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氮自掺杂暴露(001)晶面TiO2微米片的可见光光催化CO2还原性能增强

Maxwell Selase Akple , 刘敬祥 , 秦志扬 , S. Wageh , Ahmed. A. Al-Ghamdi , 余家国 , 刘升卫

催化学报 doi:10.1016/S1872-2067(15)60989-5

化石能源的使用可产生大量CO2,带来严重的温室效应。光催化CO2还原生产太阳燃料技术既有望缓解温室效应,又可以将低能量密度的太阳能转化为高能量密度的化学能储存起来方便使用。高效光催化材料的开发是发展光催化技术的关键。迄今,在已开发的所有半导体光催化材料中, TiO2仍是广泛研究的明星材料。在实际使用中, TiO2的光催化效率仍受限于其极弱的可见光利用率和较高的电子-空穴复合几率。近年来,越来越多的研究表明TiO2的结构与形貌特征极大地影响其光催化效率。尤其, TiO2的外露晶面设计与晶面效应研究引起了广泛关注。由于具有较高表面能和较多表面不饱和键,起初大多数理论和实验研究认为锐钛矿TiO2(001)晶面是光催化活性晶面。后来,越来越多研究表明并非锐钛矿TiO2(001)晶面的暴露比例越高其光催化活性就越高。最近,我们发现锐钛矿TiO2(001)晶面与(101)晶面在调控光催化CO2还原性能上具有良好的协同效应。密度泛函理论计算表明,锐钛矿TiO2的(001)晶面与(101)晶面的能带结构有差异,(001)晶面的导带位置相对于(101)晶面而言较高,而(101)晶面的价带位置相对于(001)晶面而言较低。基于此我们提出,具有合适比例的锐钛矿TiO2的(001)晶面与(101)晶面的交界处可以形成最佳的表面异质结或晶面异质结。表面异质结的形成导致光生电子倾向于向(101)扩散,光生空穴倾向于向(001)扩散,从而促进光生电子-空穴分离,降低光生电子-空穴复合几率。在此工作基础上,我们直接以氮化钛为原料,氢氟酸为添加剂,通过简单的水热反应一步合成了氮自掺杂的TiO2微米片。利用X射线粉末衍射、扫描电镜、X射线光电子能谱、紫外-可见漫反射光谱、氮气吸附-脱附以及电化学阻抗谱等方法手段对所制备的光催化剂进行了基本结构与理化性质表征分析,并研究了其可见光光催化CO2还原性能。电镜照片结果表明,我们所制备的氮自掺杂锐钛矿TiO2微米片的(001)晶面与(101)晶面比例分别为65%和35%。基于我们前期研究结果, TiO2微米片的(001)晶面与(101)晶面可以形成表面异质结,具有良好的电荷分离效率,这也得到了电化学阻抗谱研究结果的证明。同时,由于N的原位掺杂,所制备的TiO2微米片具有优异的可见光捕获能力。由于可见光利用效率增强与光生电子-空穴分离效率提高这两方面的综合作用,所制备的氮自掺杂TiO2微米片具有非常好的可见光光催化CO2还原制甲醇性能,比商用P25及氮掺杂TiO2纳米粒子等参考样品的可见光光催化性能更优异。研究表明,通过原位自掺杂方法与晶面设计方法相结合,可以同时改善TiO2的可见光利用效率和光生电子-空穴分离效率,优化TiO2的可见光光催化性能,这也为后续开发新型高效光催化材料提供了新思路。

关键词: 氮自掺杂 , 二氧化钛 , (001)晶面 , 二氧化碳还原 , 表面异质结

FORMATION OF AMORPHOUS GE-S SEMICONDUCTOR ALLOYS BY MECHANICAL ALLOYING

Applied Physics Letters

Amorphous Ge1-xSx(x=0.61, 0.67, and 0.72) semiconductor alloys have been found formed by ball milling of powder mixtures of elemental Ge and S. The amorphization process and the ball-milled products have been investigated by x-ray diffraction, transmission electron microscopy, and Raman scattering. The results show that amorphous Ge-S alloys may form in a self-heating reaction, driven by the large heat of formation of amorphous and/or liquid Ge-S alloys. The structure of mechanically alloyed amorphous Ge-S alloys is similar to but not exactly identical with that of rapidly cooled amorphous Ge-S alloys. The amorphization transition mechanism reported is believed to be suitable for preparing other amorphous semiconductor alloys with similar thermodynamic conditions.

关键词: magnetic-properties;ni-zr;amorphization;powders;transition;interdiffusion;germanium;systems;glasses;metals

VIM法中采用CaO坩埚对Ni基高温合金脱S的影响

牛建平 , 杨克努 , 管恒荣 , 胡壮麒

机械工程材料 doi:10.3969/j.issn.1000-3738.2002.02.002

研究了使用CaO坩埚在VIM法精炼Ni基高温合金过程中S的变化规律及加Al对脱S的影响.试验表明:当CaO坩埚中的含S量高于液态金属中的含S量时,坩埚中的S将进入金属液中而使液态金属增S.加入0.5%的Al经30min精炼后可以使液态金属中的S含量从30mg/kg降低至小于5mg/kg.对CaO坩埚内壁的XRD及成分分析表明,加Al脱S是由于在CaO坩埚壁和金属液间形成低熔点的具有很强脱S能力的3CaO@Al2O3渣.

