添加稀土Gd的氧化锆的物相分析

以硝酸锆、硝酸钆和柠檬酸为原料,按n(Gd)∶n(Zr)分别为1∶993、∶97、5∶95、8∶92和10∶90的配比在1 200℃煅烧6 h制备了稀土Gd掺杂ZrO2试样,以研究Gd与ZrO2的化学相容性;进而按n(Gd2Zr2O7)∶n(ZrO2)分别为1∶10、1∶8、1∶41、∶21、∶1、4∶1和8∶1的配比于1 200℃煅烧6 h原位合成了Gd2Zr2O7-ZrO2复合材料。采用XRD和拉曼光谱研究了稀土Gd掺杂ZrO2和Gd2Zr2O7-ZrO2复合材料的物相组成和结构。结果表明:稀土Gd容易进入ZrO2晶格形成固溶体,当稀土Gd掺杂量较少时,随着稀土Gd掺杂量的增加,m-ZrO2逐渐转变为t-ZrO2;当稀土Gd添加量较多时,随着Gd量的增加,逐渐原位生成了萤石结构的稀土锆酸盐Gd2Zr2O7,从而合成了由Gd2Zr2O7和t-ZrO2构成的Gd2Zr2O7-ZrO2复合材料。     

（Y2O3·CeO2）-ZrO2纳米粉的制备

用化学沉淀法合成了Y2O3、CeO2共掺杂的ZrO2纳米粉。通过XRD、TEM和粒度分布仪等检测手段对产品进行了表征,结果表明:Y2O3含量为2mol%,CeO2含量为9mol%时,在550℃得到了全稳定立方相ZrO2,粒径约为58.8nm。     

掺杂Eu3+或Tb3+的(Gd,Lu)2O3粉体的发光性能

采用高温固相法在空气中合成了(Od,Lu)2O3,(Gd,Lu)2O3:Eu3+和(Gd,Lu)2O3:Tb3+系粉体.研究了二元系中Lu2O3的摩尔分数对抑制Gd2O3高温相变、粉体的发光性质和光谱性质的影响.结果表明:在(Gd,Lu)2O3系粉体中,当Lu2O3的摩尔分数(下同)大于40%时,能在煅烧温度不低于1 700℃情况下,抑制Gd2O3的相变得到利于制备透明陶瓷的立方相结构.而且随着Lu3+离子的浓度增加,先后观察到红移和蓝移现象;在(Gd,Lu)203:Eu3+系粉体中,粉体的发光强度随着Lu3+掺杂量增加而减小,Eu3+的最佳掺杂量为7%;在(Gd,Lu)2O3:Tb3+系粉体中,Tb3+离子的最佳掺量为1%.     

CeO2夹层在YSZ基SOFC中的研究进展

回顾了Y2O3、Sm2O3和Gd2O3掺杂的CeO2夹层（YDC、SDC和GDC）在Y2O3稳定的ZrO2（YSZ）基SOFC中的发展历史以及目前发展状况,分析了粉体的制备方法、夹层的沉积工艺、陶瓷烧结工艺对CeO2夹层性能的影响。从材料的化学相容性和热膨胀匹配等方面阐述了制备CeO2夹层的目的,对CeO2夹层大大提高电极性能进行了详尽的机理分析。指明了CeO2夹层对SOFC的重要作用和发展前景。     

添加ZrO_2对Ta_2O_5陶瓷结构与性能的影响

以ZrO2和Ta2O5粉体为原料,采用固相反应法制备了ZrO2掺杂Ta2O5陶瓷。研究了ZrO2掺杂对Ta2O5陶瓷的相组成、微观结构、抗弯强度、热膨胀系数和抗热震性能的影响。结果表明:ZrO2掺杂可在烧成过程中抑制β-Ta2O5相向α-Ta2O5相的转变,5%(质量分数,下同)ZrO2掺杂Ta2O5陶瓷为β-Ta2O5单相固溶体。3%ZrO2掺杂,显著抑制了Ta2O5陶瓷高温烧结过程中的晶粒长大,避免了晶界开裂;掺杂量达到5%以上时,可显著促进Ta2O5陶瓷的烧结致密化。5%ZrO2掺杂的Ta2O5陶瓷表现出较高的抗弯强度(74.5MPa),低的热膨胀系数(1.96×10-6/℃)和良好的抗热震性能。     

