Cd-driven surface reconstruction and photodynamics in gold nanoclusters

Liu, Xu; Guo, Yinglu; Cheng, Xinglian; Xu, Jiayu; Cai, Xiao; Hu, Weigang; Xu, Wen; Zhang, Chunfeng; Zhu, Yan

doi:10.1039/d0sc05163b

Cited by 35 publications

(34 citation statements)

References 35 publications

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“…By doping with Cd atoms and ligand-induced surface remodeling, it is easy to convert the core–shell structure of Au 25 (PET) 18 clusters into bimetallic Au 19 Cd 3 (S-tol) 18 clusters: the surface staples (Au 2 (PET) 3 ) attached to the Au 13 core are replaced by Au 2 Cd(S-tol) 6 , while the structural integrity of the Au 13 core is maintained (Figure C) . As shown in Figure D, Au 38 Cd 4 (d-MBT) 30 contains a Au 26 core, two Au 5 Cd 2 (d-MBT) 12 and two Au(d-MBT) 2 surface staples, and two bridge d-MBT ligands; the Au 26 core can be seen as eight tetrahedral Au 4 units assembled in a double helix . It is worth pointing out that the Cd atoms in Au 24 Cd 1 replace the Au atoms in the core–shell layer, while the Cd atoms in Au 19 Cd 3 and Au 38 Cd 4 are located on the outer surface staples.…”

Section: Resultsmentioning

confidence: 99%

“…The Au 44 (d-MBT) 28 clusters were prepared according to the previous literature method . Synthesis of Au 38 Cd 4 (d-MBT) 30 : 10 mg Au 44 (d-MBT) 28 was dissolved in 2 mL of toluene, and 1 mL of acetonitrile solution containing 5 mg of Cd(NO 3 ) 2 and 200 μL of d-MBT ligand were added, respectively.…”

Section: Methodsmentioning

confidence: 99%

“…Then the product was separated by PTLC. When methanol was diffused into 4- tert -butyltoluene solution of Au 38 Cd 4 (d-MBT) 30 for more than one month, needle-like black crystals were obtained …”

Section: Methodsmentioning

confidence: 99%

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Active-Site Tailoring of Gold Cluster Catalysts for Electrochemical CO₂ Reduction

et al. 2021

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Constructing the structure and composition of active sites of catalysts to discriminate between reaction molecules remains a grand challenge in heterogeneous catalysis, as the ability to precisely control the interfacial chemistry within molecular-scale environments is largely lacking. Here, we recognize the reaction sites of thiolate-ligand protected gold nanoclusters for CO2 electroreduction (CO2RR) by cleaving the Au–S or C–S bonds selectively that can be controlled by Cd doping. Our study reveals that the C–S bond cleavage occurring on partial ligands leads to the creation of open S sites that are able to readily bind the CO2 molecule and catalyze its reduction, while the breaking of Au–S bonds creates exposed metal sites to favor H2 evolution that is considered as the main complete reaction of CO2RR. We further tailor the reactivities of these two types of reaction sites by only the ligand derivatization, which holds great promise in rational design of high-performance catalysts.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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Active-Site Tailoring of Gold Cluster Catalysts for Electrochemical CO₂ Reduction

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“…[120] A combined method of heteroatomic doping and ligand-induced surface restructuring is applied to modify the surface of Au 9f). [121] Recently, with the advances in its synthesis and structure determination, AuCd bimetallic NCs have drawn considerable attention on catalytic applications. For instance, Wu et al investigated the Au 47 Cd 2 NCs supported on XC-72 as an electrocatalyst for CO 2 RR (Figure 10).…”

Section: Dopingmentioning

confidence: 99%

The Factors Dictating Properties of Atomically Precise Metal Nanocluster Electrocatalysts

Xiang

Liu

Cheng

et al. 2022

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Metal nanoparticles occupy an important position in electrocatalysis. Unfortunately, by using conventional synthetic methodology, it is a great challenge to realize the monodisperse composition/structure of metal nanoparticles at the atomic level, and to establish correlations between the catalytic properties and the structure of individual catalyst particles. For the study of well‐defined nanocatalysts, great advances have been made for the successful synthesis of nanoparticles with atomic precision, notably ligand‐passivated metal nanoclusters. Such well‐defined metal nanoclusters have become a type of model catalyst and have shown great potential in catalysis research. In this review, the authors summarize the advances in the utilization of atomically precise metal nanoclusters for electrocatalysis. In particular, the factors (e.g., size, metal doping/alloying, ligand engineering, support materials as well as charge state of clusters) affecting selectivity and activity of catalysts are highlighted. The authors aim to provide insightful guidelines for the rational design of electrocatalysts with high performance and perspectives on potential challenges and opportunities in this emerging field.

