高比表面积二硫化钼的制备及其对喹啉选择加氢反应的催化性能_马崇乐

文章编号:0253 9837(2009)01 0078 05

研究论文:78~82

收稿日期:2008 09 16.

联系人:梁长海.T el:(0411)39608806;Fax:(0411)88993991;E mai l:changhai@dl .基金来源:新世纪优秀人才支持计划(NCET 07 0133);大连市科学技术基金(2007J22JH008).

高比表面积二硫化钼的制备及其对喹啉

选择加氢反应的催化性能

马崇乐, 金 鑫, 丁 玲, 张秋民, 邱介山, 梁长海

(大连理工大学化工学院精细化工国家重点实验室炭素材料研究室,辽宁大连116012)

摘要:通过四硫代钼酸铵与四甲基氯化铵的甲基取代反应合成了四甲基四硫代钼酸铵,并通过四甲基四硫代钼酸铵热解制备了具有较高比表面积的二硫化钼.结果显示,由四甲基四硫代钼酸铵热解可以得到比表面积为108m 2/g 以上的二硫化钼,而由四硫代钼酸铵热解得到的二硫化钼样品的比表面积仅为16m 2/g.由四甲基四硫代钼酸铵热解得到的二硫化钼样品具有较低的结晶度,样品具有像干酪样状的半球形和卵形孔穴排列的特点,其孔径尺寸为4~12nm.四甲基四硫代钼酸铵热解制备的二硫化钼在喹啉选择加氢中显示出较高的催化活性和选择性.

关键词:四硫代钼酸铵;四甲基氯化铵;四甲基四硫代钼酸铵;二硫化钼;喹啉;选择加氢中图分类号:O643/T Q 42 文献标识码:A

Preparation of High Surface Area MoS 2and Its Catalytic Performance

for Selective Hydrogenation of Quinoline

MA Chongle,JIN Xin,DING Ling,ZHANG Qiumin,QIU Jieshan,LIANG Changhai *

(Car bon Resear ch Labor atory ,S tate K ey L aboratory of Fine Chemicals,School of Chemical Engineer ing ,

D alian U niver sity of T echnology ,Dalian 116012,Liaoning,China)

Abstract :T etramethylammonium thiomolybdate,being used as a precursor for molybdenum disulfide,w as synthesized at r oom tem perature using an aqueous solution of ammonium tetrathiomolybdate and tetramethylammonium chloride.M olybdenum disulfide w as prepared by t he decomposition of tetr amethylammonium thiomolybdate or ammonium tetrathiomolybdate and w as char acterized by N 2physisor ption,X r ay diffraction,and scanning electron microscopy.T he results showed that molybdenum disulfide pr epared fr om te tramethylammonium thiomolybdate had higher specific surface area of 108m 2/g with narr ower pore size distribution of 4-12nm,

w hile the sample prepared from ammonium tetr athiomolybdate had a specific sur face area of only 16m 2

/g.T he cr ystalline of the molybdenum disulfide prepared from tetramet hylammonium thiomolybdate was low er than that from ammonium tetrathio molybdate.T he high sur face area molybdenum disulfide possessed higher catalytic activity and higher selectivity for 1,2,3,4 tetrahydr oquinoline in the selective hydrog enation of quinoline in a fix ed bed reactor.T he catalytic perfo rmance of hig h surface area molybdenum di sulfide w as similar to that of noble metal catalysts in the selective hydr ogenation of quinoline.

Key w ords :ammonium tetrathiomolybdate;tetramethylammonium chloride;tetr amethylammonium thiomoly bdate;molybdenum disulfide;quinoline;selective hydrogenation

1,2,3,4 四氢喹啉及其衍生物广泛应用于药物中间体、农药及染料等的合成[1]

.工业上合成1,2,3,4 四氢喹啉及其衍生物的方法主要有化学合成和催化喹啉加氢[2~

4]

.采用催化喹啉加氢制取1,2,

3,4 四氢喹啉是最简单可行的途径,具有反应步骤少、原料成本低的优点.喹啉加氢的主产物可以是1,2,3,4 四氢喹啉、5,6,7,8 四氢喹啉或十氢喹啉.Ru 和Rh 等贵金属催化剂对喹啉加氢具有较高的

第30卷第1期催 化 学 报

2009年1月Vol.30No.1

Chinese Jour nal of Catalysis

Januar y 2009