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[1]郑建辉,王成,崔文文,等.1(TiO2)n(n=1~3)催化水解异氰酸的反应机制[J].南京工业大学学报(自然科学版),2013,35(04):82-86.[doi:10.3969/j.issn.1671-7627.2013.04.017]
 ZHENG Jianhui,WANG Cheng,CUI Wenwen,et al.Hydrolysis reaction mechanism of isocyanic acid catalyzed by titanium dioxide clusters[J].Journal of NANJING TECH UNIVERSITY(NATURAL SCIENCE EDITION),2013,35(04):82-86.[doi:10.3969/j.issn.1671-7627.2013.04.017]
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1(TiO2)n(n=1~3)催化水解异氰酸的反应机制()
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《南京工业大学学报(自然科学版)》[ISSN:1671-7627/CN:32-1670/N]

卷:
35
期数:
2013年04期
页码:
82-86
栏目:
出版日期:
2013-07-01

文章信息/Info

Title:
Hydrolysis reaction mechanism of isocyanic acid catalyzed by titanium dioxide clusters
文章编号:
1671-7627(2013)04-0082-05
作者:
郑建辉王成崔文文朱小蕾
南京工业大学 化学化工学院 材料化学工程国家重点实验室,江苏 南京 210009
Author(s):
ZHENG JianhuiWANG ChengCUI WenwenZHU Xiaolei
State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemistry and Chemical Engineering,Nanjing University of Technology,Nanjing 210009,China
关键词:
过渡金属氧化物 异氰酸 催化机制 势能面
Keywords:
transition metal oxide isocyanic acid catalytic mechanism potential energy surface
分类号:
O643.12
DOI:
10.3969/j.issn.1671-7627.2013.04.017
文献标志码:
A
摘要:
采用B3LYP方法对N、H、C、O使用6-311++G(d,p)基组,对Ti使用LANL2DZ赝势基组,研究计算1(TiO2)n(n=1~3)催化水解HNCO的微观反应机制。研究HNCO和H2O在1(TiO2)n上的不同进攻方式。为了考察催化剂对反应的影响,研究了在没有催化剂作用下的HNCO+H2O的微观反应机制。结果表明:无催化剂条件下反应的发生需要克服活化能158.20 kJ/mol。1(TiO2)n对反应有着良好的催化效果,显著降低了反应的活化能垒,使反应能够在温和的条件下进行。H2O优先进攻催化剂的方式是能量上有利的过程,与实验结果吻合。
Abstract:
The reaction mechanism of HNCO and H2O catalyzed by 1(TiO2)n (n=1-3)was investigated.The properties of non-covalent interactions in intermediates and transition states with weak bond were obtained by using standardized 6-311++G(d,p)for carbon,oxygen, hydrogen, and nitrogen atoms and the effective core potential(ECP)of Hay and Wadt with a double-ζ basis set(LANL2DZ)for Ti using B3LYP method.The different attack modes of HNCO and H2O on 1(TiO2)n(n=1-3)were explored,and the reaction mechanism of HNCO+H2O without any catalyst was also investigated to examine the effect of 1(TiO2)n catalysts on the HNCO hydrolysis reaction.The results demonstrated that the reaction HNCO+H2O should overcome the highest activity energy of 158.20 kJ/mol if there was no catalyst.1(TiO2)n was active for the hydrolysis of the isocyanic acid and lowered the activity barrier in the process.The catalytic reaction could take place at a lower temperature.The first attack of H2O on the catalyst was energetically favorable,which was consistent with the experimental results.

参考文献/References:

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备注/Memo

备注/Memo:
收稿日期:2012-12-12
基金项目:国家自然科学基金(20706029,20876073,21136001)
作者简介:郑建辉(1986—),男,江苏丹阳人,硕士,主要研究方向为催化反应; 朱小蕾(联系人),教授,E-mail:xlzhu@njut.edu.cn..
更新日期/Last Update: 2013-07-07