Evidence for bicarbonate formation on vacuum annealed TiO2(110) resulting from a precursor-mediated interaction between CO2 and H2O

The reaction of CO₂ and H₂O to form bicarbonate (HCO⁻₃) was examined on the nearly perfect and vacuum annealed surfaces of TiO₂(110) with temperature programmed desorption (TPD), static secondary ion mass spectrometry (SSIMS) and high resolution electron energy loss spectrometry (HREELS). The vacuum annealed TiO₂(110) surface possesses oxygen vacancy sites that are manifested in electronic EELS by a loss feature at 0.75 V. These oxygen vacancy sites bind CO₂ only slightly more strongly (TPD peak at 166 K) than do the five-coordinated Ti⁴⁺ sites (TPD peak at 137 K) typical of the nearly perfect TiO₂(110) surface. Vibrational HREELS indicates that CO₂ is linearly bound at the latter sites with a ν_a(OCO) frequency similar to the gas phase value. In contrast, oxygen vacancies dissociate H₂O to bridging OH groups which recombine to liberate H₂O in TPD at 490 K. No evidence for a reaction between CO₂ and H₂O is detected on the nearly perfect surface. In sequentially dosed experiments on the vacuum annealed surface at 110 K, CO₂ adsorption is blocked by the presence of preadsorbed H₂O, adsorbed CO₂ is displaced by postdosed H₂O, and there is little or no evidence for bicarbonate formation in either case. However, when CO₂ and H₂O are simultaneously dosed, a new CO₂ TPD state is observed at 213 K, and the 166 K state associated with CO₂ at the vacancies is absent. SSIMS was used to tentatively assign the 213 K CO₂ TPD state to a bicarbonate species. The 213 K CO₂ TPD state is not formed if the vacancy sites are filled with OH groups prior to simultaneous CO₂+H₂O exposure. Sticking coefficient measurements suggest that CO₂ adsorption at 110 K is precursor-mediated, as is known to be the case for H₂O adsorption on TiO₂(110). A model explaining the circumstances under which the proposed bicarbonate species is formed involves the surface catalyzed conversion of a precursor-bound H₂O–CO₂ van der Waals complex to carbonic acid, which then reacts at unoccupied oxygen vacancies to generate bicarbonate, but falls apart to CO₂ and H₂O in the absence of these sites. This model is consistent with the conditions under which bicarbonate is formed on powdered TiO₂, and is similar to the mechanism by which water catalyzes carbonic acid formation in aqueous solution.     

Radiation induced chemisorption of oxygen on chromia

The effect of nuclear radiation on the chemisorption of oxygen on Cr₂O₃, Cr₂O₃-Al₂O₃ and Cr₂O₃-SnO₂ catalysts has been studied. An iodometric method was used to measure the amount of chemisorbed oxygen; simultaneously the increase in the catalytic activity of the catalyst in the decomposition of H₂O₂ was determined. It was found that the radiation present within a nuclear reactor promotes the chemisorption of oxygen on chromia (either pure or supported on Al₂O₃ or SnO₂) at temperatures at which such a chemisorption does not normally occur. The radiochemisorption of oxygen on chromia increases with the degree of dispersion of chromia on Al₂O₃ or SnO₂ and is accompanied by an increased catalytic activity of this catalyst in the decomposition reaction of H₂O₂. It seems that the radiochemisorption is largely due to the action of γ-rays and fast neutrons on the gas.     

Density functional theory study of formaldehyde adsorption and decomposition on Co-doped defective CeO_2(110) surface

Formaldehyde as an air pollutant to adverse health effects for humanity has been getting attention. The adsorption and dissociation of formaldehyde(HCHO) on the Co_xCe_(1-x_O_(2-δ)(110) surface were investigated by the density functional theory(DFT) calculations. We calculated the oxygen vacancy formation energy as the function of its site around dopant Co in detail. The results showed that Co doping was accompanied by compensating oxygen hole spontaneous formation.The adsorption configurations and bindings of HCHO at different locations on the Co_xCe_(1-x)O_2(110) were presented.Four possible pathways of oxidation of formaldehyde on the catalytic surface were explored. The results suggested that formaldehyde dissociation at different adsorption sites on the doped CeO_2(110) — first forming dioxymethylene(CH_2O_2)intermediate, and then decomposing into H_2O, H_2, CO_2, and CO molecules. It was found that the presence of cobalt and oxygen vacancy significantly prompted the surface activity of CeO_2.     

