纳米团簇Au19Pd和Au19Pt催化解离N2O
采用密度泛函理论研究Au-Pd和Au-Pt纳米团簇催化解离N2O.首先根据计算得到Au19Pd和Au19Pt团簇的最优构型（杂原子均位于团簇的表面）.以Au19Pd催化解离N2O为例研究催化解离的反应机理.对此主要考虑两个反应机理,分别是Eley-Rideal（ER）和Langmuir-Hinshelwood（LH）.第一个机理中N2O解离的能垒是1.118 e V,并且放热0.371 e V.N2分子脱附后,表面剩余的氧原子沿着ER路径消除需要克服的能垒是1.920e V,这比反应沿着LH路径的能垒高0.251 e V.此外根据LH机理,氧原子在表面的吸附能是-3.203 e V,而氧原子在...
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| Published in | 物理化学学报 Vol. 31; no. 3; pp. 425 - 434 |
|---|---|
| Main Author | |
| Format | Journal Article |
| Language | Chinese |
| Published |
福州大学化学系,福州,350116%成都理工大学核技术与自动化工程学院,成都,610059
2015
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| Subjects | |
| Online Access | Get full text |
| ISSN | 1000-6818 |
| DOI | 10.3866/PKU.WHXB201501191 |
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| Abstract | 采用密度泛函理论研究Au-Pd和Au-Pt纳米团簇催化解离N2O.首先根据计算得到Au19Pd和Au19Pt团簇的最优构型（杂原子均位于团簇的表面）.以Au19Pd催化解离N2O为例研究催化解离的反应机理.对此主要考虑两个反应机理,分别是Eley-Rideal（ER）和Langmuir-Hinshelwood（LH）.第一个机理中N2O解离的能垒是1.118 e V,并且放热0.371 e V.N2分子脱附后,表面剩余的氧原子沿着ER路径消除需要克服的能垒是1.920e V,这比反应沿着LH路径的能垒高0.251 e V.此外根据LH机理,氧原子在表面的吸附能是-3.203 e V,而氧原子在表面转移所需的能垒是0.113 e V,这表明氧原子十分容易在团簇表面转移,从而促进氧气分子的生成.因此,LH为最优反应路径.为了比较Au19Pd和Au19Pt对N2O解离的活性,根据最优的反应路径来研究Au19Pt催化解离N2O,得到作为铂族元素的铂和钯对N2O的解离有催化活性,尤其是钯.同时,将团簇与文献中的Au-Pd合金相比较,得到这两种团簇对N2O解离有较高的活性,尤其是Au19Pd团簇.再者,O2的脱附不再是影响反应的主要原因,这可以进一步提高团簇解离N2O的活性. |
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| AbstractList | 采用密度泛函理论研究Au-Pd和Au-Pt纳米团簇催化解离N2O.首先根据计算得到Au19Pd和Au19Pt团簇的最优构型（杂原子均位于团簇的表面）.以Au19Pd催化解离N2O为例研究催化解离的反应机理.对此主要考虑两个反应机理,分别是Eley-Rideal（ER）和Langmuir-Hinshelwood（LH）.第一个机理中N2O解离的能垒是1.118 e V,并且放热0.371 e V.N2分子脱附后,表面剩余的氧原子沿着ER路径消除需要克服的能垒是1.920e V,这比反应沿着LH路径的能垒高0.251 e V.此外根据LH机理,氧原子在表面的吸附能是-3.203 e V,而氧原子在表面转移所需的能垒是0.113 e V,这表明氧原子十分容易在团簇表面转移,从而促进氧气分子的生成.因此,LH为最优反应路径.为了比较Au19Pd和Au19Pt对N2O解离的活性,根据最优的反应路径来研究Au19Pt催化解离N2O,得到作为铂族元素的铂和钯对N2O的解离有催化活性,尤其是钯.同时,将团簇与文献中的Au-Pd合金相比较,得到这两种团簇对N2O解离有较高的活性,尤其是Au19Pd团簇.再者,O2的脱附不再是影响反应的主要原因,这可以进一步提高团簇解离N2O的活性. O641; 采用密度泛函理论研究Au-Pd和Au-Pt纳米团簇催化解离N2O.首先根据计算得到Au19Pd和Au19Pt团簇的最优构型(杂原子均位于团簇的表面).以Au19Pd催化解离N2O为例研究催化解离的反应机理.对此主要考虑两个反应机理,分别是Eley-Rideal (ER)和Langmuir-Hinshelwood (LH).第一个机理中N2O解离的能垒是1.118 eV,并且放热0.371 eV. N2分子脱附后,表面剩余的氧原子沿着ER路径消除需要克服的能垒是1.920 eV,这比反应沿着LH路径的能垒高0.251 eV.此外根据LH机理,氧原子在表面的吸附能是-3.203 eV,而氧原子在表面转移所需的能垒是0.113 eV,这表明氧原子十分容易在团簇表面转移,从而促进氧气分子的生成.因此, LH为最优反应路径.为了比较Au19Pd和Au19Pt对N2O解离的活性,根据最优的反应路径来研究Au19Pt催化解离N2O,得到作为铂族元素的铂和钯对N2O的解离有催化活性,尤其是钯.同时,将团簇与文献中的Au-Pd合金相比较,得到这两种团簇对N2O解离有较高的活性,尤其是Au19Pd团簇.再者, O2的脱附不再是影响反应的主要原因,这可以进一步提高团簇解离N2O的活性. |
| Abstract_FL | The catalytic decomposition of N2O using Au19Pd and Au19Pt clusters as catalysts with optimized geometries was studied using density functional theory (DFT). The optimized geometries of the Au19Pd and Au19Pt clusters were obtained as a function of structural and thermodynamic analyses, in which the heteroatoms are on the surfaces of the clusters. We selected the Au19Pd cluster as a model cluster to investigate the reaction mechanism of N2O decomposition. There are two reaction pathways to be considered:Eley-Rideal (ER) and Langmuir-Hinshelwood (LH). We found that the first N2O decomposition needs to surmount an energy barrier of 1.118 eV, and is exothermic by 0.371 eV. The elimination of the residual oxygen atom on the surface has an energy barrier of 1.920 eV along the ER pathway after N2 desorption, which is higher than that along the LH channel (1.669 eV). The adsorption energy of the oxygen atom on the surface is-3.203 eV, and the oxygen atom diffusion on the surface needs to surmount an energy barrier of 0.113 eV along the LH pathway. This indicates that the oxygen atom is prone to transfer on the cluster to promote the generation of