稀土在负载型非晶态NiB/Al2O3合金上作用研究

本文采用脉冲技术研究了稀土氧化物对负载型非晶态 Ni B/Al2 O3合金催化剂苯加氢活性和抗硫性能的影响。用 XRD鉴定了非晶态结构 ,用 TPR、TPD表征了催化剂的表面性质 ,用 CO化学吸附法测定了活性镍表面积。实验结果表明 ,非晶态合金催化剂上至少有两种吸附中心 ,稀土氧化物能明显地提高催化剂的苯加氢活性和抗硫性能 ,其原因是稀土氧化物有助于氧化镍的还原 ,从而在反应温度下有更多的活性镍物种被还原 ,稀土氧化物还能使镍物种颗粒细化 ,提高了活性镍面积。     

不同稀土及不同含量的助催化剂对重整反应的影响

考察了不同含量的稀土助剂L a对催化剂比表面积和催化活性的影响,其中以L a含量为1.5%(质量分数)时最佳。催化剂经过973K反应后得到的产物中,H2的量明显大于CO的量,≥1023K时H2/CO的值接近1,这是由于不同温度下催化剂对CH4和CO2活化的程度不同。添加不同稀土助剂催化剂的反应活性与其比表面积有正向关系,比表面积大则活性相对较高,反之则低,其中以L a和Ho为最佳。     

LnSrCoO4稀土复合催化材料制备与表征

首次采用聚乙二醇凝胶法制备了Co系类钙钛矿LnSrCoO4(Ln=La,Pr,Nd,Sm,Eu) 复合氧化物,研究了稀土对催化剂的结构和催化性能的影响,考察了它们对 CO和C3H8 的氧化反应活性,并运用XRD、BET、TPD等方法对催化剂进行了表征.结果表明该类复合氧化物具有K2NiF4结构,它们的结构和催化性能随稀土不同而变化,其中以LaSrCoO4催化活性最好,这是由LaSrCoO4的晶格氧更易移动、Co3+离子含量更高,氧空位和反应时化学吸附氧更多所致.     

Ni/海泡石及Ni-Sm/海泡石催化剂的研究

采用海泡石为载体,金属镍为活性组份,稀土为助剂,用不同方法制备了Ｎｉ／Ｓｅｐ 和Ｎｉ－Ｓｍ ／Ｓｅｐ 催化剂,并考察了它们的苯加氢反应性能。结果表明：Ｎｉ／Ｓｅｐ 催化剂的活性明显高于Ｎｉ／Ａｌ２Ｏ３,稀土Ｓｍ 对Ｎｉ／Ｓｅｐ 催化剂有较大的改性作用。ＴＰＲ、ＴＰＤ、ＣＯ吸附结果表明,海泡石和钐能使镍的还原温度降低,氢吸附量增大,活性中心增加,同时使镍原子电子密度增高。     

稀土掺杂对LaSrCoO4催化剂性能的影响

采用聚丙烯胺溶胶-凝胶法制备了类钙钛矿La0.7Nd0.3SrCoO4和La0.7Ce0.3SrCoO4复合氧化物催化剂,考察了它们对CO和C3H8的催化氧化活性,并运用XRD,IR,TPR和TPD等手段对催化剂进行了表征.结果表明,稀土掺杂后的LaSrCoO4复合氧化物均为K2NiF4型结构,不同稀土掺杂对LaSrCoO4复合氧化物的CO和C3H8氧化活性的影响不同,Nd掺杂能增加Co3+、化学吸附氧和晶格氧的数量,提高复合氧化物的活性.     

H_2O对不同状态Pd催化剂上低浓度CO催化氧化性能的影响

采用不同的Pd前驱体,通过浸渍法制备了系列Al_2O_3负载Pd催化剂,研究表明:Pd的化学状态、卤素离子的引入等不仅可直接影响催化剂的氧化活性,还可影响气氛中H_2O的作用。当Pd以氧化态存在时,以Pd(NO_3)_2的HBr溶液为前驱体所制备得到的BrC催化剂具有最高的反应活性,而以PdCl_2的HCl溶液为前驱体所得ClC催化剂的活性最低;经H2还原后,催化剂的活性均有显著的提高,其中以Pd(NO_3)_2为前驱体所得CH催化剂表现出最高的CO氧化活性,另外两种催化剂活性相差不大。同时对于还原态催化剂,气氛中的H_2O可抑制CH表面CO的吸附,并有利于O_2的吸附和活化,从而显著提高了CO的氧化活性;但Cl和Br引入后,H_2O的存在对CO吸附和活性影响不明显。当Pd以氧化态形式存在时,H_2O的引入可促进BrC和C催化剂上的CO氧化,其中BrC催化剂上的促进作用最为明显,但却抑制了以PdCl2的HCl溶液为前驱体所得ClC催化剂上的CO氧化。     

