Au25 Clusters as Electron-Transfer Catalysts Induced the Intramolecular Cascade Reaction of 2-nitrobenzonitrile

Chong, Hanbao; Wang, Shuxin; Fu, Fangyu; Ji, Xiang; Zhu, Manzhou; Li, Yadong

doi:10.1038/srep03214

Cited by 59 publications

(60 citation statements)

References 25 publications

(27 reference statements)

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“…The Au 25 (SePh) 18 /MoS 2 nanocomposite exhibits a larger onset potential with a smaller current density as compared to that of Au 25 (SR) 18 /MoS 2 , indicating their distinct difference in electron relaying capability. Our results indicate that the Au 25 (SR) 18 is more efficient in relaying electrons than the Au 25 (SePh) 18 , which provides insight into the Au 25 catalysts for other types of electron‐transfer catalytic reactions . The stronger electronic interaction in the Au 25 (SR) 18 /MoS 2 nanocomposite is also reflected in Au 4f XPS spectra (Figure d), where a larger positive shift of electron binding energy of Au 4f is observed for Au 25 (SR) 18 /MoS 2 as compared to Au 25 (SePh) 18 /MoS 2 .…”

Section: Xps‐measured Mo:s:au Relative Atomic Ratio Of the Working Elmentioning

confidence: 67%

Atomically Precise Gold Nanoclusters Accelerate Hydrogen Evolution over MoS₂ Nanosheets: The Dual Interfacial Effect

Zhao

Jin

Song

et al. 2017

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Hydrogen generation via electrocatalytic water splitting holds great promise for future energy revolution. It is desirable to design abundant and efficient catalysts and achieve mechanistic understanding of hydrogen evolution reaction (HER). Here, this paper reports a strategy for improving HER performance of molybdenum disulfide (MoS ) via introducing gold nanoclusters as a cocatalyst. Compared to plain MoS nanosheets, the Au (SR) /MoS nanocomposite exhibits enhanced HER activity with a small onset potential of -0.20 V (vs reversible hydrogen electrode) and a higher current density of 59.3 mA cm at the potential of -0.4 V. In addition to the interfacial interaction between nanoclusters and MoS , the interface between the Au core and the surface ligands (thiolate vs selenolate) is also discovered to distinctly affect the catalytic performance. This work highlights the promise of metal nanoclusters in boosting the HER performance via tailoring the interfacial electronic interactions between gold nanoclusters and MoS nanosheets, as well as the interface between metal core and surface ligands.

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Section: Xps‐measured Mo:s:au Relative Atomic Ratio Of the Working Elmentioning

confidence: 67%

Atomically Precise Gold Nanoclusters Accelerate Hydrogen Evolution over MoS₂ Nanosheets: The Dual Interfacial Effect

Zhao

Jin

Song

et al. 2017

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“…3 Our recent effort focuses on direct and high-yield synthesis of magic-sized gold nanoclusters in the medium-sized range (∼40 < n < ∼100). Compared to the already attained rich discoveries of the structures and properties in the small-sized region (e.g., n < ∼40, Scheme 1) such as Au 25 (SC 2 H 4 Ph) 18 − , Au 38 (SC 2 H 4 Ph) 24 , Au 36 (SPh-t-Bu) 24 , Au 28 (SPh-t-Bu) 20 , and Au 23 (S-c-C 6 H 11 ) 16 − , 29−34 the medium-sized gold nanoclusters remain to be pursued. Although several species have been identified, 15−18 such as Au 44 (SR) 28 , Au 55 (SR) 31 , and Au 67 (SR) 35 , they are all obtained through postsynthetic separation of a mixture of magic-sized nanoclusters by HPLC or solvent fractionation; that is, no direct synthesis methods have been developed for these medium-sized nanoclusters.…”

Section: ■ Introductionmentioning

confidence: 94%

Magic Size Au₆₄(S-c-C₆H₁₁)₃₂ Nanocluster Protected by Cyclohexanethiolate

Zeng

Chen

et al. 2014

Chem. Mater.

