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[1]朱鹏,黎军,陆小华.Ag9团簇上由H2和O2直接合成H2O2的密度泛函理论研究[J].南京工业大学学报(自然科学版),2019,41(04):514-519.[doi:10.3969/j.issn.1671-7627.2019.04.018]
 ZHU Peng,LI Jun,LU Xiaohua.Density functional theory study of direct synthesis of H2O2 from H2 and O2 on Ag9 cluster[J].Journal of NANJING TECH UNIVERSITY(NATURAL SCIENCE EDITION),2019,41(04):514-519.[doi:10.3969/j.issn.1671-7627.2019.04.018]
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Ag9团簇上由H2和O2直接合成H2O2的密度泛函理论研究()
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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:
41
期数:
2019年04期
页码:
514-519
栏目:
出版日期:
2019-07-24

文章信息/Info

Title:
Density functional theory study of direct synthesis of H2O2 from H2 and O2 on Ag9 cluster
文章编号:
1671-7627(2019)04-0514-06
作者:
朱鹏黎军陆小华
南京工业大学 材料化学工程国家重点实验室,江苏 南京 211800
Author(s):
ZHU PengLI JunLU Xiaohua
State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, Nanjing 211800, China
关键词:
直接法合成H2O2 Ag团簇 反应机制 密度泛函理论计算
Keywords:
direct synthesis of hydrogen peroxide Ag cluster reaction mechanism density functional theory calculations
分类号:
O641.4
DOI:
10.3969/j.issn.1671-7627.2019.04.018
文献标志码:
A
摘要:
应用密度泛函理论对H2和O2在Ag9团簇上直接合成H2O2的可能性进行研究。计算H2和O2在Ag9团簇上的吸附性质以及由H2和O2生成H2O2的反应机制。结果表明:O2可以在Ag9团簇上稳定吸附,但H2很难与Ag9团簇作用,只有通过Ag—O键才能发生解离。生成H2O2的过程可以分为两个阶段:首先解离两个H2分子形成第一个H2O2分子,其中裂解第二个H2分子为速度控制步骤,所需活化能为108.7 kJ/mol; 再吸附的O2分子夺取Ag9团簇上两个H原子形成第二个H2O2分子,其中OOH自由基夺取Ag9团簇上的H原子为速度控制步骤,活化能为124.7 kJ/mol。与文献中Pd、Au和Pd-Au团簇上由H2和O2生成H2O2的理论研究结果相比,Ag9团簇具有促进H2和O2直接合成H2O2的催化活性。
Abstract:
The theoretical possibility of direct synthesis of H2O2 from H2 and O2 on Ag9 cluster was studied with density functional theory calculations. The adsorption of H2 and O2 and the mechanism for H2O2 formation on Ag9 cluster was considered. Results showed that O2 could be steadily adsorbed on Ag9 cluster, but H2 could not interact with Ag9 cluster. H2 only could react with the Ag—O bond. There were two stages through the path of H2O2 production from H2 and O2 on Ag9 cluster: the first H2O2 molecule was formed by cleaving two H2 molecules, in which the rate-limiting step was the dissociation of the second H2 with an activation energy of 108.7 kJ/mol. The second H2O2 molecule was formed from the reaction of the H atoms on Ag9 cluster with a new O2 molecule, in which the rate-limiting step was the coupling of the hydroperoxy(OOH)raclical intermediate with an H atom with an activation energy of 124.7 kJ/mol. By comparison with the theoretical study results on Pd, Au and Pd-Au clusters in the literature, it was known that Ag9 cluster should have catalytic activity for the direct synthesis of H2O2 from H2 and O2.

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备注/Memo

备注/Memo:
收稿日期:2018-04-26
基金项目:国家重点基础研究发展计划(973计划,2013CB733505,2013CB733501); 国家自然科学基金(91334202); 江苏省自然科学基(BK2012421); 教育部博士点专项科研基金(20123221120015)
作者简介:朱鹏(1989—),男,E-mail:njzhupeng@foxmail.com; 黎军(联系人),教授,E-mail:lijun@njtech.edu.cn.
引用本文:朱鹏,黎军,陆小华.Ag9团簇上由H2和O2直接合成H2O2的密度泛函理论研究[J].南京工业大学学报(自然科学版),2019,41(4):514-519..
更新日期/Last Update: 2019-07-20