Experimental and Mechanistic Understanding of Aldehyde Hydrogenation Using Au-25 Nanoclusters with Lewis Acids: Unique Sites for Catalytic Reactions
文献类型：期刊论文
| 作者 | Li, Gao3,4; Abroshan, Hadi1; Chen, Yuxiang1; Jin, Rongchao1; Kim, Hyung J.1,2 |
| 刊名 | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
 |
| 出版日期 | 2015-11-18 |
| 卷号 | 137期号:45页码:14295-14304 |
| ISSN号 | 0002-7863 |
| DOI | 10.1021/jacs.5b07716 |
| 文献子类 | Article |
| 英文摘要 | The catalytic activity of Au-25(SR)(18) nanoclusters (R = C2H4Ph) for the aldehyde hydrogenation reaction in the presence of a base, e.g., ammonia or pyridine, and transition-metal ions Mz+, such as Cu+, Cu2+, Ni2+ and Co2+, as a Lewis acid is studied. The addition of a Lewis acid is found to significantly promote the catalytic activity of Au-25(SR)(18)/CeO2 in the hydrogenation of benzaldehyde and a number of its derivatives. Matrix-assisted laser desorption ionization (MALDI) and electrospray ionization (ESI) mass spectrometry in conjunction with UV-vis spectroscopy confirm the generation of new species, Au25-n(SR)(18-n) (n = 1-4), in the presence of a Lewis acid. The pathways for the speciation of Au-24(SR)(17) from its parent Au-25(SR)(18) nanocluster as well as its structure are investigated via the density functional theory (DFT) method. The adsorption of M(z+) onto a thiolate ligand "-SR-" of Au-25(SR)(18), followed by a stepwise detachment of "-SR-" and a gold atom bonded to "-SR-" (thus an "Au-SR" unit) is found to be the most likely mechanism for the Au-24(SR)(17) generation. This in turn exposes the Au-13-core of Au-24(SR)(17) to reactants, providing an active site for the catalytic hydrogenation. DFT calculations indicate that Mz+ is also capable of adsorbing onto the Au13-core surface, producing a possible active metal site of a different kind to catalyze the aldehyde hydrogenation reaction. This study suggests, for the first time, that species with an open metal site like adducts [nanoparticle-M]((z-1)+) or fragments Au25-n(SR)(18-n) function as the catalysts rather than the intact Au-25(SR)(18). |
| WOS关键词 | SUPPORTED GOLD CATALYSTS ; CHEMOSELECTIVE HYDROGENATION ; SELECTIVE HYDROGENATION ; MOLECULAR CALCULATIONS ; OPTICAL-PROPERTIES ; CRYSTAL-STRUCTURE ; CO OXIDATION ; ACTIVE-SITE ; CLUSTERS ; LIGAND |
| WOS研究方向 | Chemistry |
| 语种 | 英语 |
| WOS记录号 | WOS:000365148500015 |
| 出版者 | AMER CHEMICAL SOC |
| 源URL | [http://cas-ir.dicp.ac.cn/handle/321008/171584]  |
| 专题 | 大连化学物理研究所_中国科学院大连化学物理研究所 |
| 通讯作者 | Jin, Rongchao |
| 作者单位 | 1.Carnegie Mellon Univ, Dept Chem, Pittsburgh, PA 15213 USA 2.Korea Inst Adv Study, Sch Computat Sci, Seoul 130722, South Korea 3.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Catalysis, Dalian 116023, Peoples R China 4.Chinese Acad Sci, Dalian Inst Chem Phys, Gold Catalysis Res Ctr, Dalian 116023, Peoples R China |
| 推荐引用方式 GB/T 7714 | Li, Gao,Abroshan, Hadi,Chen, Yuxiang,et al. Experimental and Mechanistic Understanding of Aldehyde Hydrogenation Using Au-25 Nanoclusters with Lewis Acids: Unique Sites for Catalytic Reactions[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2015,137(45):14295-14304. |
| APA | Li, Gao,Abroshan, Hadi,Chen, Yuxiang,Jin, Rongchao,&Kim, Hyung J..(2015).Experimental and Mechanistic Understanding of Aldehyde Hydrogenation Using Au-25 Nanoclusters with Lewis Acids: Unique Sites for Catalytic Reactions.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,137(45),14295-14304. |
| MLA | Li, Gao,et al."Experimental and Mechanistic Understanding of Aldehyde Hydrogenation Using Au-25 Nanoclusters with Lewis Acids: Unique Sites for Catalytic Reactions".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 137.45(2015):14295-14304. |
入库方式： OAI收割
来源：大连化学物理研究所
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