首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 281 毫秒
1.
Two series of mixed oxides, CoAlM and MgAlM (M= Cr, Mn, Fe, Co, Ni, Cu) , were prepared by calcining their corresponding hydrotalcite-like compounds (HTLc) . The ratio of Mg: Al: M (or Co: Al: M) was 3:1:1. The catalytic activity of all samples for the reaction of NO CO was investigated. The results showed that the activity of CoAlM was much higher than that of MgAlM. The structure and the property of redox were characterized by XRD and H2-TPR. The results indicated that only MgO phase was observed after calcining MgAlM hydrotalcites, and the transition metals became more stable. The spinel-like phase appeared in all of CoAlM samples after the calcination, and the transition metals were changed to be more active, and easily reduced . The activities of three series of mixed oxides CoAlCu obtained from different preparation methods, different ratio of Co:Al:Cu and at different calcination temperatures, were studied in detail for proposing the mechanism of reaction. The ability of adsorption of NO and CO  相似文献   

2.
以水滑石为前体的Mg-Al-M复合氧化物对催化消除NOx的活性   总被引:21,自引:0,他引:21  
刘钰  杨向光  张忠良  吴越 《催化学报》1999,20(4):450-454
通过H2TPR,XRD,TGDTA及比表面积测定等对MgAl水滑石化合物进行了表征,研究了焙烧温度对水滑石物理性质的影响.在此基础上,研究了MgAl水滑石中加入过渡金属(M)离子后对NO+CO反应的催化活性.结果发现,含有Cu离子的样品对NO+CO反应有较高的催化活性,并与CoAlM的催化性能进行了比较  相似文献   

3.
刘钰  杨向光  王学中  吴越 《化学学报》1999,57(7):782-789
以共沉淀法制提得的水滑石类化合物为催化剂前体,经焙烧可得到一系列尖晶石类化合物Co-M-Al[M=Cr,Mn,Fe,Ni,Cu;n(Co):n(M):n(Al)=3:1:1].通过XRD,比表面测定,化学分析,NO吸附等方法对其进行表征,测定了此系列催化剂对NO催化还原和催化分解的活性,结果发现此系列催化对消除NO具有很高的活性.同时对催化消除NO的机理及过渡金属离子中d轨道电子对催化活性的影响进行了一些探讨。  相似文献   

4.
机动车在给人类生活带来便利的同时,也造成了严重的大气污染.其尾气净化成为人们关注的焦点.一氧化氮(NO)、一氧化碳(CO)和碳氢化合物(HCs)是机动车尾气中的三大典型污染物,主要通过三效催化(TWC)技术进行脱除. TWC技术涉及几个重要的催化反应,其中 CO催化还原 NO由于能够同时消除 CO和 NO两种污染物而引起研究者的极大关注.研究表明,负载型贵金属催化剂在该反应中显示出优异的催化性能,但存在资源匮乏、价格昂贵以及热稳定性欠佳等不足.因此,低价、高效的过渡金属氧化物催化剂成为近年研究重点.稀土金属氧化物 CeO2由于具有良好的氧化还原性能、较高的储释氧容量以及丰富的表面氧空位而被广泛用于 CO催化还原 NO反应.研究表明,对 CeO2进行离子掺杂可进一步增大其比表面积,改善其氧化还原性能和储释氧容量.并且,我们在先前的研究中还发现,将具有多种可变价态的钛离子或锡离子掺入 CeO2晶格由于掺杂离子能与 Ce4+/Ce3+发生电子转移而更有利于改善 CeO2的理化性质.此外,锰氧化物(MnOx)在氧化还原气氛中容易实现不同价态之间的切换,从而在一些重要的氧化还原反应中表现出优异的催化性能.近年来,有研究者将 CeO2与 MnOx相结合制备了 CeO2-MnOx催化剂用于 NO消除、碳烟燃烧和挥发性有机物(VOCs)氧化等反应,并取得一些有意义的结果.然而,对于实际应用来说, CeO2-MnOx催化剂存在比表面积偏小等不足.众所周知,γ-Al2O3是一种常用的具有高比表面积和高热稳定性的催化剂载体材料,可有效增大催化剂比表面积.我们前期研究结果表明,通过共沉淀法将 Al3+掺入铈基复合氧化物的晶格相比于以γ-Al2O3为载体更有利于改善铈基复合氧化物的理化性质和催化性能.因此,我们通过简单的氨水反滴加共沉淀法制备了一系列 CeO2-MnOx-Al2O3(Ce:Mn:Al摩尔比=6:4:x,x =0.25,0.5,1,2)复合氧化物催化剂用于 CO催化还原 NO反应.并运用 X射线衍射、拉曼光谱、氮气物理吸附、氢气程序升温还原、X射线光电子能谱以及原位漫反射红外光谱等表征技术对上述催化剂进行了系统分析.重点考察了 Al3+掺杂量对 CeO2-MnOx-Al2O3复合氧化物催化剂理化性质和催化性能的影响.结果表明,在 CeO2-MnOx复合氧化物中掺入少量 Al3+会导致其晶粒尺寸减小,从而增大其比表面积和孔体积,并增加 Ce3+和 Mn4+的含量.比表面积和孔体积增大有助于催化剂与反应物分子之间充分接触; Ce3+和 Mn4+含量增加能分别促进 CO物种吸附以及吸附态 NO物种脱附、转化和解离.这些变化有利于提高 CeO2-MnOx复合氧化物在 CO催化还原 NO反应中的催化性能.最后,基于催化剂的理化性质表征及其催化性能评价,我们尝试提出了一个可能的催化反应机理,以进一步理解 CeO2-MnOx-Al2O3复合氧化物催化剂在 CO催化还原 NO反应中的优异性能.  相似文献   

