固/液界面原位红外显微镜和步进扫描时间分辨FTIR反射光谱及其在纳米材料科学中的应用

结合红外显微镜和步进扫描FTIR光谱仪 ,发展了固 /液界面电化学原位显微镜红外反射光谱和步进扫描快速时间分辨FTIR反射光谱 ,并应用于纳米材料特殊性能和电化学反应动力学的研究。研制纳米结构Pt微电极 ,获得CO吸附的红外特征随纳米结构和纳米尺度变化的原位显微镜红外谱图。利用纳米结构Pt微电极的异常红外效应 ,显著提高电化学原位红外反射光谱的灵敏度 ,获得分辨率达 5 0 μs的步进扫描时间分辨光谱。不仅发展了固 /液界面显微镜原位红外反射光谱新方法 ,并且拓展了电化学原位红外反射光谱在纳米材料科学研究中的应用。     

纳米结构Pt膜上CO吸附的异常红外效应机理研究

CO吸附在经方波电势处理后的纳米结构Pt金属膜电极上可观察到异常红外效应（AIREs）.在实验基础上用粒子间的相互作用和电子-空穴衰减机理分析、模拟了AIREs，表明Pt金属表面的纳米岛状结构增强了CO分子间及CO分子与纳米结构表面的相互作用，电子-空穴衰减引起的能量转移和粒子间相互作用的增强可以导致异常红外吸收谱线变化特征的出现. 关键词： 异常红外效应 粒子相互作用 电子-空穴衰减     

Pt纳米微粒自组装体系的电化学和原位FTIR反射光谱研究

用化学还原法制备了铂金属纳米微粒 ,透射电子显微镜 (TEM)表征纳米Pt微粒的平均直径为 2 5nm。通过二硫醇将Pt纳米微粒组装到多晶金电极表面。以Fe(CN) 4- 3-6 的氧化还原作为探针反应的电化学研究表明 ,Au表面组装二硫醇后抑制了电极 /溶液界面的电子传递过程 ,而在二硫醇上再组装铂纳米微粒后 ,电子传递又可进行。运用电化学FTIR反射光谱研究了Pt纳米微粒组装电极在酸性介质中CO的吸附 ,检测到CO的线型、桥式吸附态 ,分别在 2 0 30和 184 5cm- 1 附近给出红外吸收谱峰 ,并且有增强红外效应。此外 ,还观察到Pt纳米微粒上的CO孪生吸附态。红外吸收峰位于 2 10 0cm- 1 附近。     

掺杂不同一维纳米材料的空穴缓冲层对有机电致发光器件性能的影响

对一维纳米材料在空穴缓冲层PEDOT中的作用进行了研究。光致发光表明在PEDOT中掺杂一维纳米材料(二氧化钛纳米管和氧化锌纳米棒)可以提高双层样品PEDOT/MEH-PPV的发光效率。拉曼光谱的结果说明正是由于一维纳米材料与PEDOT之间存在的强相互作用,才减少了PEDOT/MEH-PPV界面上猝灭发光的缺陷态的产生。在以MEH-PPV作为发光层的聚合物电致发光器件中,在PEDOT中掺杂二氧化钛纳米管和氧化锌纳米棒后,器件的最大效率分别提高了2倍和2.5倍。     

CO探针原位红外光谱研究Pt/Sn双金属重整催化剂

催化重整是生产芳烃原料和高辛烷值清洁汽油调和组分的重要工艺。以目前应用广泛的铂锡工业重整催化剂金属含量为参比,用工业剂制备方法合成了Pt含量为0.6%的一系列铂锡重整催化剂,建立CO探针原位红外的表征方法,并对其进行系统表征,首次获得了1%以下低含量助剂Sn的CO探针红外谱图。研究结果表明,系列剂的金属Pt的CO吸附特征峰主要以线式吸附状态存在。0.6%纯Pt剂上1 826 cm-1处CO桥式吸附特征峰,因添加助剂Sn后,强度下降,而CO线式吸附特征峰的强度则增加,说明Sn的加入使得Pt的分散度增加。变温CO探针吸附原位红外研究表明,对负载质量分数0.3%的纯Sn催化剂,当脱附温度升高至120 ℃时,吸附在Sn上的CO特征峰会完全消失。对负载质量分数0.6%的纯Pt催化剂,当脱附温度升高至300℃时,吸附在Pt中心上的CO特征峰会完全消失。当Pt-Sn双金属负载质量分数Pt为0.6%、Sn为0.3%时,CO的脱附温度明显提高达350 ℃。与纯Pt剂相比,随着Sn助剂的加入,使得CO的脱附温度稍有提升,Pt-Sn催化剂Pt的CO特征峰向高波数方向移动,说明Sn的加入一定程度上减弱了活性金属Pt中心上的电荷密度。因而,CO探针原位红外是表征低金属铂锡工业重整催化剂的有效手段,为阐明多金属重整催化剂的助剂作用和研究反应机理提供重要信息。     

