ZrO2包覆对层状氧化物正极材料储钠性能的改善

层状氧化物正极材料具有良好的结构稳定性和较高的充放电比容量,是一类理想的钠离子电池正极材料。本工作研究了层状氧化物正极材料NaNi1/3Fe1/3Mn1/3O2表面修饰对其电化学性能的影响,采用固相球磨法在正极材料表面包覆一层纳米ZrO2,采用形貌、结构、电化学方法等研究了包覆后性能改进机理。研究结果表明,ZrO2在NaNi1/3Fe1/3Mn1/3O2表面形成一层惰性保护层,有效隔开了电解液与正极材料的接触,缓解了电解液的分解速度,抑制了金属离子的溶出速度,从而显著改善了电池的循环性能以及高温性能。在ZrO2包覆修饰后,55℃下正极材料相比于未包覆的正极材料有明显提升,100次循环后容量保持率达到83.6%,高于未包覆的75.2%。此外,包覆后的NaNi1/3Fe1/3Mn1/3O2正极材料在空气环境存储后,稳定性得到明显提高。     

On the Modification of Hydration Resistance of CaO with ZrO2 Additive

Various ZrO₂/CaO samples were fabricated by cold isostatic pressing and sintered at 1750°C for 4 h. It was observed that the sample with 12% ZrO₂ additive possessed the good hydration resistance and had the lowest apparent porosity of about 0.75%; its weight additive stored after 56 days was less than 0.6 wt%, and it contributed to the occurrence of CaZrO₃ on the surface of CaO. The CaO crucible with 12 mol% ZrO₂ additive did not react with titanium melt during melting TiNi alloy. This provides a support for searching a new refractory with the good hydration resistance for induction melting titanium alloys.     

B位前躯体法制备PZT/ZrO2纳米复相压电陶瓷的力学性能研究

采用改进的聚合物法制备B位前驱体PZT/ZrO2纳米复相陶瓷.采用TEM观察到马氏体相变和热失配产生的应力条纹和应力斑,发现ZrO2粒子截断电畴和使电畴弯曲的现象.应力场有效吸收裂纹扩展能量,加之ZrO2粒子强化基体晶界,PZT/ZrO2纳米复相陶瓷得到了强韧化.SEM分析显示陶瓷断裂模式随ZrO2加入向穿晶断裂模式转变.抗弯强度和断裂韧性随Zr2加入量增加明显提高,可达141.6 MPa和2.3 MPa·m1/2.     

Pt-SO_4~(2-)/ZrO_2-Al_2O_3催化剂的制备及其催化正戊烷异构化性能

制备了Pt-SO42-/ZrO2-A l2O3固体超强酸催化剂,采用XRD,TG-DTA,FT-IR,TPR,SEM,BET,ICP等表征方法对催化剂进行了表征。以正戊烷异构化反应为探针,在高压固定床-色谱联合装置上,评价了催化剂的活性,考察了空速v空、反应温度t、反应压力p和氢与正戊烷摩尔比对正戊烷异构化反应的影响。在t=200℃,p=2.0 MPa,v空=1.5 h-1,n(氢)/n(正戊烷)=4∶1的条件下反应时,正戊烷转化率为72.9%,异戊烷收率为67.6%,异戊烷选择性为92.8%,液收率为94.8%。     

固体酸SO42-/ZrO2-Fe2O3催化合成L-乳酸酯的研究

将固体酸SO42-/ZrO2-Fe2O3用于催化L-乳酸和2-异亚丙基氨基氧基乙醇的酯化反应.确定了最佳反应条件:带水剂为甲苯,醇酸摩尔比为3.5:1,催化剂用量为L-乳酸质量的6%,反应时间为8 h,在此条件下酯化率可达62.5%.     

醇醛物质的量比对不饱和醛催化氢转移反应的影响

探讨了ZrO₂/SiO₂催化柠檬醛和异丙醇的氢转移反应醇醛物质的量比对反应速率的影响。结果表明,实验条件下,反应混合物的沸点随醇醛物质的量比的增大而降低;柠檬醛转化率和目标产物选择性明显受醇醛物质的量比的影响,醇醛物质的量比变化导致混合物沸点的改变可能是影响反应速率的主要因素。研究条件下,反应最适宜的醇醛物质的量比为5,表观活化能为100.5 kJ·mol^-1.     

