碱性介质电催化体系活性氧的生成及其光谱学研究

亚熔盐液相氧化技术可在相对低温下实现难分解两性金属矿物的高效转化,基于此进一步提出了碱性介质电化学活性氧协同强化新方法。利用紫外-可见光光谱和电子自旋共振波谱等手段对电催化体系活性氧的生成与转化机理进行了系统解析。通过阴极电催化的作用,在电极表面定向进行两电子氧气还原反应,原位产生大量的活性氧组分。研究发现过渡金属离子与两电子氧气还原产物HO-₂之间的“自诱发”效应,可生成具有更高氧化活性的羟基自由基,大幅促进两性金属转化过程,实现了碱性介质电化学高级氧化过程。利用紫外-可见光光谱检测到电化学体系活性氧催化氧化低价两性金属氧化物(Cr₂O₃和V₂O₃)的转化过程。与此同时,根据标准自由能变化的热力学数据计算可知,V₂O₃比Cr₂O₃更易在活性氧存在的条件下发生溶出反应。采用电子自旋共振波谱(ESR)对电催化体系内的羟基自由基进行检测,结果表明由V₂O₃引发的电化学-类Fenton反应激发产生的羟基自由基ESR信号比Cr₂O₃信号强。利用猝灭剂实验验证了具有高氧化电位的羟基自由基可以对两性金属液相氧化起到促进作用。该研究为碱性介质电化学矿物溶出实际反应提供理论参考。     

Electrical property effect of oxygen vacancies in the heterojunction of LaGaO_3/SrTiO_3

Density functional theory within the local density approximation is used to investigate the effect of the oxygen vacancy on the LaGaO_3/SrTiO_3(001) heterojunction. It is found that the energy favorable configuration is the oxygen vacancy located at the 3~(rd) layer of the STO substrate, and the antiferrodistortive distortion is induced by the oxygen vacancy introduced on the SrTiO_3 side. Compared with the heterojunction without introducing oxygen vacancy, the heterojunction with introducing the oxygen vacancy does not change the origin of the two-dimensional electron gas(2DEG), that is, the 2DEG still originates from the d_(xy) electrons, which are split from the t~(2g) states of Ti atom at interface; however the oxygen vacancy is not beneficial to the confinement of the 2DEG. The extra electrons caused by the oxygen vacancy dominantly occupy the 3d_(x~2-y~2) orbitals of the Ti atom nearest to the oxygen vacancy, thus the density of carrier is enhanced by one order of magnitude due to the introduction of oxygen vacancy compared with the density of the ideal structure heterojunction.     

SnO2/氮掺杂石墨烯纳米复合材料的制备及其电化学性能研究

采用温和的水热法在氧化石墨烯(GO)片层上原位生长纳米SnO2颗粒, 通过氨水调节体系pH值并对石墨烯进行掺氮,成功制备出了SnO2/氮掺杂石墨烯(N-rGO)和SnO2/石墨烯(rGO)纳米复合材料,并对它的电池和电催化性能进行研究.XRD和SEM等分析结果表明,SnO2颗粒均匀地分布在N-rGO和rGO表面,粒径分别为50 nm和100 nm左右.进一步的TEM结果表明,SnO2颗粒是由更细小的粒径为5~7 nm SnO2颗粒所组成的二次团聚体.半电池性能测试结果表明:在100 mA/g电流密度下,SnO2/N-rGO和SnO2/rGO的可逆容量分别为901 mAh/g、756 mAh/g,比同等条件下纯的纳米SnO2高6.0和4.9倍;在2 A/g的高电流密度放电情况下, SnO2/N-rGO和SnO2/rGO的放电比容量分别可以达到619 mAh/g和511 mAh/g,表现出优异的倍率性能.电催化性能测试表明:SnO2/N-rGO的催化活性要高于SnO2/rGO,催化氧还原反应(ORR)主要按照四电子转移过程进行,为非铂催化剂的研究提供了一个新的思路.     

铂合金纳米立方块催化剂的氧还原反应活性比较

氧还原反应是质子交换膜燃料电池和金属-空气电池的重要反应,贵金属铂（Pt）与元素周期表中第一排的非贵过渡金属（M）形成铂合金催化剂（PtM）可以提高氧还原反应活性. 但是,有关活性的提高有多大程度上是来自合金元素的贡献却仍然存在争议. 为了研究合金元素对PtM催化活性的影响,本工作合成了颗粒形状与合金元素含量相似的铂锰（PtMn）, 铂铁（PtFe）, 铂钴（PtCo）和铂镍（PtNi）纳米立方块催化剂,并考察了不同铂合金催化剂在酸性介质中的氧还原反应活性. 选择制备立方块形状纳米颗粒催化剂进行比较,可以将颗粒表面结构对催化活性的影响降到最小. 结果表明,氧还原反应活性与铂d-带中心值曲线呈现火山形关系,其中PtCo纳米立方块催化剂的活性最高. 本文所得到的实验结果与基于d-带理论框架已知表面的密度泛函理论计算结果一致.     

