Density functional study of selective oxidation of ethanol over silver catalysts

XU Xinchao; TIAN Pengfei; XU Jing; HAN Yifan

doi:10.11949/0438-1157.20190480

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Density functional study of selective oxidation of ethanol over silver catalysts

Catalysis\, kinetics and reactors | 更新时间：2026-07-24

- Density functional study of selective oxidation of ethanol over silver catalysts
- CIESC Journal Vol. 70, Issue 10, Pages: 3967-3975(2019)
- 作者机构：
  
  华东理工大学化学工程联合国家重点实验室，上海 200237
- 作者简介：
- 基金信息：
- DOI：10.11949/0438-1157.20190480
  CLC： TQ 032.4
- Received：07 May 2019，
  
  Revised：2019-08-14，
  
  Online First：24 July 2026，
  
  Published：05 October 2019
- 稿件说明：
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徐新潮, 田鹏飞, 徐晶, 韩一帆. Ag表面乙醇选择性催化氧化的密度泛函理论研究[J]. 化工学报, 2019, 70(10): 3967-3975

XU Xinchao, TIAN Pengfei, XU Jing, HAN Yifan. Density functional study of selective oxidation of ethanol over silver catalysts[J]. CIESC Journal, 2019, 70(10): 3967-3975
徐新潮, 田鹏飞, 徐晶, 韩一帆. Ag表面乙醇选择性催化氧化的密度泛函理论研究[J]. 化工学报, 2019, 70(10): 3967-3975 DOI： 10.11949/0438-1157.20190480.

XU Xinchao, TIAN Pengfei, XU Jing, HAN Yifan. Density functional study of selective oxidation of ethanol over silver catalysts[J]. CIESC Journal, 2019, 70(10): 3967-3975 DOI： 10.11949/0438-1157.20190480.

摘要

采用密度泛函理论计算对Ag(111)和Ag(211)表面乙醇催化氧化过程进行了系统性研究。研究发现原子氧物种是常温下乙醇氧化的关键中间体。在表面原子氧物种辅助下，乙醇O—H键和

-C—H键依次断裂，生成乙氧基中间体和乙醛产物（活化能（

）

38.0 kJ/mol）。乙醛随后与表面原子氧和羟基氧物种作用，导致CCOO（在Ag(111)表面发生CCOO

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=113939036&type=

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=113939058&type=

7.02733326

2.87866688

C+ CO

）和CH

COO（在Ag(211)表面发生CH

COO

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=113939060&type=

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=113939070&type=

7.02733326

2.87866688

+ CO

）中间体C—C键断裂生成CO

，该过程是速率控制步骤（

95.5 kJ/mol）。计算结果表明乙醇在Ag表面催化氧化过程为结构敏感反应，降低表面缺陷位数量可提高产物中乙醛选择性。

Abstract

A systematic study on the catalytic oxidation of Ag(111) and Ag(211) on the surface of Ag(111) was carried out by density functional theory. It was found that atomic O* is necessary to initiate the reaction at the ambient conditions. The O—H bond in the ethanol is activated with the help of adsorbed atomic O* to form ethoxy

which then further transfers hydrogen in

-C—H to adsorbed O* forming the acetaldehyde (

38 kJ/mol)

which

in turn

reacts with atomic O*/OH* to form final product CO

. To generate CO

C—C bond breaking (CCOO

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=113939061&type=

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=113939046&type=

7.02733326

2.87866688

C+ CO

on Ag(111) and CH

COO

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=113939062&type=

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=113939047&type=

7.02733326

2.87866688

+ CO

on Ag(211)) exhibits the highest barriers (

95.5 kJ/mol)

which indicated it is the rate-determining step. The results indicate that the catalytic oxidation of ethanol on silver surfaces is structural sensitive. Selectivity towards value-added products like acetaldehyde would be improved by reducing the density of defected sites.

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Keywords

references

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