Gd~(3+)和Zn~(2+)共掺杂二氧化钛介孔粉末的制备及光催化性能

采用溶胶-凝胶法制备了Gd3+和Zn2+共掺杂Ti O2粉末。研究了Gd3+和Zn2+掺杂对样品的相组成、表面形貌和光催化活性的影响;以亚甲基蓝为目标降解物评价了其光催化活性。结果表明:制备的样品为锐钛矿相并具有良好的介孔结构。Gd3+和Zn2+在抑制光生电子与空穴的复合起到不同的作用,Gd3+起到光生电子陷阱的作用,Zn2+可以在起到光生空穴陷阱的作用,Gd3+和Zn2+共同作用可以显著降低电子和空穴的复合速率,进而增大Ti O2的光催化活性。当Gd3+的掺杂量为0.5%、Zn2+的掺杂量为0.3%时,Ti O2粉末的光催化活性最高,经过40 min光催化降解亚甲基蓝溶液,降解率达到99.5%,比单掺杂0.5%Gd3+的Ti O2粉末降解率提高了11.5%,比单掺杂0.3%Zn2+的Ti O2粉末降解率提高了9.3%。     

含稀土ZnO-B2O3-SiO2玻璃的化学稳定性

为了探索稀土氧化物掺杂对硼硅酸盐玻璃化学稳定性的影响,利用熔融冷却法制备了掺杂Nd2O3、Gd2O3和Y2O3的ZnO-B2O3-SiO2系玻璃.在一定的条件下,对玻璃在去离子水、酸、碱液态侵蚀介质中的腐蚀行为进行了研究.利用扫描电镜和能谱分析对腐蚀后的玻璃样品表面形貌和成分变化进行了表征,对酸性侵蚀介质中出现的白色沉淀进行了X射线物性分析,同时利用电感耦合等离子光谱仪测定了去离子水中浸出离子的浓度.结果表明:该系统玻璃的化学稳定性顺序为:耐酸性＜耐碱性＜耐水性.稀土氧化物的添加降低了玻璃侵蚀过程中的质量损失,减轻了玻璃的腐蚀程度和抑制了各组分的浸出量.Y2O3、Gd2O3和Nd2O3的添加使得该玻璃在去离子水中钠离子的浸出量从148.703 μg/cm2分别降低到43.751,63.984和138.828 μg/cm2.Nd2O3、Gd2O3和Y2O3掺杂对硼硅酸盐玻璃化学稳定性的改善作用顺序为Y2O3＞ Gd2O3＞ Nd2O3.     

Gd_2O_3掺杂对BaTiO_3陶瓷电性能的影响

采用溶胶-凝胶法制备了掺杂不同量Gd2O3(分别为0 001、0 002、0 003、0 005、0 007mol mol)的BaTiO3陶瓷,并对其电性能进行了研究。结果表明:Gd2O3掺杂使BaTiO3陶瓷的电阻率明显下降,当添加量为0 002mol mol时,电阻率最小,为1 27×105Ω·m;晶粒电阻随着温度的变化,呈现NTC效应,而晶界电阻随着温度的变化,呈现PTC效应,而且晶界电阻远远大于晶粒电阻,说明Gd2O3掺杂BaTiO3陶瓷的PTC效应是一种晶界效应;Gd2O3掺杂使BaTiO3陶瓷的介电常数和介电损耗在低频时明显增大,在高频时又明显降低。     