5.
The coprecipitation method was used to prepare a series of different oxides (CuO: 0, 5%, 10%, 15%, 20%, 30% and 40%) derived from Cu substituted Mg/Al mixed anionic clay precursors (hydrotalcites) at the ratio of M2+/M3+ =3. In order to study influences of Cu and Mg content upon the performance of these materials, such characterization techniques as X-ray diffraction, thermogravimetrical analysis, differential scanning calorimetry, temperature programmed reaction and Fourier transform infrared reflectance spectra, were used. The results showed that complete structure of hydrotalcite precursors could be formed when CuO≤30%. When CuO≥40%, Cu(OH)2 phase appeared. Homogeneous composite oxides can be obtained by high temperature calcination at CuO≤20%. When CuO>20%, CuO phase was isolated. The content of Cu and Mg had significant influences on thermal stability of materials. The reduction ability of materials was related to calcination temperatures and material composition.  相似文献   

6.
以共沉淀法合成的水滑石(HT)和类水滑石(HTLc)为前体制备了镁铝、钴铝、钴镁铝混合氧化物,采用了BET、XRD、TG-DTA、TPR、FTIR和微量量热吸附及异丙醇催化反应进行了研究。结果表明:以HT和HTLc为前体制备的混合氧化物,其比表面积较大、并随着钴含量的增加而降低。在HT中引入Co2+离子后,由于Co2+离子的氧化还原属性,削弱了水滑石层对阴离子的键合能力,从而使其热分解温度及热稳定性降低,导至焙烧后生成的混合氧化物的比表面积比不含钴的2Mg/Al混合氧化物的低。在TPR过程中,镁铝混合氧化物不被还原,而含钴的混合氧化物的还原是经由Co3+ → Co2+ → Co0的过程。混合氧化物表面含有酸性位和碱性位,并随着钴含量的变化而得到调变。含钴氧化物样品的表面以L酸为主和含有很少量的B酸。异丙醇催化反应生成丙酮的选择性最高,表明样品表面的氧化还原位是主要的,随着钴的加入及含量的增大,异丙醇催化反应的转化率也是增大的。  相似文献   