氧化锌纳米棒场发射性能研究

采用简单物理气相沉积法制备出取向和非取向的氧化锌纳米棒，他们的场致电子发射性能测量结果表明，ZnO纳米棒具有较好的场发射性能，但是高度取向的ZnO纳米棒阵列并不利于获得高的场致电子发射电流密度.这可能是由于高密度ZnO纳米棒之间具有较高的屏蔽效应，降低了ZnO纳米棒阵列的场放大因子，从而影响了其场发射性能.相反，非取向ZnO纳米棒由于相互之间的屏蔽效应比较弱，而且表面存在容易成为发射中心的微小突起，表现出较好的场发射效果.这些结果不仅有助于加深我们对准一维纳米材料场致电子发射性能的理解，也为未来场发射电子器件的实际应用提供了可靠的依据. 关键词： 氧化锌 场发射 非取向     

WO3/Pt复合薄膜的制备及其光电催化性能

导电玻璃作为基底水热法生长了WO₃纳米棒,通过电沉积法改变沉积Pt的时间(40 s,80 s,120 s),以WO₃纳米棒为基底沉积得到不同的WO₃/Pt复合薄膜样品。通过X射线衍射分析和扫描电子显微镜等测试手段将WO₃纳米棒薄膜和WO₃/Pt复合薄膜样品进行表征。结果表明成功制备了WO₃/Pt复合薄膜样品。漫反射结果显示WO₃/Pt复合薄膜与WO₃薄膜相比具有更强的光吸收。交流阻抗谱显示WO₃/Pt复合薄膜与WO₃纳米棒薄膜相比增强了电荷转移效率。利用光电流、光电催化对WO₃/Pt复合薄膜进行光电性能测试,结果表明WO₃/Pt复合薄膜相较于单一WO₃薄膜光电流活性更高和光电催化活性更强,并且沉积时间为80 s的WO₃/Pt复合薄膜显示最为优异的光电流和光电催化性能。同时,沉积时间为80 s的WO₃/Pt复合薄膜的光电催化性能优于其光催化和电催化性能。     

(SiO2)nO2H4的红外振动光谱的理论研究

运用密度泛函理论,在6-31G(d)基组水平上,计算了纳米尺度的(SiO2)nO2H4链状、环状、笼状三种不同构型的红外振动光谱.对准一维的链状和环状结构,红外振动较强峰的频率随着长度的增加单调变化,显示了较强的尺寸依赖性;沿纳米线(环)轴向和垂直于轴向的振动模式,频率对尺寸的依赖关系相反,揭示了纳米材料的振动性质的各向异性.笼状结构由于构型的复杂性而使得其不具备准一维的特性,同时结构的对称性降低,红外振动模式数目增加.三种构型中二元环和硅羟基的振动以及笼状构型中硅氧四面体骨架的振动与实验上所观测到的振动峰相吻合.红外光谱方面的理论计算结果对实验合成的SiO2纳米材料的表征具有指导意义.     

原位红外光谱研究Pt/FeO_x催化剂的CO氧化反应机理

低浓度CO氧化是催化领域的重要研究方向之一,在大气污染治理、CO气体防护面具、燃料电池气体净化、CO气体传感器、封闭式CO2激光器等方面具有重要应用前景。近年来,我们课题组采用胶体沉积法制备出Pt/FeOx催化剂,该催化剂具有良好的CO低温催化氧化性能[1,2]。利用原位红外光谱监测Pt/FeOx催化剂上的低温CO氧化反应过程,研究结果发现氧气活化能力对Pt/FeOx催化剂的低温CO催化性能影响较大。     

表面合金电催化剂上甲酸氧化的原位FTIR反射光谱研究

运用原位红外反射光谱(FTIRS)和电化学循环伏安法(CV)研究了甲酸在三种不同电极上的电催化特性。结果表明甲酸在碳载铂电极(Pt/GC)上的电催化氧化机理与本体铂电极(Pt)相类似,即可以通过活性中间体或毒性中间体氧化至CO_2。Pt/GC对甲酸的氧化比Pt具有更高的电催化活性。Pt/GC表面以Sb吸附原子修饰的电极(Sb-Pt/GC)上,甲酸氧化的起始电位(E;)提前至-0.10V,氧化电流峰电位(Ep)提前至0.34V,氧化峰电流(jp)值增加了7.28倍,半峰宽(FWHM)为0.30V。同样,Surface al-loy/GC电极上,E_I为-0.12V,E_p为0.32V和j_p为7.25mA·cm~(-2),相对Pt/GC分别负移了0.22,0.02V和增大了8.15倍,半峰宽(FWHM)为0.5V。表明Sb-Pt/GC和Surface alloy/GC电极不仅能够有效地抑制毒性中间体CO的生成,而且还可以显著地提高其对活性中间体的氧化的电催化活性。     

碱性溶液中纳米钯膜电极表面CO、CN-吸附的红外反射光谱研究

以原位ＦＴＩＲ反射光谱研究碱性介质中ＣＯ和ＣＮ＾－在纳米Ｐｄ膜电极上的吸附和共吸附,进一步揭示了纳米薄膜材料的异常红外效应和ＣＯ与ＣＮ＾－共吸附时的相互作用规律。     

Magneto-optical Static Recording Performances of Sputtered CoPt Alloy Films

CoPt alloy films with good magnetic and mageto-optical properties were prepared on Pt buffer layer or directly on glass subst rate by sputtering a composite target. Their static recording properties were investigated. The results showed that static signals could be easily written into the CoPt alloy films without Pt buffer layers using moderate recording power. The introduction of Pt buffer layer in CoPt alloy films not only led to a smaller Kerr rotation but also greatly increased the recording power.     