基于辐射法和原子发射光谱法的转炉口火焰温度测量

转炉炼钢的终点控制包括钢水出钢时温度及其成分的控制,炉口火焰能够反映炉内脱碳速率及转炉运行参数等。工业炉燃烧火焰可见光谱段,普遍存在着钾(K)和钠(Na)等碱金属元素的原子发射谱线,利用K的特征谱线相对比值可以计算火焰温度。基于辐射双色法,三色法和谱线相对强度法对转炉口火焰温度进行了测量;数据处理过程中对特征谱线进行了基线拟合提取,小波脊线拟合提取;特征谱线进行了Gauss函数和Lorenz函数拟合。结果表明,辐射测温法对谱线比较敏感,选择合理的波段能够有效,精确地测量火焰温度;采用谱线相对强度法受制于特征谱线的数学模型、谱线的跃迁机率、能级的简并度及火焰的光学厚度,需要分辨率非常高的光谱仪才能进行高温转炉火焰中电子温度的测量。     

Understanding oxygen reactions in aprotic Li-O_2 batteries

Although significant progress has been made in many aspects of the emerging aprotic Li-O_2 battery system, an indepth understanding of the oxygen reactions is still underway. The oxygen reactions occurring in the positive electrode distinguish Li-O_2 batteries from the conventional Li-ion cells and play a crucial role in the Li-O_2cell's performance(capacity, rate capability, and cycle life). Recent advances in fundamental studies of oxygen reactions in aprotic Li-O_2 batteries are reviewed, including the reaction route, kinetics, morphological evolution of Li_2O_2, and charge transport within Li_2O_2. Prospects are also provided for future fundamental investigations of Li-O_2 chemistry.     

Identification of surface oxygen vacancy-related phonon–plasmon coupling in TiO_2 single crystal

Oxygen vacancies(OVs) play a critical role in the physical properties and applications of titanium dioxide nanostructures, which are widely used in electrochemistry and photo catalysis nowadays. In this work, OVs were artificially introduced in the surface of a pure TiO_2 single crystal by pulsed laser irradiation. Raman spectra showed that the intensity of E_g mode was enhanced. Theoretical calculations disclose that this was caused by the strong coupling effect between the phonon vibration and plasmon induced by the OVs-related surface deformation, and good agreement was achieved between the experiments and theory.     

Coexistence of unipolar and bipolar modes in Ag/ZnO/Pt resistive switching memory with oxygen-vacancy and metal-Ag filaments

In this study, the unipolar resistive switching(URS) and bipolar resistive switching(BRS) are demonstrated to be coexistent in the Ag/Zn O/Pt memory device, and both modes are observed to strongly depend on the polarity of forming voltage. The mechanisms of the URS and BRS behaviors could be attributed to the electric-field-induced migration of oxygen vacancies(VO) and metal-Ag conducting filaments(CFs) respectively, which are confirmed by investigating the temperature dependences of low resistance states in both modes. Furthermore, we compare the resistive switching(RS)characteristics(e.g., forming and switching voltages, reset current and resistance states) between these two modes based on VO- and Ag-CFs. The BRS mode shows better switching uniformity and lower power than the URS mode. Both of these modes exhibit good RS performances, including good retention, reliable cycling and high-speed switching. The result indicates that the coexistence of URS and BRS behaviors in a single device has great potential applications in future nonvolatile multi-level memory.     

多次透射反射红外光谱法灵敏和准确地测量单晶硅中间隙氧和代位碳的含量

建立了室温下使用多次透射反射红外光谱法(MTR-IR)测量单晶硅中间隙氧和代位碳含量的新红外光谱吸收方法,在理论和实验上证明了MTR-IR优于常规使用的单次垂直透射红外(IR)吸收测量方法。与IR法相比较,MTR-IR法的优点为:(1)间隙氧在1 107 cm^-1处和代位碳在605 cm^-1处的吸收峰与MTR-IR法中红外光透过硅片的的次数N(6~12)成线性增加的正比例关系,因此单晶硅中间隙氧和代位碳含量的检测限至少比IR法低一个数量级;(2)MTR-IR法测量薄硅片如0.2 mm的厚度时产生的干涉条纹强度是单次垂直透射红外吸收法(IR)的1/23、是单次Brewster角透射红外吸收法的1/11;(3)单次垂直透射红外吸收法(IR)1次只测量样品上的1个点,MTR-IR法则在更长的样品上1次测量多个样品点,每次测量更具有代表性。理论计算和实验结果都证实了MTR-IR吸收法测量晶体硅中间隙氧和代位碳杂质含量的高灵敏度、可靠性和重复性。