INS investigation on disaccharide/H2O mixtures

New Inelastic Neutron Scattering findings on homologues disaccharides (C₁₂H₂₂O₁₁)/H₂O mixtures are presented. The comparison among the spectra of trehalose, maltose and sucrose/H₂O mixtures, besides evidencing a different destructuring effectiveness on the H₂O hydrogen bond network, and hence different cryoprotectant properties, shows a higher ‘crystallinity’ degree for the trehalose/H₂O system which accounts for its higher ‘rigidity’. This result justifies the better cryptobiotic action of trehalose in respect to maltose and sucrose.     

TBAB‐CO2水合物形成过程的微观实验

四丁基溴化铵（TBAB）半笼型水合物在二氧化碳（CO₂）捕集和封存技术中具有巨大的发展与应用潜力。由于晶体结构的复杂性,TBAB半笼型水合物的动力学过程尚未得到充分的研究。为了解TBAB半笼型水合物在储气方面的动力学特性,实验采用原位激光拉曼技术和多晶粉末X射线衍射仪（PXRD）对nCO₂·TBAB·26H₂O和nCO₂·TBAB·38H₂O水合物的光谱特征进行了鉴别与分析,利用原位激光拉曼技术考察了CO₂分子分别进入2种晶体结构的动力学过程。研究结果表明,2种晶体结构的拉曼光谱具有较高的相似性,值得注意的是nCO₂·TBAB·26H₂O中位于1 309.5和1 326.9 cm-1的拉曼峰为TBA+阳离子中C-C键的变形振动峰,在nCO₂·TBAB·38H₂O水合物中峰基本不发生改变,但半峰宽降低,峰形也变得相对清晰;同时,nCO₂·TBAB·26H₂O中位于1 446.6和1 458 cm-1的拉曼峰为TBA+阳离子中C-H键的剪切振动峰,在nCO₂·TBAB·38H₂O水合物中分别向左、右两边发生了位移,峰形的重叠度也随之下降。依据上述2处拉曼光谱特征可以对2种晶体结构进行辨别。通过PXRD图谱可以发现2种晶体结构的衍射图谱存在着比较明显的差距。nCO₂·TBAB·26H₂O晶体属于四方晶系,空间群(P4/m),而nCO₂·TBAB·38H₂O属于正交晶系,空间群(Pmma)。图谱中2θ=8.406°和10.941°分别为nCO₂·TBAB·38H₂O的(200)和(220)晶面的特征峰,而2θ=5.976°和6.969°分别为nCO₂·TBAB·26H₂O的(012)和(003)晶面特征峰,可以用来判别样品中水合物的晶体结构。在原位拉曼测量过程中,nCO₂·TBAB·26H₂O和nCO₂·TBAB·38H₂O分别在已经合成好的TBAB·26H₂O和TBAB·38H₂O水合物表面形成。在276 K,2 MPa条件下,气相中的CO₂分子分别进入2种晶体结构中用于储气的512笼形结构,在1 275.4和1 379.3 cm-1处形成特征峰并逐渐增长。实验以2种TBAB水合物位于1 110.3 cm-1的拉曼峰作为参考,比较了CO₂在水合物中的增长速率。研究发现在反应初期的75 min内CO₂在2种水合物中的含量基本保持线性增长且上升速率的差别不大。由于测量点位于水合物表面,受气体在水合物中扩散的阻力较小同时2种TBAB水合物均采用512笼形结构储气导致了储气速率相近。以上的微观晶体结构研究结果对TBAB水合物法捕集和封存CO₂技术应用具有重要的意义。     

Oxygen ion conductivity of yttria-niobia mixed oxide with fluoride related structure

The oxygen ion conductivity of Y₂O₃---Nb₂O₅ with a fluorite-like structure was studied. Substitutional solid solutions of Nb₂ O₅ in Y₂O₃ lattice formed the defect fluorite phase and remarkably enhanced the oxygen ion conductivity. Doping with tetravalent cations, especially Ti⁴⁺ or Ce⁴⁺, in yttria-niobia oxide is effective in enhancing the oxygen ion conductivity. Although the n-type semiconducting property appeared below P_O2 = 10⁻¹⁸ atm at 1243 K, the yttria-niobia mixed oxide doped with Ce⁴⁺, Ti⁴⁺, and Zr⁴⁺ stably exhibited oxygen-ion conduction in the wide range of oxygen partial pressures studied.     