The influence of sulphur on the processing of zirconia based ceramics

Yttria stabilized zirconia powders were synthesized by the coprecipitation route. Zirconium oxychloride containing sulphur as contamination and analytical grade yttrium chloride were used as raw materials. Powders were calcined at temperatures between 600 and 1100 °C and ground by ball and attrition milling. The ceramic bodies were sintered at 1350 and 1550 °C for 1 h and the apparent density was measured. In the present work it is shown that the most deleterious effect of sulphur was observed in 3 mol% yttria stabilized zirconia, especially when the pellets were obtained at high pressures and sintered at 1500 °C. The elimination of sulphur at higher calcination temperatures minimizes the effects caused by this contamination, despite the reduction of powder surface area. The best processing condition to obtain high density zirconia ceramics from powders contaminated with sulphur was established.     

The catalytic activity of FeOx/ZrO2 for the abatement of NO with propene in the presence of O2

FeO_x/ZrO₂ samples, prepared by impregnation with Fe(NO₃)₃, were characterised by means of DRS, XRD, FTIR, redox cycles and volumetric CO adsorption. Volumetric CO adsorption, combined with FTIR, showed that 45% of iron in the sample containing 2.8 Fe atoms nm⁻² was capable of forming iron carbonyls. DRS evidenced Fe₂O₃ on samples with Fe-content≥2.8 atoms nm⁻². The selective catalytic reduction of NO with C₃H₆ in the presence of O₂ was studied with a reactant mixture containing NO=4000 ppm, C₃H₆=4000 ppm, O₂=2%. The dependence on iron-content suggests that only isolated iron, prevailing in dilute FeO_x/ZrO₂, is active for NO reduction, whereas iron on the surface of small oxide particles, prevailing in concentrated FeO_x/ZrO₂, is active for C₃H₆ combustion.     

NOX removal in excess oxygen by plasma-enhanced selective catalytic reduction

In the off-gases of internal combustion engines running with oxygen excess, non-thermal plasmas (NTPs) have an oxidative potential, which results in an effective conversion of NO to NO₂. In combination with appropriate catalysts and ammonia (NH₃-SCR) or hydrocarbons (HC-SCR) as a reducing agent, this can be utilized to reduce nitric oxides (NO and NO₂) synergistically to molecular nitrogen.

The combination of SCR and cold plasma enhanced the overall reaction rate and allowed an effective removal of NO_X at low temperatures. Using NH₃ as a reducing agent, NO_X was converted to N₂ on zeolites or NH₃-SCR catalysts like V₂O₅–WO₃/TiO₂ at temperatures as low as 100–200 °C. Significant synergetic effects of plasma and catalyst treatment were observed both for NH₃ stored by ion exchange on the zeolite and for continuous NH₃ supply.

Certain modifications of Al₂O₃ and ZrO₂ have been found to be effective as catalysts in the plasma-assisted HC-SCR in oxygen excess. With an energy supply of about 30 eV/NO-molecule, 500 ppm NO was reduced by more than half at a temperature of 300 °C and a space velocity of 20 000 h⁻¹ at the catalyst. The synergistic combinations of NTP and both NH₃- and HC-SCR have been verified under real diesel engine exhaust conditions.     

水热法制备ZrO_2纳米微晶及对乙醇和丁烷气敏性研究

用水热法制备 Zr O2 纳米微晶的平均尺寸为直径 5 nm,长 7.5 nm。由 X射线衍射确认晶相为单斜相。并对其形状和大小进行了透射电镜和激光散射分析 ,结果表明 Zr O2 纳米粒子在水溶液中存在软团聚 ,团聚体平均尺寸约 90 nm。着重研究了 Zr O2 纳米微晶对乙醇及丁烷的气敏性能 ,结果表明用纳米级 Zr O2 粒子制备的气敏元件对乙醇和丁烷有好的气敏性。并且随着纳米粒子尺寸降低 ,对气体敏感性增强