7.
Hydrotalcite-like compounds (HTlcs) can be used as the catalysts as it is since they contain various transition metal cations as the catalytically active species well dispersed on the basic support materials. Moreover, increasing numbers of the applications of HTlcs after the heat treatment have been found since the oxides with very small crystal size, stable to thermal treatments, are obtained after the calcination. The oxides possess interesting properties such as high surface area, basic properties and further form small and thermally stable metal crystallites by reduction. Moreover, the calcined oxides show a unique property, i.e., “memory effect,” which allows the reconstitution of the original hydrotalcite structure. We have developed the catalytic applications of hydrotalcites as it is and moreover the mixed oxides derived from hydrotalcites for various catalytic reactions, i.e., oxidation, dehydrogenation and reforming of hydrocarbons, and even for the reforming of methanol and the CO shift reaction. Aerobic oxidation of alcohols, Baeyer−Villiger oxidation of ketones and O3 oxidation of oxalic acid have been successfully carried out with the Mg−Al hydrotalcites containing Ni, Fe and Cu, respectively, as the catalysts in liquid phase. In the O3 oxidation of oxalic acid, the catalytic activity was enhanced by the “memory effect,” i.e., Mg(Cu)–Al hydrotaclite was reconstituted on the surface of Mg(Cu,Al)O periclase particles and oxalic acid was incorporated as anions in the hydrotalcite layer, resulting in an enhanced oxidation of oxalic acid. As the catalysts in the vapor phase reactions, Mg/Fe/Al mixed oxides prepared from Mg–Al(Fe) hydrotalcites and effectively catalyzed the dehydrogenation of ethylbenzene. Supported Ni metal catalysts have been prepared from Mg(Ni)–Al hydrotalcites and successfully used in the steam reforming and the oxidative reforming of methane and propane. Moreover, the Ni catalysts have been improved by combining a trace amount of noble metals by adopting the “memory effect” and used in the production of hydrogen for the PEFC under the daily startup and shutdown operation. Also starting from aurichalcite or hydrotalcite precursor as the precursor, Cu/Zn/Al catalysts with high Cu metal surface area have been prepared and successfully applied in the steam reforming of methanol and dimethyl ether, and moreover in the CO shift reaction.  相似文献   

8.
Co-M(M=La,Ce, Fe,Mn, Cu,Cr)复合金属氧化物催化分解N2O   总被引:1,自引:0,他引:1  
薛莉  贺泓 《物理化学学报》2007,23(5):664-670
通过共沉淀法制备了一系列Co-M(M= La, Ce, Fe, Mn, Cu, Cr)复合金属氧化物及纯Co3O4催化剂, 考察了其催化分解N2O 的活性. 结果表明在研究的系列催化剂中, Co-Ce 复合氧化物催化剂具有最好的催化分解N2O的活性; 其活性与Ce/Co 摩尔比有直接的关系, 当Ce/Co 摩尔比为0.05 时(CoCe0.05 催化剂)催化活性最佳; 当有NO 和O2共存时, 可能在催化剂活性中心上形成表面硝酸盐或亚硝酸盐吸附物种而使其活性受到较大影响. 通过对Co-M 催化剂的XRD、BET、O2-TPD及H2-TPR 等表征结果的分析, 发现作为主要活性位的Co2+的氧化还原能力是影响催化剂活性的主要原因. 这是因为根据反应机理, N2O 的表面分解步骤与Co2+氧化成Co3+的能力相关, 而吸附氧的脱附与Co3+还原成Co2+的能力相关. 在所研究的催化剂中, 添加除CeO2之外的其它过渡金属氧化物时, 催化剂中Co3+/Co2+的氧化还原能力降低, 因此其催化性能降低. 另外, 添加不同过渡金属氧化物也改变了N2O 催化分解反应的速控步骤.  相似文献   

9.
MgAl and MgMAl oxides(M = Co,Ni and Cu) with a Mg:M:Al molar ratio = 4:1:1 were synthesized from the calcination of their corresponding layered double hydroxide(LDHs) precursors.Their catalytic activities were examined for the oxidation of ethylbenzene using tert-butylhydroperoxide(TBHP) as an oxidant.The oxidized product was mainly acetophenone.The catalytic activities were in the order of MgCuAl>MgNiAl~NiAl~MgCoAl~CoAl>CuAl>MgAl oxides.Reusability studies show that the catalysts are stable under the re...  相似文献   

