基于氮杂Mn咔咯二维纳米材料的单原子Mn中心催化氧化烷烃制醇

咔咯是由四个吡咯共轭相连而形成的具有芳香性的新型卟啉类大环化合物,但咔咯分子中存在一个直接连结两个吡咯环的C?C键,与卟啉相比,仅仅是少了一个“meso”位置的C原子.因此,在结构上,咔咯含有三个“吡咯型”氮原子和一个“吡啶型”氮原子,当咔咯失去三个内氢原子后变成了三价阴离子,易与金属形成高价态的稳定配合物.氮杂咔咯是一种咔咯的meso位上的C被取代为N的咔咯衍生物.与正常的咔咯相比,它更易于与过渡金属形成稳定配合物.正是由于这些独特的结构特点,使其在金属催化、染料敏化太阳能电池、光敏剂、金属传感器、甚至在医学上都有很好的应用前景.金属有机大环均相催化剂的非均相化,是改进反应产物分离和实现催化剂循环使用的最简单有效方法之一.环境友好的Mn氮杂咔咯催化剂,在温和条件下可以利用氧气直接将有机底物氧化.本文选用Mn氮杂咔咯催化剂作为基本构建单元,通过理论计算,构建了一种新型的具有高催化活性的含Mn氮杂咔咯环结构单元的二维纳米催化材料.我们分别使用高斯软件(Gaussian 09)和维也纳从头算模拟软件包(VASP)对孤立分子和周期性体系进行结构优化以及性质的计算.在这种二维材料中,每一个Mn原子作为相对独立的金属单原子中心(SAC),保留了单环中Mn金属中心的高催化活性.在温和的光照条件下,Mn金属中心可以直接活化氧气生成类自由基[Mn]-O-O中心,随后[Mn]-O-O中心可以有效地通过夺取有机底物中的H和紧接着新生自由基的偶合反应,选择性氧化C?H键为C?OH键.另外,通过沿[Mn]-O-O反应轴施加不同强度的外电场,可对此二维纳米材料的催化反应活性进行精细调控.本文为实验上制备基于Mn氮杂咔咯的非均相催化剂以及单原子Mn基催化剂提供了理论依据.     

Study of structural and magnetic properties of Fe_(80)P-_9B_(11) amorphous alloy by ab initio molecular dynamic simulation

The structural and magnetic properties of Fe_(80)P_9B_(11) amorphous alloy are investigated through ab initio molecular dynamic simulation. The structure evolution of Fe_(80)P_9B_(11) amorphous alloy can be described in the framework of topological fluctuation theory, and the fluctuation of atomic hydrostatic stress gradually decreases upon cooling. The left sub peak of the second peak of Fe–B partial pair distribution functions(PDFs) becomes pronounced below the glass transition temperature, which may be the major reason why B promotes the glass formation ability significantly. The magnetization mainly originates from Fe 3d states, while small contribution results from metalloid elements P and B. This work may be helpful for developing Fe-based metallic glasses with both high saturation flux density and glass formation ability.     

Spin current transmission in Co1-xTbx films

We investigate the spin to charge conversion phenomena in Y₃Fe₅O₁₂/Pt/Co_1-xTb_x/Pt multilayers by both the spin pumping and spin Seebeck effects.We find that the spin transport efficiency is irrelevant to magnetization states of the perpendicular magnetized Co;Tb;films,which can be attributed to the symmetry requirement of the inverse transverse spin Hall effect.Furthermore,the spin transmission efficiency is significantly affected by the film concentration,revealing the dominant role of extrinsic impurity scattering caused by Tb impurity.The present results provide further guidance for enhancing the spin transport efficiency and developing spintronic devices.     

Au/SrTiO3/Au界面电阻翻转效应的低频噪声分析

本文研究了Au/SrTiO₃/Au三明治结构中的双极电阻翻转效应, 观察到高、低阻态的电阻弛豫现象. 低频噪声测量表明高、低阻态的电阻涨落表现出1/f行为. 对比试验表明, 高阻态的低频噪声来源于反向偏置肖特基势垒和氧空位的迁移, 强度较大, 低阻态的噪声则源于类欧姆接触底电极区域的氧空位迁移导致的载流子涨落, 强度较低. 同时, 界面上氧空位浓度的弛豫导致了高、低阻态的弛豫过程. 关键词： 电阻翻转效应 低频噪声 氧空位     

点接触金属/Pr0.7Ca0.3MnO3/Pt结构稳定的低电流电阻开关特性

利用自主开发的导电原子力显微镜控制Pt,W探针构成点接触金属/Pr0.7Ca0.3MnO3(PCMO)/Pt三明治结构,对其电流-电压(I-V)及脉冲诱导电阻开关(EPIR)特性进行了研究.研究发现,在10 nA限流下两种电极对应结构的I-V都表现出相当稳定的双极性电阻开关特性,以及大于100的电阻开关比.进一步测试发现,点接触W/PCMO/Pt器件具有在10 nA限流下稳定的EPIR特性以及100 pA限流下重复的双极性电阻开关特性.此电流比已报道的电流低3个数量级,表明此结构在低功耗存储器件方面的潜在应用.通过对比样品不同位置、不同限流、不同接触面积点接触Pt/PCMO/Pt的I-V回滞特性,把点接触器件在低电流下稳定、显著的电阻开关效应归结于小的器件面积导致强的局域电场加强了O离子迁移效应.     

