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Experimental and Mechanistic Understanding of Aldehyde Hydrogenation Using Au-25 Nanoclusters with Lewis Acids: Unique Sites for Catalytic Reactions
Li, Gao1,2; Abroshan, Hadi3; Chen, Yuxiang3; Jin, Rongchao3; Kim, Hyung J.3,4
Source PublicationJOURNAL OF THE AMERICAN CHEMICAL SOCIETY
2015-11-18
ISSN0002-7863
DOI10.1021/jacs.5b07716
Volume137Issue:45Pages:14295-14304
Indexed BySCI
SubtypeArticle
WOS HeadingsScience & Technology ; Physical Sciences
WOS SubjectChemistry, Multidisciplinary
WOS Research AreaChemistry
WOS KeywordSUPPORTED GOLD CATALYSTS ; CHEMOSELECTIVE HYDROGENATION ; SELECTIVE HYDROGENATION ; MOLECULAR CALCULATIONS ; OPTICAL-PROPERTIES ; CRYSTAL-STRUCTURE ; CO OXIDATION ; ACTIVE-SITE ; CLUSTERS ; LIGAND
AbstractThe 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).
Language英语
WOS IDWOS:000365148500015
PublisherAMER CHEMICAL SOC
Citation statistics
Document Type期刊论文
Identifierhttp://cas-ir.dicp.ac.cn/handle/321008/171585
Collection中国科学院大连化学物理研究所
Corresponding AuthorJin, Rongchao
Affiliation1.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Catalysis, Dalian 116023, Peoples R China
2.Chinese Acad Sci, Dalian Inst Chem Phys, Gold Catalysis Res Ctr, Dalian 116023, Peoples R China
3.Carnegie Mellon Univ, Dept Chem, Pittsburgh, PA 15213 USA
4.Korea Inst Adv Study, Sch Computat Sci, Seoul 130722, South Korea
Recommended Citation
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.
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