In-Phase (INPH) and Out-of-Phase (OPH) loads. The INPH loads are independent of interlayer vdW interactions while the OPH loads depend on vdW interactions. It is seen that the decreasing effect of nonlocal parameter on the OPH buckling loads dwindles as the interlayer vdW interactions become stronger. Also, it is found that the small scale and polymer substrate have noticeable effects on the buckling loads of embedded MLGS.     

Method for modulating the wafer bow of free-standing GaN substrates via inductively coupled plasma etching

The bowing curvature of the free-standing GaN substrate significantly decreased almost linearly from 0.67 to 0.056 m⁻¹ (i.e. the bowing radius increased from 1.5 to 17.8 m) with increase in inductively coupled plasma (ICP) etching time at the N-polar face, and eventually changed the bowing direction from convex to concave. Furthermore, the influences of the bowing curvature on the measured full width at half maximum (FWHM) of high-resolution X-ray diffraction (HRXRD) in (0 0 2) reflection were also deduced, which reduced from 176.8 to 88.8 arcsec with increase in ICP etching time. Decrease in the nonhomogeneous distribution of threading dislocations and point defects as well as V_Ga–O_N complex defects on removing the GaN layer from N-polar face, which removed large amount of defects, was one of the reasons that improved the bowing of the free-standing GaN substrate. Another reason was the high aspect ratio of needle-like GaN that appeared at the N-polar face after ICP etching, which released the compressive strain of the free-standing GaN substrate. By doing so, crack-free and extremely flat free-standing GaN substrates with a bowing radius of 17.8 m could be obtained.