掺杂稀土BaTiO3的制备及镍基催化剂的活性

采用柠檬酸盐法和溶胶-凝胶法合成出稀土掺杂的BaTiO3,并考察了稀土离子掺杂对BaTiO3颗粒粒径的影响。测定了掺杂BaTiO3的比表面积、晶相、粒度等粉体性能,指出稀土离子有抑制BaTiO3晶粒长大的作用。稀土掺杂的BaTiO3作镍基催化剂载体,以CO2/CH4重整制合成气为探针反应,评价了这些催化剂的催化活性,实验表明掺杂稀土有助于提高催化活性。     

固体法制备Cu/La2O3-NiO催化剂及其光催化性能

采用3种不同的顺序制备了镧镍复合氧化物前驱体后,再在这3种物质上用等体积浸渍法制备了一系列Cu/La2O3-NiO催化剂。用XRD、TEM分别对催化剂表面结构、表面形貌进行了表征,以CO2和H2O光催化合成甲醇反应为探针反应研究了不同的制备方法对催化剂性能的影响。结果表明:先混合碾磨并一起焙烧后再处理的Cu/La2O3-NiO催化剂,其光催化活性最强,而先分开碾磨后一起焙烧再处理的催化剂光催化活性其次,而机械混合后再一起处理的催化剂对目的反应没有光催化活性。其中0.5%Cu/La2O3-NiO催化剂的催化效果最好。     

Ce、Sm改性Cu2O/MgO催化环己醇脱氢制环己酮的研究

采用浸渍还原法以水合肼为还原剂制备Cu2O/MgO催化剂,以环己醇脱氢制环己酮为探针反应,考察了Ce、Sm的添加对Cu2O/MgO催化性能的影响;采用程序升温还原(TPR)、二氧化碳程序升温脱附(CO2-TPD)和X射线衍射(XRD)等手段对催化剂进行了表征.研究结果表明,Ce-Cu2O/MgO、 Sm-Cu2O/MgO的催化性能优于Cu2O/MgO.其原因是Ce、Sm的添加使Cu2O分散度变大,导致催化剂中活性组分与载体的相互作用力增强,Cu2O更稳定;同时增加了催化剂的弱、中碱中心强度并削弱了其强碱中心强度,从而有利于反应的进行.     

载体对Ni基催化剂活性和抗积炭性能的影响

考察了载体对催化剂的活性和抗积炭性能的影响;并测定了催化剂上的积炭量;运用CO2-TPD、TPR、XPS和XRD等测试技术对催化剂进行表征,并与催化剂的抗积炭性能相关联.研究发现以钛酸钡为载体的镍基催化剂,其活性与抗积炭能力均优于Ni/γ-Al2O3,且加入助剂La后,其活性与抗积炭能力显著提高.这与催化剂的表面酸碱性、载体与活性组分间的相互作用、氧空位以及载体的结构有关.     

Synthesis and Thermal Decomposition Mechanism of Rare Earth Benzoates

Rareearthbenzoatesareakind0fstablecompounds.Theco0rdinationcomP0undsf0rmedbyrareearthandcarboxylicacidshaveunusualstructuresandinterestinglundnesceniProperties.Bymeansoff0rmingc0njugaedcomplexes,rareearthmetalsandcarb0xylicacidscanf0rmnetorlayerp0lymerandchangetheirlundnescentprop-erties.S0merareearthcomplexeshavebeenap-Pliedinagricultureaslight-transfeedngmaeri-al8-Althoughthermaldecompositi0nmechanismofrareearthbenz0ateshasbeenreported,itdealswith0nlys0lidphaseproducts["'1,litdeab0utgasPha…     

Studies on synthesis and fluorescent property of rare earth complexes RE（ABMF）2AA and copolymers RE（ABMF）2AA-co-MMA

Four new complexes RE(ABMF)2AA (RE=Sm, Eu, Tb, Dy) were synthesized by the reaction of RECl3·6H2O with acrylic acid (HAA) and 1-(2-furyl)-3-phenyl-1,3-propanedione (ABMF). The copolymerization of the rare earth complexes with methyl methacrylate was studied by using 2,2-azobis-isobutyronitrile as an initiator. The composition and structure of the four complexes were characterized by elemental analysis, UV-vis and FTIR. The glass transition temperature and molecular weight of the copolymers were determined. Photoluminescent measurement showed that ligand ABMF could efficiently transfer the energy to Sm3+ and Eu3+ ions in the complexes and sensitize the luminescence of the rare earth ions, but could not sensitize Tb3+ and Dy3+ ions. As a result, both Sm3+ and Eu3+ complexes emitted the characteristic fluorescence of Sm3+ and Eu3+ ions due to the f-f transitions. The four copolymers could emit strong fluorescence of the rare earth ions.     