Sm2O3掺杂的Bi2O3-ZnO-Nb2O5基陶瓷的烧结特性与介电性能

用传统的固相法合成了Sm2O3掺杂的Bi2O3-ZnO-Nb2O5(BZN)基陶瓷(Bi1.5-xSmxZn0.5)(Zn0.5Nb1.5)O7(0≤x≤0.6,BSZN),通过XRD、AV2782阻抗分析仪等测试手段对其烧结行为、相结构及介电性能进行了系统研究.结果表明纯BZN陶瓷的结构为立方焦绿石单相;当Sm2O3掺杂量较少(0＜x≤0.5)时,样品的相结构仍然保持立方焦绿石单相;随着Sm2O3掺杂量的进一步增加(x≥0.6),样品出现其它相.同时,试样的介电性能随结构的变化而呈现有规律的变化.     

氧化锆基复合电解质材料研究

用柠檬酸溶胶-凝胶法制备了Bi2O3p/ZrO2复合电解质材料,研究了Y元素不同掺量对电解质材料的物相,密度和导电率的影响.结果表明掺Y元素可促使立方相ZrO2稳定、增加试样的密度和电导率.当Y元素掺量为20mol%时,试样的物相为立方相ZrO2,试样的密度达5.48g/cm3,其在700℃的电导率为2.85×10-3...     

Photocatalytic activity of Cu2O/TiO2, Bi2O3/TiO2 and ZnMn2O4/TiO2 heterojunctions

Cu₂O/TiO₂, Bi₂O₃/TiO₂ and ZnMn₂O₄/TiO₂ heterojunctions were studied for potential applications in water decontamination technology and their capacity to induce an oxidation process under VIS light. UV–vis spectroscopy analysis showed that the junctions-based Cu₂O, Bi₂O₃ and ZnMn₂O₄ are able to absorb a large part of visible light (respectively, up to 650, 460 and 1000 nm). This fact was confirmed in the case of Cu₂O/TiO₂ and Bi₂O₃/TiO₂ by photocatalytic experiments performed under visible light. A part of the charge recombination that can take place when both semiconductors are excited was observed when a photocatalytic experiment was performed under UV–vis illumination. Orange II, 4-hydroxybenzoic and benzamide were used as pollutants in the experiment. Photoactivity of the junctions was found to be strongly dependent on the substrate. The different phenomena that were observed in each case are discussed.     

Properties of char particles obtained under O2/N2 and O2/CO2 combustion environments

Pulverized coal combustion in O₂/N₂ and O₂/CO₂ environments was investigated with a drop tube furnace. Results present that the reaction rate and burn-out degree of O₂/CO₂ chars (obtained in O₂/CO₂ environments) are lower than that of O₂/N₂ chars (obtained in O₂/N₂ environments) under the same experimental condition. It indicates that a higher O₂ concentration in O₂/CO₂ environment is needed to achieve the similar combustion characteristic to that in O₂/N₂ environment. The main differences between O₂/N₂ and O₂/CO₂ chars rely on the pore structure determined by N₂ adsorption and chemical structure measured by FT-IR. For O₂/CO₂ char, the surface is thick and the pores are compact which contribute to the fragmentation reduction of particles burning in O₂/CO₂ environment. The organic functional group elimination rate from the surface of O₂/CO₂ chars is slower or delayed. The present research results might have important implications for further understanding the intrinsic kinetics of pulverized coal combustion in O₂/CO₂ environment.     

ZrB2质与TiB2质耐火材料

介绍了ZrB     

ZrO2/SiO2- and La2O3/Al2O3-supported platinum catalysts for CH4/CO2 reforming

Surface-phase ZrO₂ on SiO₂ (SZrOs) and surface-phase La₂O₃ on Al₂O₃ (SLaOs) were prepared with various loadings of ZrO₂ and La₂O₃, characterized and used as supports for preparing Pt/SZrOs and Pt/SLaOs catalysts. CH₄/CO₂ reforming over the Pt/SZrOs and Pt/SLaOs catalysts was examined and compared with Pt/Al₂O₃ and Pt/SiO₂ catalysts. CO₂ or CH₄ pulse reaction/adsorption analysis was employed to elucidate the effects of these surface-phase oxides.