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We report a new magic-sized gold nanocluster of atomic precision formulated as Au 64 (S-c-C 6 H 11 ) 32 . The Au 64 nanocluster was obtained in relatively high yield (∼15%, Au atom basis) by a two-step size-focusing methodology. Obtaining this new magic size through the previously established "size focusing" method relies on the introduction of a new synthetic "parameter"the type of protecting thiolate ligand. It was found that Au 64 (S-c-C 6 H 11 ) 32 was the most thermodynamically stable specie of the cyclohexanethiolate-protected gold nanoclusters in the size range from~5k to 20k (where, k = 1000 dalton); hence, it can be selectively synthesized through a careful control of the size-focusing kinetics. The Au 64 nanocluster is the first gold nanocluster achieved through direct synthesis (i.e., without postsynthetic size separation) in the medium size range (i.e., ∼40 to ∼100 gold atoms). This medium-sized Au 64 (S-c-C 6 H 11 ) 32 exhibits a highly structured optical absorption spectrum, reflecting its discrete electronic states. The discovery of this new Au 64 (S-c-C 6 H 11 ) 32 nanocluster bridges the gap of the gold nanoclusters in the medium size range and will facilitate the understanding of the structure and property evolution of magic-size gold nanoclusters. ■ INTRODUCTIONIt is well-known that when the size of ligand-protected gold nanoparticles reaches the ultrasmall size range (i.e., less than 2− 3 nm, equivalent to a few hundred gold atoms), a series of discrete sizes (or "magic sizes") of gold nanoparticles can be obtained. 1,2 These "magic-sized" gold nanoparticles are often classified as nanoclusters; they possess higher stability than other sizes and hence can be enriched during the synthetic process and obtained in pure form. 3,4 The ultrasmall gold nanoclusters also exhibit unique properties compared to their larger counterparts due to the quantum confinement effect, 5,6 such as the multiband absorption spectra, enhanced fluorescence, etc. 7−9 This class of gold nanomaterials provides a new platform for applications in catalysis, biosensor, as well as energy harvesting. 10−12 Many magic-sized gold nanoclusters protected by thiolate ligands, Au n (SR) m (SR = thiolate), have been identified in recent years, with size ranging from several to hundreds of gold atoms, as shown in Scheme 1. 13−21 Among those magic sizes, Au 25 (SR) 18 , Au 38 (SR) 24 , and Au 144 (SR) 60 , where SR = SC 2 H 4 Ph or SC n H 2n+1 , have been achieved through direct synthesis (i.e., without postsynthetic size separation) in molecular purity and relatively high yields (>10%, gold atom basis), Scheme 1 (red dots). 22−24 The ease of obtaining these ubiquitous sizes has enabled wide research on these three nanoclusters. 10,25−28 A "size focusing" synthetic methodology has been summarized, which has been demonstrated to be quite universal and allows one to achieve controlled synthesis of many atomically precise gold nanoclusters. 3 In this method, a mixture of crude nanoclusters with a controlled, proper size range was synth...

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“…However, we were intrigued by the outcome of the reaction as, instead of the expected hydroxylamine 2 j , o ‐aminobenzamide 4 was isolated in 98 % yield. The formation of 4 can be rationalized, as suggested by Li et al ., by cyclization of hydroxylamine 2 j into a five‐membered ring intermediate 3 which then evolves, in the reductive environment, into aminobenzamide 4 (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

Selective Conversion of Nitroarenes to N‐Aryl Hydroxylamines Catalysed by Carbon‐Nanotube‐Supported Nickel(II) Hydroxide

et al. 2017

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International audienceA novel nanohybrid was assembled by a layer-by-layer strategy that permitted the immobilization of nickel(II) hydroxide on multi-walled carbon nanotubes. The heterogeneous catalyst was used for the reduction of a wide variety nitroaromatics to hydroxylamines in a binary solvent mixture (tetrahydrofuran/ water), in the presence of sodium borohydride and under mild conditions. The reaction is highly selective as it afforded cleanly the expected aromatic hydroxylamines in the presence of other sensitive groups such as halogens, esters, double bonds or nitriles. The catalyst could also be readily recycled by a simple centrifugation and reused in subsequent reduction reactions with no decrease in catalytic activities, over five cycles. Analysis of the spent catalyst indicated neither alteration in the morphology, metal-content, nor oxidation state of the carbon nanotube-supported nickel(II). The catalytic nanohybrid assembly reported in this work thus compares favorably with known systems, as it is very stable, operates at room temperature with limited nickel loading (0.8 mol%), and selectively leads to N-aryl hydroxylamines without the formation of the corresponding anilines

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Au25 Clusters as Electron-Transfer Catalysts Induced the Intramolecular Cascade Reaction of 2-nitrobenzonitrile

Cited by 59 publications

References 25 publications

Atomically Precise Gold Nanoclusters Accelerate Hydrogen Evolution over MoS₂ Nanosheets: The Dual Interfacial Effect

Atomically Precise Gold Nanoclusters Accelerate Hydrogen Evolution over MoS₂ Nanosheets: The Dual Interfacial Effect

Magic Size Au₆₄(S-c-C₆H₁₁)₃₂ Nanocluster Protected by Cyclohexanethiolate

Selective Conversion of Nitroarenes to N‐Aryl Hydroxylamines Catalysed by Carbon‐Nanotube‐Supported Nickel(II) Hydroxide

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Au25 Clusters as Electron-Transfer Catalysts Induced the Intramolecular Cascade Reaction of 2-nitrobenzonitrile

Cited by 59 publications

References 25 publications

Atomically Precise Gold Nanoclusters Accelerate Hydrogen Evolution over MoS2 Nanosheets: The Dual Interfacial Effect

Atomically Precise Gold Nanoclusters Accelerate Hydrogen Evolution over MoS2 Nanosheets: The Dual Interfacial Effect

Magic Size Au64(S-c-C6H11)32 Nanocluster Protected by Cyclohexanethiolate

Selective Conversion of Nitroarenes to N‐Aryl Hydroxylamines Catalysed by Carbon‐Nanotube‐Supported Nickel(II) Hydroxide

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Atomically Precise Gold Nanoclusters Accelerate Hydrogen Evolution over MoS₂ Nanosheets: The Dual Interfacial Effect

Atomically Precise Gold Nanoclusters Accelerate Hydrogen Evolution over MoS₂ Nanosheets: The Dual Interfacial Effect

Magic Size Au₆₄(S-c-C₆H₁₁)₃₂ Nanocluster Protected by Cyclohexanethiolate