10.
The Co–Mg–Al mixed metal oxides were prepared by calcination of co-precipitated hydrotalcite-like precursors at various temperatures (600–800 °C), characterised with respect to chemical (AAS) and phase (XRD) composition, textural parameters (BET), form and aggregation of cobalt species (UV–vis-DRS) and their redox properties (H2-TPR, cyclic voltammetry). Moreover, the process of thermal decomposition of hydrotalcite-like materials to mixed metal oxide systems was studied by thermogravimetric method combined with the analysis of gaseous decomposition products by mass spectrometry. Calcined hydrotalcite-like materials were tested as catalysts for methanol incineration. Catalytic performance of the oxides depended on cobalt content, Mg/Al ratio and calcination temperature. The catalysts with lower cobalt content, higher Mg/Al ratio and calcined at lower temperatures (600 or 700 °C) were less effective in the process of methanol incineration. In a series of the studied catalysts, the best results, with respect to high catalytic activity and selectivity to CO2, were obtained for the mixed oxide with Co:Mg:Al molar ratio of 10:57:33 calcined at 800 °C. High activity of this catalyst was likely connected with the presence of a Co–Mg–Al spinel-type phases, containing easy reducible Co3+ cations, formed during high-temperature treatment of the hydrotalcite-like precursor.  相似文献   

11.
采用硝酸铝和硝酸钴的乙醇溶液与钼酸铵的碳酸铵水溶液共沉淀制备了Al2O3负载Co-Mo双金属氧化物前驱体,结合氨程序升温还原法制得了氮化物催化剂Co-Mo-N/Al2O3.利用X射线衍射和N2物理吸附方法表征了制备的前驱体和钝化态Co-Mo-N/Al2O3催化剂的晶相和孔结构,用程序升温脱附、程序升温表面反应及扫描电子显微镜考察了共沉淀法和浸渍法制备的催化剂的晶格稳定性、活性中心和表面形貌,用氨分解反应表征了Co-Mo-N/Al2O3催化剂的活性.结果表明,焙烧温度对催化剂比表面积有较大影响,低温焙烧的样品中活性组分散性较好,673K焙烧制得催化剂的氨分解活性最高.与浸渍法制备的Co-Mo-N/Al2O3催化剂相比,共沉淀法制备的催化剂具有更高的晶格稳定性、更均匀的活性组分分布和更高的氨分解活性.  相似文献   

12.
A series of MnOx modified cobalt oxides with different atomic molar ratios of Mn/(Mn?+?Co) were prepared by a soft reactive grinding route and investigated for CO preferential oxidation in H2. It was found that as-prepared Mn-doped cobalt oxides exhibited superior activity compared to the single constituted oxides, other Mn–Co–O mixed oxides synthesized by solution-based route, and other grinding-derived mixed metal oxides M–Co–O (M?=?Zn, Ni, Cu, Fe). The grinding-derived MnCo10 catalyst with Mn/(Mn?+?Co) molar ration of 10% showed the best CO oxidation activity and higher selectivity at low temperature. The surface richness of Co3+ was not found as increasing the Mn molar ratio in the present work. However, the incoporation of MnOx with proper amount into Co3O4 could produce high surface area, high structure defects, and rich surface active oxygen species, while the ability to supply the active oxygen species was suggested to play the crucial role in promoting the catalytic performance of Mn–Co–O mixed oxides.  相似文献   

13.
Cu对Pt/Cu-Mg-Al-O催化剂上NOx储存性能的影响   总被引:3,自引:0,他引:3  
固定二价与三价阳离子摩尔比为3∶1,采用共沉淀法合成系列Cu-Mg-Al水滑石,经500 ℃焙烧制成复合氧化物Cu-Mg-Al-O(wCuO(%)分别为0、5、10、20,简称w-CMAO, w=0、5、10、20).通过浸渍法制备Pt/Cu-Mg-Al-O负载型复合氧化物催化剂.XRD结果表明Cu在催化剂及其前驱体中高度分散.采用等温NOx储存实验研究催化剂对NOx的储存性能, NOx-TPD法考察储存的NOx脱附情况.实验结果表明,尽管Cu取代减少了催化剂中MgO含量,但增强了催化剂的NO氧化活性,有效提高了催化剂的NOx储存性能.同时TPD结果进一步表明当CuO掺杂量在w=(10~20)% 时,可以明显降低催化剂上生成的硝酸盐的分解温度.  相似文献   