Electrical properties of pure and Li2O-doped CuO/Fe2O3 system precalcined at different temperatures

The electrical properties of pure and Li₂O-doped CuO/Fe₂O₃ solids were investigated. Pure and variously doped solids were subjected to thermal treatment at 1073–1273 K and the amount of dopant was varied between 0.84 to 3.36 mol%. The effect of precalcination temperature and amount of Li₂O added on the electrical conductivity σ, activation energy E_a and dielectric constant * were studied. The variation of ′ and ″ as a function of frequency for pure and variously doped solids precalcined at different temperatures was also investigated. The results obtained were discussed.     

Mixed conductivity in SrCe0.95Yb0.05O3 protonic conductors

The results of electrical conductivity measurements on SrCe_0.95Yb_0.05O₃ under controlled oxygen partial pressure and temperature are presented. A defect model consistent with experimental results is proposed which provides for P_O2^−1/4 dependent n-type, P_o2-independent oxygen ion and P_O2^+1/4 dependent p-type conductivity components. The band gap, reduction, oxidation and ion-migration energies are determined from an analysis of the data in terms of the proposed defect model. These results suggest that some earlier data interpreted in terms of protonic conduction may require re-evaluation.     

Redox reaction kinetics of UO2+x

Oxidation and reduction kinetics of UO_2+x was investigated in CO₂/CO gas mixtures at elevated temperatures of 1000°C to 1300°C by monitoring the electrical conductivity relaxation induced by an abrupt change of ambient oxygen partial pressure. By fitting the experimental relaxation data to theoretical equations, the oxidation and reduction kinetics was found to be controlled mostly by the surface reaction step in the ranges of oxygen partial pressure and temperature examined and the surface reaction rate constants were derived therefrom.     

The role of Bi2O3 as a network modifier and a network former in xBi2O3 · (1 − x)LiBO2 glass system

The effect of Bi₂O₃ on the glass transition temperature, electrical conductivity and structure of LiBO₂ glass has been investigated. T_g vs. composition curve shows three different linear regions, while there is an overall decrease in T_g with the increase in Bi₂O₃ content. The slope of these three straight lines is in a decreasing order. These results are interpreted in terms of the increase in the number of non-bridging oxygen atoms, substitution of Bi-O bond in place of B-O bond and change in Li⁺ ion concentration. The conductivity vs. composition curve exhibits two maxima which are interpreted in terms of the structural modification effect of Bi₂O₃ on LiBO₂ network and mixed-former effect, respectively. Results obtained from the XPS studies of the samples of composition x 0.005, have shown that the number of non-bridging oxygen atoms from B-O bond increases with the increase in Bi₂O₃ content. It has a maximum value at x = 0.003 where the conductivity has also exhibited a maximum value. Further increase of Bi₂O₃ content causes decrease in it. For higher Bi₂O₃ content (x * > 0.005), O 1s spectra of Bi₂O₃ has been separated out from that of Bi₂O₃. Bismuth ions have been substituted for boron ions as network former ions.     

Detection of small N2O concentrations using a frequency doubled CO2 laser

A reliable procedure for remote high-accuracy laser detection of N₂O as one of the principal destroyers of the protective ozone layer of the Earth has been developed. The procedure is based on using a CO₂-laser system emitting efficiently in the 4.5 μm range. In this case lasing from isotopic modification ¹²C¹⁸O₂ of carbon dioxide with its subsequent frequency doubling by a nonlinear crystal is used. With the object of reducing the price the composition of the active medium (both for TEA laser and low-pressure longitudinal-discharge-excitation laser) has been optimized. New high-efficiency intracavity frequency doubling schemes based on nonlinear AgGaSe₂ crystals have been developed for CO₂-lasers of both types. Low concentrations of N₂O and concentrations of the principal background gases CO and H₂O have been measured under real atmosphere conditions with the aid of the lidar complex built around these lasers.     

The stability of SiC coating and SiO2/SiC multilayer on the surface of graphite for HTGRs at normal service condition

The stability of SiC coating in helium with a low concentration of O₂, CO₂, and H₂O is a key factor for their application in improvement of oxidation resistance of graphite for high temperature gas-cooled reactors (HTGRs). Through thermodynamic analysis, it is found that the influence factor controlling the critical temperature of passive oxidation for SiC is partial pressure of active gas in helium; the critical temperature of passive oxidation for SiC increases with the partial pressure of O₂, CO₂, and H₂O, SiC is prone to undergo active oxidation in He–CO₂ and He–H₂O system. SiO₂/SiC multilayer coating can improve the oxidation resistance of graphite at higher temperature than SiC coating does under normal operation condition for HTGRs.     

