铜钴尖晶石复合氧化物催化剂的组成对二甲苯完全氧化反应催化性能的影响

具有特定结构的复合氧化物,如ABO3,A2BO4及AB2O4等对某些反应比单一氧化物具有更好的催化性能[1,2]. 然而,有关尖晶石型复合氧化物AB2O4对有机物燃烧反应催化性能的研究相对较少,且常用的模型反应大都是一氧化碳或甲烷的催化氧化反应[3]. 超微粒子由于具有大的比表面积和高的表面能等特性,在催化领域已日益引起人们的重视[4]. 低温固相合成是近十几年发展起来的一种新的超细粒子制备方法[5]; 它具有不使用溶剂,无废液排放,工艺过程简单,能耗低等优点,属于对环境友好的“绿色化学”. 目前,此法在合成多组分复合氧化物及催化化学中的应用仍不多见. 本文以含有结晶水的醋酸铜和醋酸钴为原料,采用低温固相合成法制备了单组分氧化铜和氧化钴,以及三种不同铜钴比的铜钴尖晶石型复合氧化物,并以二甲苯氧化为模型反应,采用XRD,BET及程序升温还原(TPR)等手段进行了研究.     

钙钛矿型LaNiO3、LaMnO3的形成条件

用混合硝酸盐分解法和柠檬酸络合法分别制取了单一钙铁矿型多晶粉末LaNiO_3和LaMnO_3. XRD分析表明LaNiO_3的形成经历了混合氧化物转化为LaNiO_3的同相反应; 而LaMnO_3晶相直接由无定形相转化而来。根据DTA、TG、IR分析两者的形成, NO_3~-离子都起了重要作用. 同时讨论了络合剂柠檬酸的作用.     

低镍甲烷化催化剂中镍和氧化镧的分散研究

本文用X射线衍射法(XRD), 透射电镜(TEM), 配合电子衍射对Ni/Al2O3,Ni/γ-Al_2O_3-La_2O_3等催化剂中镍晶粒度和La_2O_3的分散状态进行了测量和讨论。用透射电镜测量了不同La_2O_3含量的催化剂中镍晶粒度分布, 其平均直径可与X射线宽化法测定值相比较。催化剂中随La_2O_3加入量的增加, Ni晶粒有细化趋势, 从而提高了甲烷化催化活性。对La_2O_3在γ-Al_2O_3表面作密置单层分散的模型提出了新的旁证, 并推断由于La_2O_3在γ-Al_2O_3表面高分散并产生较强相互作用, 使γ-Al_2O_3接近表层晶格发生畸变。     

燃烧催化剂中LaAlO3作为第2载体的研究

在载体堇青石表面涂覆一层LaAlO3作为第二载体，用浸渍法制备负载型LaMnO3、LaCoO3等钙钛矿型燃烧催化剂时，发现能促进LaMnO3等活性相的生长，从而提高了二甲苯完全氧化的催化活性；对于负载型LaCo3O3催化剂，可避免因用γ－Al2O35作第二载体而生成的低活性CoAl2O4类尖晶石相，因而有利于提高催化剂的耐热性。     

负载型La0.8Sr0.2MnO3燃烧催化剂的载体效应

用浸渍法制备负载型Ｌａ_（０．８）Ｓｒ_（０．２）Ｍｎｏ_３燃烧催化剂,比较了γ－ＡＩ_２Ｏ_３、α－ＡＩ_２Ｏ_３、堇青石（２ＭｇＯ·２Ａｌ_２Ｏ_３、５ＳｉＯ_２）和ＺｒＯ_2四种载体的负载效果．用ＸＲＤ,ＤＰＲ着重研究了γ－Ａｌ_２Ｏ_３载体上由于负载量不同、焙烧温度不同引起的催化剂物相变化和二甲苯完全氧化的催化活性变化．     

