甲酸在超临界水中分解反应的密度泛函理论研究

张永春; 张军; 曾娜; 盛昌栋; 徐益谦

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甲酸在超临界水中分解反应的密度泛函理论研究

更新时间：2025-07-09

- 甲酸在超临界水中分解反应的密度泛函理论研究
- Study on Formic Acid Decomposition in Supercritical Water with Density Functional Theory
- 西安交通大学学报 2009年43卷第7期页码：30-35
- 作者机构：
  
  东南大学热能工程研究所,南京,210096
- 作者简介：
- 基金信息：
  
  : 2008-10-19. 作者简介: 张永春(1982-),男,博士生;张军(联系人),男,教授,博士生导师. 基金项目: 国家重点基础研究发展规划资助项目(2009CB220007)
- DOI：
  中图分类号： TK61
- 网络首发：2009-07-10，
  
  纸质出版：2009
- 稿件说明：
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张永春, 张军, 曾娜, 等. 甲酸在超临界水中分解反应的密度泛函理论研究[J]. 西安交通大学学报, 2009,43(7):30-35.

Study on Formic Acid Decomposition in Supercritical Water with Density Functional Theory[J]. 2009, 43(7): 30-35.
张永春, 张军, 曾娜, 等. 甲酸在超临界水中分解反应的密度泛函理论研究[J]. 西安交通大学学报, 2009,43(7):30-35. DOI：

Study on Formic Acid Decomposition in Supercritical Water with Density Functional Theory[J]. 2009, 43(7): 30-35. DOI：

摘要

采用密度泛函方法(B3LYP)在6-311+g(3df

2p)基组水平上研究了甲酸在超临界水中分解的微观反应机理.研究结果表明:甲酸在超临界水中的分解反应存在多条反应通道

反应历程复杂

其中通道R〖FY1〗IM1〖FY1〗TS4〖FY1〗IM4〖FY1〗TS5〖FY1〗P1和R〖FY1〗IM3〖FY1〗TS14〖FY1〗P2为主通道

分别对应甲酸脱羧反应和脱羰反应; H

O作为催化剂参与了甲酸分解反应

使得脱羧反应和脱羰反应的反应势垒明显降低

促进了甲酸分解

且对脱羧反应的促进作用更为明显.利用传统过渡态理论

分别计算出2条主通道的速控步骤在压力为25 MPa、温度为700～1 500 K范围内的速率常数表达式分别为k

=4.68×10

exp(-22 231.46/T)s

-1

和k

=5.34×10

exp(-24 587.05/T)s

-1

Abstract

The reaction mechanism of formic acid decomposition in supercritical water was investigated theoretically at the B3LYP/6-311+g(3df

2p)level. The results show that there are several reaction channels in the decomposition of formic acid

and the channels

R〖FY1〗IM1〖FY1〗TS4〖FY1〗IM4〖FY1〗TS5〖FY1〗P1 and R〖FY1〗IM3〖FY1〗TS14〖FY1〗P2

are the main reaction channels

corresponding to decarboxylation and dehydration reactions

respectively. H

O takes part in the formic acid decomposition reaction as a catalyst

which lowers the energy barrier heights of both decarboxylation and dehydration reactions and accelerates the decomposition of formic acid. The rate constants of decarboxylation(k

)and dehydration(k

)were obtained using the transition state theory(TST)at the pressure of 250 MPa and in the temperature range of 700-1500 K: k

=4.68×10

exp(-22 231.46/T)s

-1

and k

=5.34×10

exp(-24 587.05/T)s

-1

关键词

Keywords

references

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