氧化铝改性高铈铈锆复合氧化物的制备及其负载钯催化性能

通过共沉淀法制备高比表面积、高孔容的氧化铝改性高铈铈锆复合氧化物,并研究氧化铝改性、前驱体含水焙烧等因素对铈锆复合氧化物结构及负载钯催化性能的影响。研究结果表明:氧化铝改性能够大幅度提升高铈铈锆复合氧化物的比表面积、孔容和高温稳定性。改性样品的新鲜比表面积为122.01 m^(2)/g,孔容为0.4750 mL/g;经1000℃、4 h高温老化后样品的比表面积为66.28 m^(2)/g。前驱体含水焙烧可以提高氧化铝改性铈锆复合氧化物的储氧能力,增强铈锆复合氧化物的高温稳定性;焙烧样品经1000℃、4 h高温老化后的比表面积比常规铈锆复合氧化物提高2.28 m^(2)/g,比常规铈锆铝复合氧化物提高2.75 m^(2)/g。此外,氧化铝改性还可以增大新鲜负载Pd催化剂的空燃比窗口,对催化剂的C_(3)H_(8)、NO催化性能具有促进作用;而前驱体含水焙烧对老化态氧化铝改性负载Pd催化剂的CO、C_(3)H_(8)、NO催化性能均有明显促进作用。

Effects of co-precipitation temperature on structure and properties of La and Y doped cerium zirconium mixed oxides

Due to the oxygen storage and release properties,cerium zirconium mixed oxides are recognized as the key material in automotive three-way catalysts.To reveal the effects of co-precipitation temperature on structure,physical and chemical properties of multi-doped cerium zirconium mixed oxides,a series of La and Y doped cerium zirconium mixed oxides(CZLYs)were synthesized via a co-precipitation method,and the physical and chemical properties of CZLYs were systemically characterized by XRD,N_(2) adsorption−desorption,TEM,XPS,oxygen storage capacity(OSC)and hydrogen temperature programmed reduction(H_(2)-TPR).The results show that co-precipitation temperature is an important parameter to influence the crystal size,oxygen storage capacity and thermal stability of CZLYs.When the co-precipitation temperature was 60℃,the best redox properties and thermal stability of CZLYs were obtained.After thermal treatment at 1100℃for 10 h,the specific surface area and oxygen storage capacity of the corresponding aged sample were 15.42 m^(2)/g and 497.7μmol/g,respectively.In addition,a mechanism was proposed to reveal the effects of co-precipitation temperature on the structure and properties of CZLYs.

Tungsten separation behavior on preparation of high-purity cerium by combined vacuum gravity sedimentation-directional solidification

In light of the difficult removal of harmful impurity tungsten(W)in Ce metal,in this paper a combined vacuum gravity sedimentation-directional solidification method was innovatively designed and the W separation behavior was investigated.By reducing the electron beam power instantly and gradually at reduction rates of 1,3 and 5 kW/min,it is found that W is enriched at the bottom of ingots as the melt solidifies.The enrichment effect is much better than that of single purification method and the enrichment degree increases as the beam reduction rate decreases,attributed to the k0(W)>1 andρ(W)>ρ(Ce).Overall,the minimum content of W impurity can decrease from 630 to 0.1 ppm at the top of the ingot,and the purity of Ce increases from 99.932 wt%to 99.995 wt%by this combined method.Additionally,this paper provides a new method for the removal of high density and low evaporation coefficient impurities in low vapor pressure rare earth metals.

The structure–activity relationships of Rh/CeO_(2)-ZrO_(2) catalysts based on Rh metal size effect in the three-way catalytic reactions

With the continuous tightening of automotive emission regulations and the increasing promotion of energy-efficient hybrid vehicles,new challenges have arisen for the low-temperature performance of three-way catalysts(TWCs).To guide the design of next-generation TWCs,it is essential to further develop our understanding of the relationships between microstructure and catalytic performance.Here,Rh/CeO_(2)–ZrO_(2) catalysts were synthesized with different Rh metal dispersion by using a combination of the wet impregnation method and reduction treatment.These catalysts included Rh single-atom catalysts,cluster catalysts,and nanoparticle catalysts.The results showed that the Rh nanoparticle catalyst,with an average size of 1.9 nm,exhibited superior three-way catalytic performance compared to the other catalysts.Based on the catalytic activity in a series of simple reaction atmospheres such as CO+O_(2),NO+CO,and hydrocarbons(HCs)+O_(2) and operando infrared spectroscopy,we found that metallic Rh sites on Rh nanoparticles are the key factor responsible for the low-temperature catalytic performance.

