Structure and vibrations of chemically produced<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline"><mml:mrow><mml:msub><mml:mrow><mml:mi mathvariant="normal">Au</mml:mi></mml:mrow><mml:mrow><mml:mn>55</mml:mn></mml:mrow></mml:msub></mml:mrow></mml:math>clusters

Marcus, Matthew A.; Andrews, Mark P.; Zegenhagen, J.; Bommannavar, Arun; Montano, P. A.

doi:10.1103/physrevb.42.3312

Cited by 102 publications

(72 citation statements)

References 17 publications

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“…[29,56] It was 2.80 for Au 25 -i and 2.82 for Au 25 -bi, 0.08 and 0.06 shorter than that in Au foil, respectively, which was consistent with the previous observations. [36,38,42] The first-shell AuÀAu bonding distance was reported at 2.78 in thiolate-protected Au 38 [2] at 2.80 in Au 55 -A C H T U N G T R E N N U N G (PPh 3 ) 12 Cl 6 [40,43] and at 2.83 in Au 144 (SR) 60.…”

Section: Wwwchemeurjorgmentioning

confidence: 99%

Ligand‐Stabilized and Atomically Precise Gold Nanocluster Catalysis: A Case Study for Correlating Fundamental Electronic Properties with Catalysis

Liu

Krishna

Losovyj

et al. 2013

Chemistry A European J

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We present results from our investigations into correlating the styrene-oxidation catalysis of atomically precise mixed-ligand biicosahedral-structure [Au25(PPh3)10(SC12H25)5Cl2](2+) (Au25-bi) and thiol-stabilized icosahedral core-shell-structure [Au25(SCH2CH2Ph)18](-) (Au25-i) clusters with their electronic and atomic structure by using a combination of synchrotron radiation-based X-ray absorption fine-structure spectroscopy (XAFS) and ultraviolet photoemission spectroscopy (UPS). Compared to bulk Au, XAFS revealed low Au-Au coordination, Au-Au bond contraction and higher d-band vacancies in both the ligand-stabilized Au clusters. The ligands were found not only to act as colloidal stabilizers, but also as d-band electron acceptor for Au atoms. Au25-bi clusters have a higher first-shell Au coordination number than Au25-i, whereas Au25-bi and Au25-i clusters have the same number of Au atoms. The UPS revealed a trend of narrower d-band width, with apparent d-band spin-orbit splitting and higher binding energy of d-band center position for Au25-bi and Au25-i. We propose that the differences in their d-band unoccupied state population are likely to be responsible for differences in their catalytic activity and selectivity. The findings reported herein help to understand the catalysis of atomically precise ligand-stabilized metal clusters by correlating their atomic or electronic properties with catalytic activity.

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Section: Wwwchemeurjorgmentioning

confidence: 99%

Ligand‐Stabilized and Atomically Precise Gold Nanocluster Catalysis: A Case Study for Correlating Fundamental Electronic Properties with Catalysis

Liu

Krishna

Losovyj

et al. 2013

Chemistry A European J

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“…One of the first examples of a magic cluster is Au55 which was discovered by Schmid et al (414) and has since seen extensive study (415)(416)(417). Boyen et al recently confirmed that Au55 clusters display unusual chemical behaviour (418).…”

Section: Figure 25mentioning

confidence: 99%

Surface chemistry of catalysis by gold

et al. 2004

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IntroductionGold has long been regarded as an "inert" surface and bulk gold surfaces do not chemisorb many molecules easily. However, in the last decade, largely through the efforts of Masatake Haruta, gold particles, particularly those below 5 nm in size, have begun to garner attention for unique catalytic properties (1-8). In recent years, supported gold particles have been shown to be effective as catalysts for low temperature CO oxidation (9), selective oxidation of propene to propene oxide (10), water gas shift (11), NO reduction (12), selective hydrogenation of acetylene (or butadiene) (13)

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“…The famous Schmid cluster, Au 55 (PPh 3 ) 12 Cl 6 [43] was one of the first size-specific Au NCs studied with XAS in the 1990s [44][45][46]. Au L 3 -edge EXAFS fitting results from a few studies suggested the Au core is likely cuboctahedral instead of icosahedral.…”

Section: Introduction To Gold Nanoclustersmentioning

confidence: 99%

“…Further analysis of the Au 55 (PPh 3 ) 12 Cl 6 with EXAFS by Cluskey et al suggested a possible arrangement of phosphine and chloride ligands on the surface [44]. Marcus et al probed the thermal vibrational properties using temperature-dependent XAS measurements [46]. This early use of XAS to study Au 55 proved to be a beneficial approach for investigating the structure and properties of ultra-small Au NCs.…”

Section: Introduction To Gold Nanoclustersmentioning

confidence: 99%

Bonding properties of thiolate-protected gold nanoclusters and structural analogs from X-ray absorption spectroscopy

Chevrier

Yang

Chatt

et al. 2015

Nanotechnology Reviews

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Abstract:Subnanometer, atomically precise thiolateprotected gold nanoclusters represent an important advancement in our understanding of thiolate-protected gold nanoparticles and thiolate-gold chemistry. Aside from being a link between larger gold nanoparticles and small gold complexes, gold nanoclusters exhibit extraordinary molecule-like optical, electronic, and physicochemical properties that are promising for next-generation imaging agents, sensing devices, or catalysts. The success in elucidating a number of unique thiolate-gold surface and gold core structures has greatly improved our understanding of thiolate-gold nanoclusters. Nevertheless, monitoring the structural and electronic behavior of thiolate-protected gold nanoclusters in a variety of media or environments is crucial for the next step in advancing this class of nanomaterials. Not to mention, there are a number of thiolateprotected gold nanoclusters with unknown structures or compositions that could reveal important insights on application-based properties such as luminescence or catalytic activity. This review summarizes some of the recent contributions from X-ray absorption spectroscopy (XAS) studies on the intriguing bonding properties of thiolate-protected gold nanoclusters and some structural analogs. Advantages from XAS include a local structural, site-and elementspecific analysis, suitable for ultra-small particle sizes (1-2 nm), along with versatile experimental conditions.

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Structure and vibrations of chemically producedAu55clusters

Cited by 102 publications

References 17 publications

Ligand‐Stabilized and Atomically Precise Gold Nanocluster Catalysis: A Case Study for Correlating Fundamental Electronic Properties with Catalysis

Ligand‐Stabilized and Atomically Precise Gold Nanocluster Catalysis: A Case Study for Correlating Fundamental Electronic Properties with Catalysis

Surface chemistry of catalysis by gold

Bonding properties of thiolate-protected gold nanoclusters and structural analogs from X-ray absorption spectroscopy

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