关键词: VIM , CaO坩埚 , Ni基高温合金 , S

Thermodynamic Behaviour of Fe-S-RE,Fe-Csat.-S-RE,Ni-S-RE,Cu-S-RE Solutions

Ting DU Longmei WANG Yeming WU Yuqing ZHANG Aisheng LIU Central Iron and Steel Research Institute , Beijing , 100081 , China

材料科学技术(英文)

The temperature dependences of the equilibrium constants for the reactions RES_((S))=[RE]+[S]. (RE=Ce,La,Nd,Sm,Y),of the standard Gibbs energies for the RES formed and of the interaction coefficients between RE elements and S for the Fe-base,Ni-base and Cu-base solutions are sum- marized.

关键词: thermodynamics , null , null , null , null

Corrosion behaviour of carbon steel in different concentrations of HCl solutions containing H(2)S at 90 degrees C

Corrosion Science

The corrosion behavior of SAE-1020 carbon steel in H(2)S-containing solutions with different concentration of HCl at 90 degrees C was investigated by weight loss, electrochemical measurements, SEM and XRD analysis. The results showed that the corrosion rate of carbon steel increased with increasing HCl concentration. Uniform corrosion was found on the carbon steel surface in H(2)S + HCl solutions, while corrosion cavities were observed in the solution only containing H(2)S. The ratio of Faradaic process of total corrosion process increased with the increase of HCl concentration. The corrosion products were solely composed of mackinawite in the H(2)S-containing solutions with or without HCl. (c) 2011 Elsevier Ltd. All rights reserved.

关键词: Steel;Weight loss;EIS;SEM;XRD;Acid corrosion;acidic chloride solutions;hydrogen-sulfide;aqueous-solution;iron;sulfides;electrochemical-behavior;media;dissolution;impedance;polarization;environments

Quantum transport of Au-S-S-Au nanoscale junctions

Applied Physics Letters

Transport in S(2) molecules sandwiched between Au electrodes is investigated with a combination of density functional theory and the non-equilibrium Green's function method. We consider four different configurations and find that their conductances are related to the details of the bonding geometry. When S(2) connects to pyramidal-shaped electrodes at the top site, the transmission is governed by a resonance and is strongly affected by the bias. In contrast, the transport of the remaining three configurations is through several closely spaced broad molecular orbitals, and the transmission coefficient is almost flat around the Fermi level. (C) 2012 American Institute of Physics. [doi:10.1063/1.3665614]

关键词: conductance;molecule

恒位移加载条件下X65管线钢H2S应力腐蚀研究

孙新阁 , 霍立兴 , 张玉凤

腐蚀科学与防护技术

采用楔形张开加载恒位移实验研究了X65管线钢在H2S溶液中的应力腐蚀开裂行为,并得出了X65管线钢母材、焊缝和热影响区的临界应力强度因子KISCC分别为55.7093 MPa•m 1/2、33.3189 MPa•m1/2和38.0711 MPa•m1/2;平台处的裂纹扩展速率da/dt分别为3.38×10-9m/s、3.5×10-9 m/s和3.5×10-9m/s.研究结果还表明,焊缝比母材具有更高的应力腐蚀敏感性. 

关键词: 管线钢 , null , null

恒位移加载条件下X65管线钢H2S应力腐蚀研究

孙新阁 , 霍立兴 , 张玉凤

腐蚀科学与防护技术 doi:10.3969/j.issn.1002-6495.2006.03.004

采用楔形张开加载恒位移实验研究了X65管线钢在H2S溶液中的应力腐蚀开裂行为,并得出了X65管线钢母材、焊缝和热影响区的临界应力强度因子KISCC分别为55.7093 MPa·m1/2、33.3189 MPa·m1/2和38.0711 MPa·m1/2;平台处的裂纹扩展速率da/dt分别为3.38×10-9m/s、3.5×10-9m/s和3.5×10-9m/s.研究结果还表明,焊缝比母材具有更高的应力腐蚀敏感性.

关键词: 管线钢 , 临界应力强度因子 , 裂纹扩展速率

EQUILIBRIUM OF Mg-S IN Ni MELTS

WANG Conghua HAN Qiyong University of Science and Technology Beijing , Beijing , China WANG Conghua Faculty of Physical Chemistry of Metallurgy , University of Science and Technology Beijing , Beijing , China

金属学报(英文版)

The equilibrium of Mg-S in Ni melt was studied by the method of vapour equilibrium in a sealed chamber.At 1530℃ the equilibrium constant of the reaction MgS_(s)=Mg_(Ni)+S_(Ni)and the activity interaction coefficient were determined as K_(MgS)=6.76×10~(-5)and e_S~(Mg)=-9.1.

关键词: Equilibrium constant , null , null , null , null

S49钢轨轧制工艺设计

陈亚平 , 王彦中 , 陶功明

钢铁钒钛 doi:10.3969/j.issn.1004-7638.2002.01.007

结合攀钢轨梁厂工厂特点及S49钢轨断面特点,论述了S49钢轨的轧制工艺设计,并着重阐述了孔型系统的选择和孔型参数的确定,同时设计了导卫装置等.通过孔型系统的优化设计,使S49钢轨一次试轧成功.

关键词: S49钢轨 , 孔型设计 , 导卫装置

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