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“…This so-called surface reconstruction occurs when the symmetry of the crystal is broken from the bulk to the surface . Such structural reconstructed surfaces usually induce unconventional physical and chemical properties compared to the bulk materials. − As the existence of oxygen vacancy further breaks the local lattice symmetry, we can expect an enhanced surface reconstruction . However, this possible oxygen vacancy induced surface reconstruction has never been clearly visualized experimentally in WO 3 .…”

Section: Introductionmentioning

confidence: 99%

Atomic-Scale Observation of Oxygen Vacancy-Induced Step Reconstruction in WO₃

et al. 2021

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As the most common type of defects in WO 3 , surface oxygen deficiencies have been widely investigated in terms of their structure as well as physicochemical properties. In general, oxygen vacancy on the surface may lead to the reconstruction of the surface structure due to the need for surface energy minimization, especially for the area with high oxygen vacancy concentration. However, such a phenomenon has not been directly demonstrated or observed from the experiment. In the paper, we observed such surface reconstruction in the step area or high-index facets in WO 3 using the spherical aberration-corrected scanning transmission electron microscope (Cs-STEM) with atomic-scale resolution. This surface reconstruction results in a structure of 5-fold symmetry pentagonal columns, which is first reported. According to the DFT calculation, the formation energy of oxygen vacancy in the step edge is much lower than the smooth surface. Furthermore, the formation energy of oxygen vacancy in the higher index (110) facet is lower than the low index ( 100) and ( 010) facets. Our experimental results support these findings, i.e., that the reconstruction is pronounced in the step or high-index facets with a high concentration of oxygen vacancy. Therefore, the high concentration of oxygen vacancy in the step or high-index facet area contributes to the formation of pentagonal column structures. This work could provide a novel insight into the correlation between intrinsic defect and surface structure formation in these materials.

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Cd-driven surface reconstruction and photodynamics in gold nanoclusters

Abstract: With dual modifications of the surface and electronic structure, Au38Cd4(DMBT)30 exhibits distinct excitonic behaviors and photocatalytic performances compared to Au44(DMBT)28.

Cited by 35 publications

References 35 publications

Active-Site Tailoring of Gold Cluster Catalysts for Electrochemical CO₂ Reduction

Active-Site Tailoring of Gold Cluster Catalysts for Electrochemical CO₂ Reduction

The Factors Dictating Properties of Atomically Precise Metal Nanocluster Electrocatalysts

Atomic-Scale Observation of Oxygen Vacancy-Induced Step Reconstruction in WO₃

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Cd-driven surface reconstruction and photodynamics in gold nanoclusters

Abstract: With dual modifications of the surface and electronic structure, Au38Cd4(DMBT)30 exhibits distinct excitonic behaviors and photocatalytic performances compared to Au44(DMBT)28.

Cited by 35 publications

References 35 publications

Active-Site Tailoring of Gold Cluster Catalysts for Electrochemical CO2 Reduction

Active-Site Tailoring of Gold Cluster Catalysts for Electrochemical CO2 Reduction

The Factors Dictating Properties of Atomically Precise Metal Nanocluster Electrocatalysts

Atomic-Scale Observation of Oxygen Vacancy-Induced Step Reconstruction in WO3

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Product

Resources

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Active-Site Tailoring of Gold Cluster Catalysts for Electrochemical CO₂ Reduction

Active-Site Tailoring of Gold Cluster Catalysts for Electrochemical CO₂ Reduction

Atomic-Scale Observation of Oxygen Vacancy-Induced Step Reconstruction in WO₃