Alkynyl and halogen co-protected (AuAg)<sub>44</sub> nanoclusters: a comparative study on their optical absorbance, structure, and hydrogen evolution performance

Tang, Yun; Sun, Fang; Ma, Xiaoshuang; Qin, Lubing; Ma, Guanyu; Tang, Qing; Tang, Zhenghua

doi:10.1039/d2dt00634k

Cited by 17 publications

(12 citation statements)

References 39 publications

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“…The vacant atomic site (indicated by the dashed circle in Figure C) in both Au 43 and Au 42 Ag 1 is surprising given the precedent for 44-metal NCs, including two Au 24 Ag 20 NCs and one Au 22 Ag 22 NC, which all contain complete shells of surface metals and closed electronic shells. ,, Moreover, the previously reported 43-metal NC, PtAg 42 (CCR) 28 , has a closed-shell Ag 30 cage surrounding a Pt@Ag 12 kernel . In addition to their open surface shells, Au 43 and Au 42 Ag 1 possess an open-shell electronic configuration (23 valence electrons) with a single unpaired e – , which is rare and typically leads to poor stability.…”

Section: Resultsmentioning

confidence: 93%

A Double Open-Shelled Au₄₃ Nanocluster with Increased Catalytic Activity and Stability

et al. 2023

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Atomically precise metal nanoclusters (NCs) are an intriguing class of crystalline solids with unique physicochemical properties derived from tunable structures and compositions. Most atomically precise NCs require closed-shells and coordinatively saturated surface metals in order to be stable. Herein, we report Au43(CC t Bu)20 and Au42Ag1(CC t Bu)20, which feature open electronic and geometric shells, leading to both paramagnetism (23 valence e–) and enhanced catalytic activity from a single coordinatively unsaturated surface metal. The Au-alkynyl surface motifs of these NCs form five helical stripes around the inner Au12 kernel, imparting chirality and high thermal stability. Density functional theory (DFT) calculations suggest that there are minimal energy differences between the open-shelled NCs and hypothetical closed-shell systems and that the open-shelled electronic configuration gives rise to the largest band gap, which is known to promote cluster stability. Furthermore, we highlight how coordinatively unsaturated surface metals create active sites for the catalytic oxidation of benzyl alcohol to benzaldehyde, leading to high selectivity and increased conversion. This work represents the first example of an atomically precise Au NC with a double open-shelled structure and provides a promising platform for investigating the magnetic and catalytic properties of noble metal nanoparticles.

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Section: Resultsmentioning

confidence: 93%

A Double Open-Shelled Au₄₃ Nanocluster with Increased Catalytic Activity and Stability

et al. 2023

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“…It is interesting to note that the TOF values obtained for PdHCu 11 are higher than most efficient singleatom catalysts, including Pt single-atom catalysts, under similar conditions (Figure 4e and Table S2). More specifically, compared to other bimetallic nanoclusters reported to be efficient HER electrocatalysts (Table S3), [14,[30][31][32][33][34][35] it is the one with the best activity. Evidently, the Pd atom in PdHCu 11 is fully utilized for H 2 production, presumably owing to its unique open structure.…”

Section: Methodsmentioning

confidence: 99%

Hydride‐containing 2‐Electron Pd/Cu Superatoms as Catalysts for Efficient Electrochemical Hydrogen Evolution

Silalahi

Liao

et al. 2023

Angew Chem Int Ed

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The first hydride-containing 2-electron palladium/copper alloys, [PdHCu 11 {S 2 P(O i Pr) 2 } 6 (C�CPh) 4 ] (PdHCu 11 ) and [PdHCu 12 {S 2 P(O i Pr) 2 } 5 {S 2 PO(O i Pr)} (C�CPh) 4 ] (PdHCu 12 ), are synthesized from the reaction of [PdH 2 Cu 14 {S 2 P(O i Pr) 2 } 6 (C�CPh) 6 ] (PdH 2 Cu 14 ) with trifluoroacetic acid (TFA). X-ray diffraction reveals that the PdHCu 11 and PdHCu 12 kernels consist of a central PdH unit encapsulated within a vertex-missing Cu 11 cuboctahedron and complete Cu 12 cuboctahedron, respectively. DFT calculations indicate that both PdHCu 11and PdHCu 12 can be considered as axially-distorted 2electron superatoms. PdHCu 11 shows excellent HER activity, unprecedented within metal nanoclusters, with an onset potential of À 0.05 V (at 10 mA cm À 2 ), a Tafel slope of 40 mV dec À 1 , and consistent HER activity during 1000 cycles in 0.5 M H 2 SO 4 . Our study suggests that the accessible central Pd site is the key to HER activity and may provide guidelines for correlating catalyst structures and HER activity.

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“…60) protected by single ligands. 556 In 2018, Zheng and co-workers reported the cocrystallization of two atomically precise, different-size metal aggregates in a 1 : 1 ratio. One is an atomically closed-shell intermetallic spherical nanoparticle (AuAg) 267 (2,4-SPhMe 2 ) 80 ((AuAg) 267 , Fig.…”

Section: +mentioning

confidence: 99%

Platonic and Archimedean solids in discrete metal-containing clusters

Luo

Dong

et al. 2023

Chem. Soc. Rev.

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Alkynyl and halogen co-protected (AuAg)₄₄ nanoclusters: a comparative study on their optical absorbance, structure, and hydrogen evolution performance

Abstract: We report the synthesis, structure analysis, and electrochemical hydrogen evolution reaction (HER) performance of two alkynyl and halogen coprotected AuAg alloy nanoclusters, namely Au24Ag20(tBuPh-C≡C)24Cl2 (NC 1 for short) and Au22Ag22(tBuC≡C)16Br3.28Cl2.72...

Cited by 17 publications

References 39 publications

A Double Open-Shelled Au₄₃ Nanocluster with Increased Catalytic Activity and Stability

A Double Open-Shelled Au₄₃ Nanocluster with Increased Catalytic Activity and Stability

Hydride‐containing 2‐Electron Pd/Cu Superatoms as Catalysts for Efficient Electrochemical Hydrogen Evolution

Platonic and Archimedean solids in discrete metal-containing clusters

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Alkynyl and halogen co-protected (AuAg)44 nanoclusters: a comparative study on their optical absorbance, structure, and hydrogen evolution performance

Abstract: We report the synthesis, structure analysis, and electrochemical hydrogen evolution reaction (HER) performance of two alkynyl and halogen coprotected AuAg alloy nanoclusters, namely Au24Ag20(tBuPh-C≡C)24Cl2 (NC 1 for short) and Au22Ag22(tBuC≡C)16Br3.28Cl2.72...

Cited by 17 publications

References 39 publications

A Double Open-Shelled Au43 Nanocluster with Increased Catalytic Activity and Stability

A Double Open-Shelled Au43 Nanocluster with Increased Catalytic Activity and Stability

Hydride‐containing 2‐Electron Pd/Cu Superatoms as Catalysts for Efficient Electrochemical Hydrogen Evolution

Platonic and Archimedean solids in discrete metal-containing clusters

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Product

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Alkynyl and halogen co-protected (AuAg)₄₄ nanoclusters: a comparative study on their optical absorbance, structure, and hydrogen evolution performance

A Double Open-Shelled Au₄₃ Nanocluster with Increased Catalytic Activity and Stability

A Double Open-Shelled Au₄₃ Nanocluster with Increased Catalytic Activity and Stability