14.
673K分解Cu/AI物质的量比分别为0.5、1和2的Cu-AI水滑石转化为Cu(AI)O复合物。XRD测定仅显示CuO物相,表明组成成分较均一。微量吸附量热法测定Cu(AI)O复合物表面酸碱中心的强度和数量,给出了吸附分子CO2/NH3的吸附曲线。量热结果展示,样品的酸中心强度顺序是:0.5CAO>CAO>2CAO,而碱中心强度顺序是:0.5CAO<CAO<2CAO。显然,样品的酸性(碱性)随着AI(Cu)含量的提高而逐渐增强。研究表明,样品的NH3和CO2起始吸附热与其Sanderson电负性线性相关。  相似文献   

15.
氮氧化物(NOx)作为煤炭燃烧过程主要污染物之一, 可直接或间接引起如光化学烟雾、酸沉降、平流层臭氧损耗和全球气候变化等大气环境污染问题. NOx的选择性催化还原技术(SCR)被认为是目前处理固定源NOx的最有效方法之一. 由于燃煤工业锅炉烟气中还有1%~3%的CO, 远高于NOx的0.02%~0.04%, 因此, 以CO为还原剂进行CO-SCR脱硝具有现实意义, 它可在反应过程中同时消除CO和NO两种有害气体, 但对催化剂的活性及抗毒性提出更高要求. CeO2作为一种常用的稀土材料, 因具有良好的储放氧能力而广泛应用于SCR反应中. 过渡金属改性可进一步改善CeO2的物化性能, 从而可能达到CO-SCR的应用要求.本文利用超临界水热技术合成了MOx-CeO2(M = Co, Fe, Cu)固溶体催化剂, 并利用X射线衍射(XRD), 氢气程序升温还原(H2-TPR), 傅里叶变换原位红外(DRFTIR)等探究了催化剂在CO-SCR反应中的催化活性与作用机制. CO-SCR反应活性测试表明, CuO-CeO2催化剂活性明显优于FeOx-CeO2和CoOx-CeO2催化剂, 在126 ℃ NO去除率即可达到90%; 其N2选择性也可在179 ℃时达到90%. 为了进一步探究MOx-CeO2(M = Co, Fe, Cu)催化剂的CO-SCR反应途径,本文随后进行了系列原位DRFTIR实验, 发现NO在三种催化剂表面均能被高效吸附, 其吸附态中间产物主要为双齿硝酸根, 桥式硝酸根, 桥式硝基和亚硝酰基等. 另外, 在CuO-CeO2催化剂表面还存有螯合硝基和单齿硝酸根. CO在催化剂表面主要以COx, 碳酸根和羧酸根等形式存在. 值得注意的是, 在CuO-CeO2表面, CO因吸附于Cu+而形成Cu+-CO, 在2100 cm-1左右形成明显的特征峰. 当催化剂表面吸附CO至饱和后再通入NO发现, CO的吸附特征峰逐渐被NO的特征吸附峰取代; 而当NO被吸附至饱和后再通入CO, NO的特征峰则不出现明显变化. 这表明NO和CO在催化剂表面存在竞争吸附, NO可能优先于CO吸附在催化剂表面. 当NO和CO同时通入红外反应仓时发现, 在CoOx-CeO2和FeOx-CeO2催化剂表面只观察到NO的吸附峰, 而在CuO-CeO2催化剂表面观察到Cu+-CO的特征峰, 说明在CO-SCR反应过程中, CO可以在Cu+表面被有效吸附,其与吸附于CeO2表面的NO物种反应生成N2和CO2, 遵循Langmuir-Hinshelwood反应机理. 而在CoOx-CeO2和FeOx-CeO2催化剂表面, 因NO的竞争吸附, 使得二者主要遵循Eley-Rideal反应机理.  相似文献   