Effects of Heavy Rare Earth Elements on Properties ofAmorphous NiB Alloy Catalyst

Gas-phase hydrogenation of benzene was selected as probe reaction to study the effects of heavy rare earth ele-ments on the catalytic activity and sulfur resistance of amorphous NiB alloy. XRD, DSC, CO chemical adsorption, TPR and TPD were used to characterize the bulk and the surface properties of the alloys, respectively. The results indicate that the addition of a small amount of heavy rare earth (HRE) elements obviously improves the activity, thermal stability and sulfur resistance of amorphous NiB alloy. The HRE can alter H2 adsorption bond strength, increase the surface area of ac-tive nickel and the number of active centers over the surface of NiB alloy and it also can decrease the activation energy of NiB alloy for benzene hydrogenation. There are four kinds of adsorbing sites over the surface of NiB and NiBRE, only three kinds of them have concerned with the reaction.     

稀土金属离子对5,-AMP和3'',5''-cAMP的水解切断作用

用HPLC法研究了稀土金属离子RE3＋(如La3+,Ce3+,Nd3+,Sm3+,Eu3+,Tb3＋)对5’-腺苷-磷酸(5’-AMP)和3’,5’-腺苷环磷酸(3’,5’-cAMP)的催化水解切断作用。结果表明在温和条件下,稀土金属离子对5,-AMP无明显的切断作用,而Ce3＋对3’,5’-cAMP有很好的切断作用;另外,H2O2的加入能极大地促进稀土金属离子对5’-AMP和3’,5’-cAMP的水解切断作用。pH值对稀土金属离子水解切断5’-AMP是有影响的。     

Ln2O3/MgO催化合成增塑剂IOP的研究

采用共沉淀-焙烧法制成了LnO3／MgO(Ln=Nd，Sm，Er)担载型催化剂。该型催化剂比表面大，分散性好。在催化合成IOP中效果明显，且使Ln2O3的用量减少80％左右。     

Effect of Rare Earths on Electronic Structure of (110) Twin Martensite Boundary for Ni2MnGa Alloy

The doping effect of rare earth elements (Tb and Sm) on the electronic structure of (110) martensitic twin boundary in Ni2MnGa alloys was investigated by using ab initio method within the DFT and the supercell implementation. The calculated results show that the atomic relaxation lowers the boundary energy and the segregation energy. Sm seems easier to segregate to the boundary and has a greater doping effect compared with Tb due to its lower segregation energy and bigger bonder order with neighboring atoms. Tb makes a greater contribution to the magnetic properties of the twin boundary than Sm.     

铝对钐铕钆碳酸盐沉淀的影响

针对北方混合轻稀土矿占比2%的中重稀土,研究铝含量、溶液浓度、沉淀方式等对钐铕钆碳酸盐的晶核形成及长大过程的影响。最佳生产工艺条件为:稀土浓度200g/L、铝含量0.018g/L的钐铕钆溶液加入50%晶种、正液沉淀。沉淀由Sm2(CO3)3·2.85H2O、Eu2(CO3)3·3H2O、Gd2(CO3)3·3H2O组成的非晶型钐铕钆碳酸盐,铝含量低于0.02g/L可消除铝水解的影响,得到的钐铕钆碳酸盐晶粒尺寸大、晶化程度高,易于过滤。     

中稀土氧化物-钯催化剂对一氧化碳的氧化作用

本文研究了中稀土氧化物对钯催化剂活性的影响。实验表明 ,中稀土氧化物的添加对这种钯催化剂的一氧化碳氧化性能都有所改善 ,其中以氧化钐最为突出。它明显地降低了一氧化碳的氧化温度达 60～ 1 0 0℃之多。     

Synthesis of ion imprinted polymers for selective recognition and separation of rare earth metals

Lanthanide-ion imprinted polymers(L-IIPs) were synthesized by stoichiometric amounts of rare earth ions and the cavities in the polymers were created for the corresponding lanthanide ions. The maximum sorption capacities were estimated to be 125.3, 126.5, 127.6, 128.2 and 129.1 mg/g for Pr, Nd, Sm, Eu and Gd, respectively at p H 6. In the selectivity study, the L-IIPs exhibited good selectivity to the specific rare earth ions in the presence of coexisting cations. The imprinting results were found to be excellent with some rare earth ions over other competitor rare earth ions with the same charges and close ionic radius.     

Preparation and Easy-Cleaning Property of Rare Earth Composite Ceramic

Rare earth and far-infrared mineral composite materials were added to ceramic glazes to prepare easy-cleaning ceramic. The morphology of easy-cleaning ceramic was observed by SEM. The influence of easy-cleaning ceramic on water surface tension and contact angles of water were investigated. Through calculation of ceramic surface free energy and observation of oil drop on ceramic surface in water, the easy-cleaning mechanism of rare earth composite ceramic was studied. It is found that the rare earth composite ceramic can make water surface tension decrease. The surface free energy and the polar component of rare earth composite ceramic are increased. The rare earth composite ceramics have the easy-cleaning property.