K2O·CaO·4B2O3·12H2O∶Nd3+的合成及发光性能

以CaCl2、K2B4O7和Nd2O3为原料,采用易于工业化、无污染的水溶液法反应合成碱-碱土金属硼酸盐K2O·CaO·4B2O3·12H2O∶Nd3+晶体,利用X射线衍射、红外光谱、扫描电镜、荧光分光度计等现代分析测试手段,对所合成晶体进行了分析和表征.结果表明,所制备的K2O·CaO·4B2O3·12H2O∶Nd3...     

Sol–gel preparation and characterisation of dense proton conducting Sr3CaZr0.5Ta1.5O8.75 thin films

Dense proton conducting Sr₃CaZr_0.5Ta_1.5O_8.75 films (1.25 μm, with grain size in the 200–400 nm range) were deposited, using the sol–gel method, on Al₂O₃–8%Y₂O₃-stabilised ZrO₂ plates. The obtained gels were characterised by differential and thermogravimetric thermal analysis (DTA–TGA), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results of a study of the structural and electrical properties of Sr₃CaZr_0.5Ta_1.5O_8.75 films deposited on the mentioned substrates are presented herein. The structural data for the gels and films were compared with those obtained for the same material prepared by solid state synthesis. Electrical properties of the sandwich-type structure were investigated by AC impedance conductivity measurements at different temperatures, in both dry and wet 5% H₂/Ar atmospheres. A careful analysis of the impedance spectra for this complex structure was performed, using a model with a series of five electrical circuits, having resistance and capacitance coupled in parallel. The specific responses observed in the impedance spectra were assigned to the corresponding substrate and layer contributions. A significant improvement, by an order of magnitude, in the electrode response was observed in the presence of the interleaving Sr₃CaZr_0.5Ta_1.5O_8.75 proton conducting layer, between the electrode and electrolyte. This enhancement is lost at temperatures above that at which the Sr₃CaZr_0.5Ta_1.5O_8.75 dehydrates and its protonic conductivity diminishes. Considering the structural and electrical characterisation results, these Sr₃CaZr_0.5Ta_1.5O_8.75 sol–gel derived films have a potential use for proton conducting electrolyte or intermediate layer in fuel cells.     

光学碱度对Tb3+掺杂Bi2O3-B2O3玻璃发光性能的影响

采用熔融法制备了Tb³⁺掺杂的Bi₂O₃-B₂O₃系统玻璃,使用激发、发射及拉曼光谱分析了光学碱度与玻璃结构及发光性能的关系,同时绘制了Tb³⁺、Bi³⁺和Bi²⁺的能级图。研究结果表明：Tb³⁺掺杂的Bi₂O₃-B₂O₃玻璃由[BO₃]、[BiO₃]、[BO₄]及[BiO₆]共同组成,且随着光学碱度由0.63增加到0.93,玻璃的结构逐渐疏松。高的光学碱度使部分Bi³⁺变为Bi²⁺,发出571 nm（²P_3/2（2）→²P_1/2）的光,Bi³⁺→Tb³⁺的能量降低。在光学碱度及Tb³⁺、Bi³⁺和Bi²⁺离子的共同作用下,随着光学碱度的提高,玻璃的发光颜色由黄绿色变为白色。     

