Nb2O5/TiO2催化剂表面铌氧物种的分散状态和催化性能

化学学报 ›› 2004, Vol. 62 ›› Issue (14): 1311-1317. 上一篇下一篇

Nb₂O₅/TiO₂催化剂表面铌氧物种的分散状态和催化性能

何杰^1,2, 范以宁¹, 邱金恒¹, 陈懿¹

1. 南京大学化学系, 介观材料实验室, 南京, 210093;
2. 安徽理工大学, 化工系, 淮南, 232001

投稿日期:2003-09-18 修回日期:2004-03-12 发布日期:2014-02-17
通讯作者: 范以宁,E-mail:chem612@nju.edu.cn E-mail:chem612@nju.edu.cn
基金资助:
国家重点基础研究发展规划(No.G1999022400)和南京大学分析测试基金项目资助.

Dispersion State and Catalytic Properties of Niobia Species on the Surface of Nb₂O₅/TiO₂ Catalysts

HE Jie^1,2, FAN Yi-Ning¹, QIU Jin-Heng¹, CHEN Yi¹

1. Laboratory of Mesoscopic Materials Science, Department of Chemistry, Nanjing University, Nanjing 210093;
2. Department of Chemical Engineering, Anhui University of Science and Technology, Huainan 232001

Received:2003-09-18 Revised:2004-03-12 Published:2014-02-17

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摘要/Abstract

用X射线粉末衍射(XRD)、拉曼光谱(LRS)、Hammett指示剂和微反测试等方法考察了负载型Nb₂O₅/TiO₂催化剂表面铌氧(NbO_x)物种的分散状态、表面酸性和催化异丁烯(IB)与异丁醛(IBA)缩合生成2,5-二甲基-2,4-己二烯(DMHD)反应的催化性能.实验测得Nb₂O₅在TiO₂表面的分散容量为0.94mmol Nb/100m²TiO₂,与"嵌入模型"理论计算值相近.当负载量低于分散容量的1/3时,Nb₂O₂主要以孤立的NbO_x物种通过Nb-O-Ti链与载体表面相连,这种孤立的NbO_x物种酸性很弱,催化活性很低.随负载量的增加,孤立的NbO_x物种通过Nb-O-Nb键连接聚合,表面酸性增强,IB与IBA缩合生成DMHD的转化数(TON)增加.当Nb₂O₅负载量超过分散容量时,表面NbO_x物种主要是通过Nb-O-Nb化学键相连形成多层的Nb₂O₅,虽然催化剂的强酸中心数量有所增加,但NbO_x物种表面利用率下降,催化活性增加幅度趋缓.

关键词: Nb₂O₅, TiO₂, 分散容量, 表面酸性, 烯醛缩合反应

The dispersion state, surface acidity and catalytic properties of anatase-supported niobia species have been studied by means of X-ray powder diffraction (XRD), laser Raman spectroscopy (LRS), Hammett indicator method and the condensation reaction of isobutene (IB) with isobutyraldehyde (IBA) to 2,5-dimethyl-2,4-hexadiene (DMHD).The almost identical values of the experimental dispersion capacity of Nb₂O₅ on anatase (0.94 mmol Nb/100 m² TiO₂) and the value derived theoretically by the incorporation model (0.98 mmol Nb/100 m² TiO₂) suggest that the highly dispersed niobium cations are bonded to the vacant sites on the preferentially exposed surface (001) of anatase.When the loading amount of Nb₂O₅ is below 1/3 of its dispersion capacity, the dispersed niobia species might mainly consist of isolated NbO_x species bridging to the surface through Nb—O—Ti bonds.With the increase of Nb₂O₅ loading the isolated niobia species interact with their nearest neighbors through bridging Nb—O—Nb at the expenses of Nb—O—Ti bonds, resulting in the increase of the ratio of polymerized to isolated niobia species and the increase of surface acidic strength and catalytic activity for the condensation reaction.When the loading amount of Nb₂O₅ is higher than its dispersion capacity, the catalytic activity increases slightly with the increase of Nb₂O₅ loading due to the formation of bulk Nb₂O₅ in which Nb—O—Nb species are only partially exposed on the surface.

Key words: niobium pentaoxide, titanium oxide, dispersion capacity, surface acidity, olefin-aldehyde condensation reaction

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何杰, 范以宁, 邱金恒, 陈懿. Nb₂O₅/TiO₂催化剂表面铌氧物种的分散状态和催化性能[J]. 化学学报, 2004, 62(14): 1311-1317.

HE Jie, FAN Yi-Ning, QIU Jin-Heng, CHEN Yi. Dispersion State and Catalytic Properties of Niobia Species on the Surface of Nb₂O₅/TiO₂ Catalysts[J]. Acta Chimica Sinica, 2004, 62(14): 1311-1317.

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Nb₂O₅/TiO₂催化剂表面铌氧物种的分散状态和催化性能

Dispersion State and Catalytic Properties of Niobia Species on the Surface of Nb₂O₅/TiO₂ Catalysts

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