在Pt(111)上甲酸氧化CO形成的新的洞察:甲酸二聚体分子间脱水
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- 英文论文题名：New Insight into CO Formation during HCOOH Oxidation on Pt(111): Intermolecular Dehydration of HCOOH Dimers
- 论文作者：钟文辉 ; 江俊
- 英文论文作者：Wenhui Zhong ; Jun Jiang ; Guizhou Provincial Key Laboratory of Computational Nano-Material Science ; Guizhou Normal College ; School of Chemistry and Materials Science ; Hefei National Laboratory for Physical Sciences at the Microscale ; University of Science and Technology of China (USTC)
- 年：2016
- 作者机构：贵州师范学院;中国科学技术大学;
- 论文关键词：CO形成 ; HCOOH氧化 ; 二聚体分子 ; Pt(111)
- 会议召开时间：2016-07-01
- 会议录名称：中国化学会第30届学术年会摘要集-第四十分会：纳米体系理论与模拟
- 语种：中文
- 分类号：TM911.4;O643.36
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会-第四十分会 ; 纳米体系理论与模拟
- 会议地点：中国辽宁大连
- 主办单位：中国化学会
- 学会名称：中国化学会
- 页数：1
- 文件大小：176k
- 原文格式：D
- 会议级别：全国
摘要
直接甲酸燃料电池作为一种便携式电子设备的主要电源,具有高的能量密度、无毒以及快速的氧化动力学等优点,引起了人们广泛的兴趣[1]。然而常用的Pt基催化剂容易遭受CO中毒的影响[2],并且CO形成过程中的中间体以及相应的机理尚不清楚,迫切需要开展系统的理论研究。本文通过密度泛函理论计算研究各种甲酸二聚体模型在溶液相中Pt(111)上的CO形成机理。研究结果表明Pt催化剂的CO形成通过4条主要的分子间脱水路径进行,并且这4条路径的速控步势垒是非常低的(0.46-0.79 e V),这个工作表明甲酸二聚体的存在是对Pt基催化剂的CO中毒负责的,并且阐明了在不同的甲酸氧化实验中存在争议的中间体和CO形成机理。
Density functional theory simulations were performed to investigate CO formation during HCOOH oxidation on Pt(111) surface in aqueous phase, through the intermolecular dehydrations of various HCOOH dimer models. The formation of CO that poisoning Pt catalysts is found to proceeds via four major intermolecular dehydration pathways. The computed rate-determining energy barriers of those four pathways are low. This work demonstrates that the presence of HCOOH dimers accounts for the easy CO poisoning of Pt-based catalysts, and clarifies the controversy on the intermediates and mechanisms of CO formation found in different HCOOH oxidation experiments.
Density functional theory simulations were performed to investigate CO formation during HCOOH oxidation on Pt(111) surface in aqueous phase, through the intermolecular dehydrations of various HCOOH dimer models. The formation of CO that poisoning Pt catalysts is found to proceeds via four major intermolecular dehydration pathways. The computed rate-determining energy barriers of those four pathways are low. This work demonstrates that the presence of HCOOH dimers accounts for the easy CO poisoning of Pt-based catalysts, and clarifies the controversy on the intermediates and mechanisms of CO formation found in different HCOOH oxidation experiments.
引文
[1]Tedsree,K.;Li,T.;Jones,S.;Chan,C.W.A.;Yu,K.M.K.;Bagot,P.A.J.;Marquis,E.A.;Smith,G.D.W.;Tsang,S.C.E.Nat.Nanotechnol.2011,6:302.
[2]Rice,C.;Ha,S.;Masel,R.I.;Wieckowski,J.Power Sources 2003,115:229.
[2]Rice,C.;Ha,S.;Masel,R.I.;Wieckowski,J.Power Sources 2003,115:229.