Cu_2O/ZnO氧化物异质结太阳电池的研究进展

介绍了近年来低成本Cu_2O/ZnO氧化物异质结太阳电池方面的研究进展.应用于光伏器件的吸收层材料Cu_2O是直接带隙半导体材料,天然呈现p型;其原材料丰富,且对环境友好.Cu_2O/ZnO异质结太阳电池结构主要有平面结构和纳米线/纳米棒结构.纳米结构的Cu_2O太阳电池提高了器件的电荷收集作用;通过热氧化Cu片技术获得的具有大晶粒尺寸平面结构Cu_2O吸收层在Cu_2O/ZnO太阳电池应用中展现出了高质量特性.界面缓冲层(如i-ZnO,a-ZTO,Ga_2O_3等)和背表面电场(如p~+-Cu_2O层等)可有效地提高界面处能级匹配和增强载流子输运.10 nm厚度的Ga_2O_3提供了近理想的导带失配,减少了界面复合;Ga_2O_3非常适合作为界面层,其能够有效地提高Cu_2O基太阳电池的开路电压V_(oc)(可达到1.2 V)和光电转换效率.p~+-Cu_2O(如Cu_2O:N和Cu_2O:Na)能够减少器件中背接触电阻和形成电子反射的背表面电场(抑制电子在界面处复合).利用p型Na掺杂Cu_2O(Cu_2O:Na)作为吸收层和Zn_(1-x)Ge_x-O作为n型缓冲层,Cu_2O异质结太阳电池(器件结构:MgF_2/ZnO:Al/Zn_(0.38)Ge_(0.62)-O/Cu_2O:Na)光电转换效率达8.1%.氧化物异质结太阳电池在光伏领域展现出极大的发展潜力.     

Germanium and iron co-substituted SrCoO2.5+δ as oxygen permeable membrane

Germanium and iron co-doped SrCoO_2.5+δ was investigated in terms of phase stability, oxygen permeability and electrical conductivity. The favorable high-temperature cubic structure of SrCoO_2.5+δ was stabilized to lower temperatures by co-doping Ge (10 mol%) and Fe (10 mol%) that substituted for Co, which however could not be achieved by doping Ge (20 mol%) alone. In contrast to SrCo_0.8Ge_0.2O_2.5+δ sample which showed a sharp decrease in oxygen permeability at temperature of 875 °C upon cooling, SrGe_0.1Co_0.8Fe_0.1O_3−δ sample remained well-permeable to oxygen at lower temperatures down to at least 820 °C; an abrupt change in electrical conductivity in SrCo_0.8Ge_0.2O_2.5+δ also occurred accompanying the phase transition. The oxygen permeation flux for SrGe_0.1Co_0.8Fe_0.1O_3−δ increased significantly with the decrease of the membrane thickness, indicating the transport of oxygen ions in the bulk of the membrane as the rate-limiting step.     

Surface interaction between H2 and CO2 over silicalite-supported platinum

Infrared spectroscopic evidence is presented for the formation of linearly bonded CO species, as a result of surface interaction between H₂ and CO₂ at room temperature over silicalite-supported Pt. Comparison with direct CO adsorption results suggests that the active sites for this CO₂ reaction are the corner or step sites on platinum particles. The CO formed on these active sites then migrates to other sites on the surface of Pt particles. Co-adsorbed hydrogen and water make the linearly bonded CO species more strongly adsorbed on Pt particles. However, exposure to oxygen or air at room temperature effectively removes these CO species.     

BaO-Li2O-B2O3三元系中BaB2O4-Li2B2O4和BaB2O4-Li2O截面相平衡关系的研究

本文用X射线和差热分析方法对BaO-Li₂O-B₂O₃三元系中的两个截面:BaB₂O₄-Li₂B₂O₄和BaB₂O₄-Li₂O作了研究。在BaB₂O₄-Li₂B₂O₄赝二元系中发现了一个新的化合物4BaB₂O₄·Li₂B₂O₄。化合物在930±3℃由包晶反应形成,并与Li₂B₂O₄形成共晶反应。共晶温度为797±3℃,共晶点组分为79mol％Li₂B₂O₄。在BaB₂O₄-Li₂O截面中也存在化合物4BaB₂O₄·Li₂B₂O₄,其包晶反应温度从930±3℃随Li₂O含量增加下降到908±3℃。在组分60mol％Li₂O处形成另一个新的化合物2BaB₂O₄·3Li₂O。该化合物在630±3℃也是由包晶反应形成,并与Li₂O和Li₂CO₃分别形成共晶反应,共晶温度分别为400±3℃和612±3℃。在BaB₂O₄-Li₂B₂O₄和BaB₂O₄-Li₂O体系中都没有观察到固溶体。用计算机程序分别对化合物4BaB₂O₄·Li₂B₂O₄和2BaB₂O₄·3Li₂O的X射线粉末衍射图案进行了指标化,其结果:4BaB₂O₄·Li₂B₂O₄的空间群为Pmma,a=13.033?,b=14.630?,c=4.247?,每个单胞包含两个化合式单位;2BaB₂O₄·3Li₂O的空间群为Pmmm,a=4.814?,b=9.897?,c=11.523?,每个单胞也含有两个化合式单位。 关键词：