16.
以柠檬酸络合法制备了 CuCrO_2、 CuAlO_2和 CuFeO2等具有铜铁矿结构的 ABO2型复合氧化物,并考察了它们在氧化和还原气氛中对 CO- NO反应的影响 . CuAlO_2和 CuCrO_2具有好的催化活性, CuCrO_2更具有相当的稳定性,经过氧化和还原条件下的 CO- NO反应后,体相组成仍然保持不变 . CuAlO_2在还原条件下,部分被还原生成了零价铜 . CuFeO_2的催化活性和稳定性较差,在还原气氛中催化 CO- NO反应过程中,样品被还原,完全转化成了 Cu0和 CuFe2O4.  相似文献   

17.
采用微波辐射老化沉淀母液的方法,着重考察了沉淀方式对制备的CuO/ZnO/Al2O3催化剂及其前驱体的结构和催化性能的影响。实验结果表明,沉淀方式对催化剂的活性和稳定性影响较大,其活性顺序为分步沉淀法二>并流共沉淀法>分步沉淀法一>反加法>正加法。通过XRD、DTG、H2-TPR等表征分析表明,先并流沉淀Al(NO3)3溶液和Na2CO3溶液,再并流沉淀Cu(NO3)2-Zn(NO3)2混合溶液与剩下的Na2CO3溶液,然后微波辐射老化所制备前驱体中含有更多的绿铜锌矿 (Cu,Zn)5 (CO3)2(OH)6物相,焙烧后形成的CuO-ZnO协同作用强,且CuO分散性好,H2还原温度较低,催化活性和稳定性也较高。  相似文献   

18.
采用并流淤浆混合法制备了一系列具有不同铜锌铝比的铜基甲醇合成催化剂CuO/ZnO/Al2O3,测试了其催化性能(甲醇收率和CO转化率)及物相结构,并对该制备方法进行评价。Cu∶Zn∶Al摩尔比为4∶5∶1 的铜基催化剂显示了最好的催化活性。通过对催化剂前驱物煅烧过程进行DTA分析及对前驱物进行XRD分析表明, 催化剂前驱物的物相与Al2O3的量有关。当Al2O3的量较低时,前驱物的物相以(Cu0.3 Zn0.7)5(CO3)2(OH)6为主;当Al2O3的量较高时,前驱物中物相(Cu0.3Zn0.7)5(CO3)2(OH)6的量下降,而物相Cu2CO3(OH)2的量增加。物相(Cu0.3 Zn0.7)5(CO3)2(OH)6对终态催化剂的活性是十分有利的 。  相似文献   

19.
The transition metals (Cu, Co, and Fe) were applied to modify Ni/Ce0.2Zr0.1Al0.7Oδ catalyst.The effects of transition metals on the catalytic properties of Ni/Ce0.2Zr0.1Al0.7Oδ autothermal reforming of methane were investigated. The Ni-supported catalysts were characterized by XRD, TPR and XPS.Tests in autothermal reforming of methane to hydrogen showed that the addition of transition metals (Cu and Co) significantly increased the activity of catalyst under the conditions of lower reaction temperature,and Ni/Cu0.05Ce0.2Zr0.1Al0.65Oδ was found to have the highest conversion of CH4 among all catalysts in the operation temperatures ranging from 923 K to 1023 K. TPR, XRD and XPS measurements indicated that the cubic phases of CexZr1-xO2 solid solution were formed in the preparation process of catalysts.Strong interaction was found to exist between NiO and CexZr1-xO2 solid solution. The addition of Cu improved the dispersion of NiO, inhibited the formation of NiAl2O4, and thus significantly promoted the activity of the catalyst Ni/Cu0.05Ce0.2Zr0.1Al0.65Oδ.  相似文献   

20.
ABO2型复合氧化物上CO-NO的反应性能   总被引:4,自引:0,他引:4  
以柠檬酸络合法制备了CuCrO2、CuAlO2和CuFeO2等具有铜铁矿结构的ABO2型复合氧化物,并考察了它们在氧化和还原气氛中对CO NO反应的影响. CuAlO2和CuCrO2具有好的催化活性, CuCrO2更具有相当的稳定性,经过氧化和还原条件下的CO NO反应后,体相组成仍然保持不变. CuAlO2在还原条件下,部分被还原生成了零价铜. CuFeO2的催化活性和稳定性较差,在还原气氛中催化CO NO反应过程中,样品被还原,完全转化成了Cu0和CuFe2O4.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号