与色散介质毗邻的一维半无限光子晶体表面态

运用Bloch定理和传输矩阵方法,研究了与色散介质毗邻的由两种材料组成的半无限一维光子晶体局域表面态的电场和色散关系.和以空气为背景的一维光子晶体相比,毗邻色散介质的光子晶体表面模色散曲线在一定堆积次序下会在较低的带隙中发生断开,较高带隙中的表面模群速度在不同堆积次序下会有很大差异.当与色散介质毗邻的物质折射率较大时,较高带隙中的表面模群速度较小；与色散介质毗邻的物质折射率较小时,较高带隙中表面模的群速度较大.     

The influence of interfacial barrier engineering on the resistance switching of In₂O₃:SnO₂/TiO₂/In₂O₃:SnO₂ device

The I–V characteristics of In2O3:SnO2/TiO2/In2O3:SnO2 junctions with different interfacial barriers are inves- tigated by comparing experiments. A two-step resistance switching process is found for samples with two interfacial barriers produced by specific thermal treatment on the interfaces. The nonsynchronous occurrence of conducting filament formation through the oxide bulk and the reduction in the interfacial barrier due to the migration of oxygen vacancies under the electric field is supposed to explain the two-step resistive switching process. The unique switching properties of the device, based on interfacial barrier engineering, could be exploited for novel applications in nonvolatile memory devices.     

The influence of interfacial barrier engineering on the resistance switching of In2O3：SnO2/TiO2/In2O3：SnO2 device

The I-V characteristics of In2O3：SnO2/TiO2/In2O3：SnO2 junctions with different interracial barriers are inves- tigated by comparing experiments. A two-step resistance switching process is found for samples with two interfacial barriers produced by specific thermal treatment on the interfaces. The nonsynchronous occurrence of conducting filament formation through the oxide bulk and the reduction in the interracial barrier due to the migration of oxygen vacancies under the electric field is supposed to explain the two-step resistive switching process. The unique switching properties of the device, based on interracial barrier engineering, could be exploited for novel applications in nonvolatile memory devices.     

Clockwise vs Counter-Clockwise I-V Hysteresis of Point-Contact Metal-Tip/Pr0.7 Ca0.3MnO3/Pt Devices

Metal-tip/Pr0.7Ca0.3MnO3/Pt devices possess two types of I-V hysteresis： clockwise vs counter clockwise depending on the tip materials. The criteria for categorization of these two types of devices can be simply based on whether the Gibbs free energy of oxidation for the metal tip is lower or higher than that of PCMO, respectively. While the clockwise hysteresis can be attributed to electric field induced oxidation/reduction, the counter clockwise hysteresis can be explained by oxygen vacancy migration in an electrical field. Alternating-current conductance spectra also reveal distinct hopping barriers between these two categories of devices at high resistive states.     

MXene负载3d金属单原子高效氮还原电催化剂的理论筛选（英文）

氨是现代农业和工业不可缺少的化工原料,传统的Haber-Bosch合成氨生产工艺需要高温(～400℃)和高压(约10-15MPa)等苛刻条件,从而导致大量的CO₂排放和全球年1%-2%的能源消耗.因此,开发低温/低压和环境友好的新型合成氨催化剂对于可持续发展是非常重要的.近年来,单原子催化剂(SAC)作为一类新型的环境友好的催化材料在能源有效利用和环境保护中发挥了重要作用.MXenes是一类新型过渡金属碳化物/氮化物/碳氮化物二维纳米材料,因其具有类金属的导电性、亲水性、良好的柔性、可调节的多原子类型和原子层厚度以及表面端基修饰等物理化学特性,是较好的负载单原子催化剂的载体.MXenes负载的金属单原子催化剂(SAC)因其具有高稳定性、独特的电子结构和最高的原子利用率而成为潜在的低成本、高效环保的合成氨电催化剂.本文基于密度泛函理论(DFT)计算,系统研究了Ti₂CO₂的Ti缺陷位点被3d过渡金属M (Sc,Ti,V,Cr,Mn,Fe,Co,Ni,Cu和Zn)原子占据所形成的SAC(记为M₁@Ti<...