The zirconia can be homogeneously dispersed on SiO₂ to form a stable surface-phase oxide. The lanthana cannot be spread well on Al₂O₃, but it forms a stable amorphous oxide with Al₂O₃. The Pt/SZrOs and Pt/SLaOs catalysts showed higher steady activity than did Pt/SiO₂ and Pt/Al₂O₃ by a factor of three to four. The Pt/SZrOs and Pt/SLaOs catalysts were also much more stable than the Pt/SiO₂ and Pt/Al₂O₃ catalysts for long stream time and for reforming temperatures above 700 °C. These findings were attributed to the activation of CO₂ adsorbed on the basic sites of SZrOs and SLaOs.     

Modeling char conversion under suspension fired conditions in O2/N2 and O2/CO2 atmospheres

The aim of this investigation has been to model combustion under suspension fired conditions in O₂/N₂ and O₂/CO₂ mixtures. Experiments used for model validation have been carried out in an electrically heated Entrained Flow Reactor (EFR) at temperatures between 1173 K and 1673 K with inlet O₂ concentrations between 5 and 28 vol.%. The COal COmbustion MOdel, COCOMO, includes the three char morphologies: cenospheric char, network char and dense char each divided between six discrete particle sizes. Both combustion and gasification with CO₂ are accounted for and reaction rates include thermal char deactivation, which was found to be important for combustion at high reactor temperatures and high O₂ concentrations. COCOMO show in general good agreement with experimental char conversion profiles at conditions covering zone I-III. From the experimental profiles no effect of CO₂ gasification on char conversion has been found. COCOMO does however suggest that CO₂ gasification in oxy-fuel combustion at low O₂ concentrations can account for as much as 70% of the overall char consumption rate during combustion in zone III.     

Partial oxidation of methane to CO and H2 over nickel and/or cobalt containing ZrO2, ThO2, UO2, TiO2 and SiO2 catalysts

The influence of different metal oxide supports (i.e. ZrO₂, ThO₂, UO₂, TiO₂ and SiO₂) on the performance of Ni- and/or Co-containing catalysts [Ni and/or Co/MO₂ mole ratio (where M=Zr, Th, U, Ti or Si)=1.0] in the oxidative methane-to-syngas conversion at very low contact time (GHSV=5.2×10⁵ cm³ g⁻¹ h⁻¹ at STP) was investigated. The nickel-containing ZrO₂, ThO₂ and UO₂ catalysts (with or without pre-reduction by hydrogen at 500°C) showed good performance in the process; the order of their performance is NiO–ThO₂>NiO–UO₂>NiO–ZrO₂. The NiO–TiO₂ showed appreciable catalytic activity only after its reduction at 800°C. However, this catalyst and the NiO–SiO₂ catalyst showed poor performance in the process. These two catalysts are also deactivated very fast, mostly because of sintering of Ni and/or formation of catalytically inactive binary metal oxide phases by solid–solid reaction at the high catalyst calcination and/or catalytic reaction temperature. Although the Ni-containing ThO₂, UO₂ and ZrO₂ catalysts showed good performance, carbon deposition on them during the process is fast. However, because of the addition of cobalt to these catalysts (with Co/Ni=1.0), the rate of carbon deposition on them in the process is drastically reduced. This Co addition however resulted in a significant decrease in both the conversion and selectivity; the decrease in the selectivity was small.     

Adsorption of CO2 from dry gases on MCM-41 silica at ambient temperature and high pressure. 2: Adsorption of CO2/N2, CO2/CH4 and CO2/H2 binary mixtures