Laser ablation synthesis of monodispersed magnetic alloy nanoparticles

Monodispersed CoPt alloy nanoparticles were synthesized by a pulsed laser ablation (PLA) technique coupled with a low-pressure operating differential mobility analyzer (LP-DMA). The CoPt alloy nanoparticles were generated by laser ablating a solid Co–Pt target. In CoPt alloy nanoparticles synthesized from a target with a Co composition of 75 at%, the nanoparticle surfaces were covered by an oxide layer and exhibited a core-shell structure. In contrast, no shell was observed in particles generated from a target with a Co:Pt ratio of 50:50 at%. According to an EDX analysis, the compositions of the individual nanoparticles were almost the same as that of the target material. Finally, the magnetic hysteresis loops of the CoPt alloy nanoparticles exhibited ferromagnetism.     

Spark-based improved Basin-Hopping Monte Carlo algorithm for structural optimization of alloy clusters

CoPt alloy clusters are promising candidates for catalysts in fuel-cell applications because of their enhanced catalytic performances compared with pure Pt clusters. In this article, an improved Basin-Hopping Monte Carlo (BHMC) algorithm is proposed to optimize the stable structures of CoPt clusters with different sizes and compositions, and the Spark parallel framework is employed to accelerate the structural optimizations. The results show that the improved BHMC algorithm has higher probability to find the lowest-energy structure and more rapid convergence than the traditional BHMC one. Through the comparison of different threads during Spark parallel computing, it is found that the acceleration ratio increases with the thread number while decreases for large cluster due to the limitation of the resource allocation. By investigating the optimized structures of CoPt clusters, it is revealed that for small CoPt clusters, the most stable structures exhibit a wide variety at different Co/Pt ratios; for large CoPt clusters, however, their structures are independent of the Co/Pt ratios and close to the results of their monometallic counterparts. Besides, for all the CoPt clusters, Pt atoms tend to distribute near the surface and Co atoms are generally located in the interior.     

Effects of layering and magnetic annealing on the texture of CoPt films

The effect of magnetic field annealing of magnetron sputtered CoPt alloy films and Co/Pt bilayers on the crystallographic texture of the obtained chemically ordered (L1₀) CoPt films is presented. In CoPt alloy films the main effect of the magnetic field is to suppress (1 1 1) growth in the early stages of L1₀ formation whereas the development of (0 0 1) versus (1 0 0) texture is related to chemical ordering strain. A higher degree of (0 0 1) texture is obtained by magnetically annealing Co/Pt bilayers since the initial (1 1 1) texture in the as-sputtered films is avoided and Co-Pt alloying occurs in the presence of the magnetic field.     

Possible reaction pathway in methanol dehydrogenation on Pt and Ag surfaces/clusters starting from O-H scission: Dipped adcluster model study

The mechanism of the methanol dehydrogenation reaction on a Pt surface has been investigated using the dipped adcluster model (DAM) combined with density-functional theory (DFT) calculations. Starting from O-H bond scission, methanol decomposes to form CO exothermically on the Pt surface, where the Pt-dσ orbital effectively interacts with the O-H antibonding orbital. The donative interaction of the Pt-dσ orbitals was found to be important for catalytic activation on the Pt surface. The reaction pathway starting from C-H bond scission has a larger activation barrier and, therefore, is less kinetically favorable. Electron transfer from the bulk, which is included in the present DAM calculation, plays an important role in the reaction pathway from O-H bond scission, in particular for the dehydrogenation of formaldehyde. On the other hand, the Ag surface has been shown to be effective for formaldehyde synthesis, because formaldehyde desorbs spontaneously from the Ag surface. The present reaction has also been examined and discussed in view of the nanoscale clusters and nanorods.     

Kinetic-anisotropy-induced ordering-orientation transition in epitaxial growth: a method to synthesize ordering-orientation superlattices

The epitaxial growth has a distinct kinetic feature that the lateral surface diffusion is faster than the longitudinal bulk diffusion. We show there is an ordering-orientation transition of alloy films with the change of growth rate due to this kinetic anisotropy. As an example, we have calculated the epitaxial growth of CoPt alloy films on the Pt buffer layer. We show the ordered structure of CoPt films changes from the L1(0) [001] (a compositional modulation along the [001] direction) variant to the L1(0) [100] variant with the increase of growth rate. This ordering-orientation transition also occurs with the decrease of temperature at adequate growth rate. Based on this mechanism, we propose a simple method to synthesize the ordering-orientation superlattices.