the O2 molecule, and therefore the LH is the optimized reaction pathway. We investigated the catalytic activity of Au19Pt for N2O decomposition along the LH pathway in comparison with the Au19Pd cluster. Both platinum and pal adium have catalytic activities for N2O decomposition, especial y the pal adium in this study. Comparison between this work and the theoretical study on periodic systems shows that these two clusters can be used as better catalysts for N2O decomposition, especial y the Au19Pd cluster. Furthermore, the O2 desorption is no longer the main barrier to the reaction, which further enhances the catalytic activities of these two clusters for N2O decomposition. |
| Author | 俞炜铃 左会文 陆春海 李奕 章永凡 陈文凯 |
| AuthorAffiliation | 福州大学化学系,福州350116 成都理工大学核技术与自动化工程学院,成都610059 |
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| Author_FL | ZUO Hui-Wen CHEN Wen-Kai LI Yi ZHANG Yong-Fan YU Wei-Ling LU Chun-Hai |
| Author_FL_xml | – sequence: 1 fullname: YU Wei-Ling – sequence: 2 fullname: ZUO Hui-Wen – sequence: 3 fullname: LU Chun-Hai – sequence: 4 fullname: LI Yi – sequence: 5 fullname: ZHANG Yong-Fan – sequence: 6 fullname: CHEN Wen-Kai |
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| Copyright | Copyright © Wanfang Data Co. Ltd. All Rights Reserved. |
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| DOI | 10.3866/PKU.WHXB201501191 |
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| DocumentTitleAlternate | Nitrous Oxide Decomposition Catalyzed by Au19Pd and Au19Pt Clusters |
| DocumentTitle_FL | Nitrous Oxide Decomposition Catalyzed by Au19Pd and Au19Pt Clusters |
| EndPage | 434 |
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| Issue | 3 |
| Keywords | Nanocluster 纳米团簇 反应机理 N2O decomposition 催化活性 N2O解离 Reaction mechanism Catalytic activity |
| Language | Chinese |
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| Notes | 11-1892/06 YU Wei-Ling, ZUO Hui-Wen, ZHANG Yong-Fan, LU Chun-Hai, LI Yi, CHEN Wen-Kai （1.Department of Chemistry, Fuzhou University, Fuzhou 350116, P R. China; 2.College of Nuclear Technology and Automation Engineering, Chengdu University of Technology, Chengdu 610059, P. R. China） Nanocluster; Catalytic activity; N2O decomposition; Reaction mechanism The catalytic decomposition of N2 O using Au19 Pd and Au19 Pt clusters as catalysts with optimized geometries was studied using density functional theory（DFT）. The optimized geometries of the Au19 Pd and Au19 Pt clusters were obtained as a function of structural and thermodynamic analyses, in which the heteroatoms are on the surfaces of the clusters. We selected the Au19 Pd cluster as a model cluster to investigate the reaction mechanism of N2 O decomposition. There are two reaction pathways to be considered： Eley-Rideal（ER） and Langmuir-Hinshelwood（LH）. We found that the first N2 O decomposition needs to surmount an energy barrier of 1.118 e V, and is exothermic b |
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| PublicationTitle | 物理化学学报 |
| PublicationTitleAlternate | Acta Physico-Chimica Sinica |
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| PublicationYear | 2015 |
| Publisher | 福州大学化学系,福州,350116%成都理工大学核技术与自动化工程学院,成都,610059 |
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| Snippet | 采用密度泛函理论研究Au-Pd和Au-Pt纳米团簇催化解离N2O.首先根据计算得到Au19Pd和Au19Pt团簇的最优构型（杂原子均位于团簇的表面）.以Au19Pd催化解离N2O为例研究催化解离... O641; 采用密度泛函理论研究Au-Pd和Au-Pt纳米团簇催化解离N2O.首先根据计算得到Au19Pd和Au19Pt团簇的最优构型(杂原子均位于团簇的表面).以Au19Pd催化解离N2O为例研究催化... |
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| StartPage | 425 |
| SubjectTerms | N2O解离 催化活性 反应机理 纳米团簇 |
| Title | 纳米团簇Au19Pd和Au19Pt催化解离N2O |
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