Adsorption equilibrium capacity of CO₂, CH₄, N₂, H₂ and O₂ on periodic mesoporous MCM-41 silica was measured gravimetrically at room temperature and pressure up to 25 bar. The ideal adsorption solution theory (IAST) was validated and used for the prediction of CO₂/N₂, CO₂/CH₄, CO₂/H₂ binary mixture adsorption equilibria on MCM-41 using single components adsorption data. In all cases, MCM-41 showed preferential CO₂ adsorption in comparison to the other gases, in agreement with CO₂/N₂, CO₂/CH₄, CO₂/H₂ selectivity determined using IAST. In comparison to well known benchmark CO₂ adsorbents like activated carbons, zeolites and metal-organic frameworks (MOFs), MCM-41 showed good CO₂ separation performances from CO₂/N₂, CO₂/CH₄ and CO₂/H₂ binary mixtures at high pressure, via pressure swing adsorption by utilizing a medium pressure desorption process (PSA-H/M). The working CO₂ capacity of MCM-41 in the aforementioned binary mixtures using PSA-H/M is generally higher than 13X zeolite and comparable to different activated carbons.     

Kinetics of CO and H2 oxidation over CuO-CeO2 catalyst in H2 mixtures with CO2 and H2O

The kinetics of CO and H₂ oxidation over a CuO-CeO₂ catalyst were simultaneously investigated under reaction conditions of preferential CO oxidation (PROX) in hydrogen-rich mixtures with CO₂ and H₂O. An integral packed-bed tubular reactor was used to produce kinetic data for power-law kinetics for both CO and H₂ oxidations. The experimental results showed that the CO oxidation rate was essentially independent of H₂ and O₂ concentrations, while the H₂ oxidation rate was practically independent of CO and O₂ concentrations. In the CO oxidation, the reaction orders were 0.91, −0.37 and −0.62 with respect to the partial pressure of CO, CO₂ and H₂O, respectively. In the H₂ oxidation, the orders were 1.0, −0.48 and −0.69 with respect to the partial pressure of H₂, CO₂ and H₂O, respectively. The activation energies of the CO oxidation and the H₂ oxidation were 94.4 and 142 kJ/mol, respectively. The rate expressions of both oxidations were able to predict the performance of the PROX reactor with accuracy. The independence between the CO and the H₂ oxidation suggested different sites for CO and H₂ adsorption on the CuO-CeO₂ catalyst. Based on the results, we proposed a new reaction model for the preferential CO oxidation. The model assumes that CO adsorbs selectively on the Cu⁺ sites; H₂ dissociates and adsorbs on the Cu⁰ sites; the adsorbed species migrates to the interface between the copper components and the ceria support, and reacts there with the oxygen supplied by the ceria support; and the oxygen deficiency on the support is replenished by the oxygen in the reaction mixture.     

New acrylic monolithic carbon molecular sieves for O2/N2 and CO2/CH4 separations

The modification of activated carbon fibres prepared from a commercial textile acrylic fibre into materials with monolithic shape using phenolic resin as binder was studied. The molecular sieving properties for the gas separations CO₂/CH₄ and O₂/N₂ were evaluated from the gas uptake volume and selectivity at 100 s contact time taken from the kinetic adsorption curves of the individual gases. The pseudo-first order rate constant was also determined by the application of the LDF model. The samples produced show high CO₂ and O₂ rates of adsorption, in the range 3-35 × 10⁻³ s⁻¹, and in most cases null or very low adsorption of CH₄ and N₂ which make them very promising samples to use in PSA systems, or similar. Although the selectivity was very high, the adsorption capacity was low in certain cases. However, the gas uptake in two samples reached 23 cm³ g⁻¹ for CO₂ and 5 cm³ g⁻¹ for O₂, which can be considered very good. The materials were heat-treated using a microwave furnace, which is a novel and more economic method, when compared with conventional furnaces, to improve the molecular sieves properties.     

Gas-solid oxidations with RuO2---TiO2 and RuO2---SiO2 membranes

The activity of the RuO₂---TiO₂ and RuO₂---SiO₂ membrane catalysts in oxidation with air of the isopropylic alcohol was determined at temperatures ranging from 40 to 120°C. The RuO₂---TiO₂ and RuO₂---SiO₂ membranes were prepared by the sol-gel process and supported on microporous glass membranes. The catalysts were characterized by scanning electron microscopy, IR spectroscopy and X-ray diffraction studies.