等离子区域熔炼提纯金属Y过程中的杂质迁移规律

利用等离子体区域熔炼提纯金属钇,获得了区熔提纯过程中Al、Si、Fe、Ni、Cu和Mo等杂质的迁移规律。计算结果表明,金属钇中Al、Si、Fe、Ni、Cu和Mo等常见杂质的平衡分配系数分别是0.2173、0.2201、0.5065、0.1586、0.1742和0.8576。由于上述杂质平衡分配系数小于1,杂质在液相中的溶解度大于固相溶解度,所以从理论上可判断出Al、Si、Fe、Ni、Cu和Mo等杂质将随着熔区移动富集在金属钇锭的尾端,也就是最后凝固区。实验结果证明了该理论预判的准确性。此外,探究了区熔次数与杂质迁移的内在联系,结果表明:随着区熔次数由5次增加至10次,杂质在金属钇锭尾端富集程度增加,即去除率升高。10次区熔后,Al、Si、Fe、Ni、Cu和Mo等杂质的去除率分别为45.71%、61.54%、33.98%、64.15%、52.14%和46.28%。由于上述杂质饱和蒸气压与金属钇接近,所以很难通过常规方法予以去除。等离子体区域熔炼提纯金属钇的研究为制备高纯钇提供了一种新方向。

SO_(4)^(2-)-modified La,Y-doped ceria-zirconia with high oxygen storage capacity and its application in Pd-only three-way catalysts

As the oxygen redox ability shows great effects on the catalytic performances of ceria-zirconia based materials,many strategies have been utilized to improve the oxygen storage capacity.Here in this study,we report a simple and facile approach to prepare a SO_(4)^(2-)-modified La,Y-doped ceria-zirconia material(SO/CZLY-f)with high oxygen storage capacity.Due to the additional redox process between SO_(4)^(2-)and S^(2-),oxygen storage capacity of SO/CZLY-f(745.3μmol O_(2)/g)is about 1.6 times higher than that of La,Ydoped ceria-zirconia material without SO_(4)^(2-)modification.Moreover,the catalytic activities and stability of the corresponding Pd-only three-way catalyst were measured.Compared to that of Pd@CZLY-f,the operation window of CO,full conversion temperature of HC and NO over Pd@SO/CZLY-f are obviously widened and lowered,respectively.After aging treatment at 1100℃for 4 h,the superiority of aged Pdloading composite is still maintained.

Separation and purification of Yb_(2)O_(3) by ion exchange chromatography and preparation of ultra-high purity Yb_(2)O_(3)

Ultra-high purity Yb_(2)O_(3) is the critical material of many high-tech materials such as laser glass and fiber,in which impurities seriously affect the laser color quality,intensity and power.In order to reduce the influence of impurities on the properties of laser materials,the purification process of Yb_(2)O_(3) was studied by comparing two kinds of resins(RT-1 and RS-1)using improved ion-exchange chromatography(IEC)method.In this study,through the synergistic improvement of resin structure and eluting system,the environmental pollution caused by ammonia water in the traditional IEC method was reduced,and the requirements of high temperature and pressure were cut.The ion exchange behavior and impurity removal mechanism in the resin column during the loading and eluting process were compared and analyzed.The experimental results show that RS-1 resin is all superior to RT-1resin in elements selectivity,ion exchange capacity and impurities removal rate.After separation and purification by IEC with RS-1 resin,the total removal rate of rare earth impurities was 77.59%and that of non-rare earth impurities was 95.86%when Yb recovery was more than 70%,both higher than that of RT-1 resin(73.26%and 83.18%).This indicates that the improved IEC method is very effective in separating and removing different metal impurities from Yb_(2)O_(3).The pilot test results of IEC method separating and purifying Yb_(2)O_(3) with RS-1 resin show that the purity of Yb_(2)O_(3) can be increased from 99.9929%to 99.9997%by IEC method.It has exhibited huge potential of preparing ultra-high purity Yb_(2)O_(3),especially the deep removal of non-rare earth impurities.