负载型La0.8Sr0.2MnO3燃烧催化剂的载体效应

Combustion catalysts La0.8Sr0.2MnO3 supported on γ-Al2O3, α-Al2O3, cordierite (2MgO•2Al2O3•5SiO2) and ZrO2 were compared. Further investigation was focused on LSM/ γ-Al2O3 catalyst. It was observed that LSM/γ－Al2O3 catalyst loaded with 20% (mass fraction) LSM (La0.8Sr0.2MnO3 or corresponding oxides), heated at 750℃ or above, perovskite-type oxides were found by XRD examination, whereas, the same catalyst loaded with 10% or less LSM, perovskite oxides were absent, calcination temperature about 750℃ is necessary for the formation of perovskite structure in LSM/γ-Al2O3 catalysts. High activity of complete oxidation of xylen will be obtained when perovskite-type oxides.
Investigation of TPR showed that neat LSM or LSM/γ-Al2O3(20%) was reduced by H2-N2 mixed gas. Two degradation processes took place. In the first, reduced temperature peak was about 350 - 450℃. If reduction ended at 400℃, perovskite structure was retained, which may be due to the reduction of Mn3+to Mn2+ on the surface of LSM only. In the second process, perovskite structure was destroied, and La2O3, Mn2O3, Mn - Sr - O oxides could be obtained, which took place in the temperature range 685 - 750℃ and ended at 800℃. This was proved by TPR experiments (Fig. 3, 5) and XRD patterns (Fig. 4)
Catalysts LSM/γ-Al2O3(10% or 20%) heated at 500℃ have only one TPR peak, i. e. lower temperature peak. This is due to the absence of perovskite-type oxides in the catalysts. However, neat LSM or LSM/γ-Al2O3(20%) heated 750℃ or above, not only the first low temperature TPR peak but also the second peak, which is contributed by the perovskite-type oxides in these catalysts appeared. Therefore, the second TPR peak, i. e. the higher temperatue peak is a characteristic peak for perovskite-type oxides in the reduced process. When LSM/ γ-Al2O3 (10%) catalys is heated at 750℃, no perovskite-type oxides were detected by XRD, and the second reduction peak was absent also in TPR process. \
The order of the second reduction peak temperature(characteristic peak of perovskite - type ox- ides) is: neat LSM(750℃）> LSM/γ-Al2O3 20% (685-698℃) -deposited LSM/γ-Al2O3 (698℃) > LSM/γ-Al2O3 15% (677 - 680℃) >(LSM/γ-AL2O3 10% 620 - 630℃, for Mn - Al - O medium oxides on surface). It is correleted with the increasing of the effect of support sequentially.
When LSM/γ-Al2O3 catalysts were heated at 900℃, more stable phase, spinel MnAl2O4 appeared, which could be proved by TPR of model catalyst MnAl2O4/γ-Al2O3.     

焙烧温度对La2O3—NiO体系结构和导电性及某些催化性能的影响

稀土氧化物特别是La2O3作为助催化剂，对CO甲烷化反应有促进作用，已为人们所知［‘j．研究焙烧温度对La。O。－NIO催化剂结构、导电性，特别是对其在不同类型反应中催化性能的影响，目前文献报道较少．本文通过多晶X射线衍射（XRD），差热一热重分析（DTA－TG），导电性测量，CO甲烷化及二甲苯完全氧化反应活性测定等手段，考察了所制备的La。Os－NIO催化剂经不同温度焙烧后，结构、热效应、导电性的变化，并研究了该体系催化剂在上述两种不同类型反应中的催化性能．用分析纯试剂La（NO3)·6H2O和La（NO3）3·6H2O（北京化工…     

负载型Ln—Ba—Mn—Cu系复合氧化物燃烧催化剂的结构特征

用XRD剖析了载在多孔陶瓷载体上Ln—Ba—Mn—Cu系复合氧化物燃烧催化剂的晶相组成。用TEM观察了载体和催化剂的形貌特征,鉴别出呈粒状分布的La_(1-y)Ba_yMn_(1-x)Cu_xO_(3 δ)。用XPS研究了催化剂的表面状态。     

LaMnO_3和La_（0．927）φ_（0．073）MnO_3的结构与性能的对

合成了两个稀土复合氧化物ＬａＭｎＯ３和Ｌａ（０．９２７）φ（０．０７３）ＭｎＯ３，并对其进行了结构、电阻率、ＸＰＳ表面分析、水汽转化及二氧化碳甲烷化反应的催化性能测定。初步解释了结构与性能的关系。     

LaCo0.9Cu0.1O3的蔗糖溶胶-凝胶法合成及二甲苯催化氧化性能研究

蔗糖溶胶 凝胶法合成了稀土钙钛矿型复合氧化物LaCo0 .9Cu0 .1 O3,并对其进行了XRD ,BET ,TPR表征和二甲苯催化氧化性能测试 ,并与柠檬酸溶胶 凝胶法作了比较。结果表明 ,蔗糖作为络合剂成胶和干胶容易 ,粒径较小 ,具有进一步降低LaCo0 .9Cu0 .1 O3形成温度的作用 ,以蔗糖作为络合剂在 70 0℃所制备的催化剂LaCo0 .9Cu0 .1 O3低温活性较好。