Homoleptic Alkynyl‐Protected Ag₁₅ Nanocluster with Atomic Precision: Structural Analysis and Electrocatalytic Performance toward CO₂ Reduction

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(50), P. 26136 - 26141

Published: Sept. 24, 2021

We report the fabrication of homoleptic alkynyl-protected Ag15 (C≡C-t Bu)12+ (abbreviated as ) nanocluster and its electrocatalytic properties toward CO2 reduction reaction. Crystal structure analysis reveals that possesses a body-centered-cubic (BCC) with an Ag@Ag8 @Ag6 metal core configuration. Interestingly, we found can adsorb in air spontaneously self-assembled into one-dimensional linear material during crystal growth process. Furthermore, convert CO faradaic efficiency ca. 95.0 % at -0.6 V maximal turnover frequency 6.37 s-1 -1.1 along excellent long-term stability. Finally, density functional theory (DFT) calculations disclosed Bu)11+ one alkynyl ligand stripping off from intact cluster expose uncoordinated Ag atom catalytically active site for formation.

Language: Английский

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Cluster-Based Multifunctional Copper(II) Organic Framework as a Photocatalyst in the Degradation of Organic Dye and as an Electrocatalyst for Overall Water Splitting

Crystal Growth & Design, Journal Year: 2021, Volume and Issue: 21(7), P. 4242 - 4248

Published: June 15, 2021

On the basis of unprecedented one-dimensional {Cu2(tetrazole)(SO4)(OH)}n cluster, a novel two-dimensional layered copper(II) organic framework, {[Cu2(TTB)(SO4)(OH)]·H2O·MeCN}n (1), is constructed from 1-(tetrazo-5-yl)-4-(triazo-1-yl) benzene (HTTB) and CuSO4 under hydrothermal conditions. Photocatalytic experiments revealed that 1 an outstanding semiconducting material (Eg = 2.21 eV) for degradation methyl blue UV light irradiation. Besides, electrocatalytic research showed 1@NF electrode shows better oxygen evolution reaction (OER) performance than RuO2@NF, reaching current density 10 mA·cm–2 when overpotential OER 377 mV in 1.0 M KOH electrolyte Tafel slope 15.6 mV·dec–1. Meanwhile, hydrogen (HER) 242 at mA·cm–2, with being 23.1 mV·dec–1, also suggesting HER Pt/C@NF. The durability test activity was maintained 90% after 12 h. properties show excellent candidate as multifunctional to solve environmental pollution energy shortages.

Language: Английский

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Rod-Shaped Silver Supercluster Unveiling Strong Electron Coupling between Substituent Icosahedral Units

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(31), P. 12261 - 12267

Published: July 29, 2021

The first linear silver supercluster based on icosahedral Ag13 units has been constructed via bridging of dpa ligands: Ag61(dpa)27(SbF6)4 (Hdpa = dipyridylamine) (Ag61). Single-crystal X-ray diffraction reveals that this rod-shaped cluster consists four vertex-sharing icosahedra in a arrangement. This Ag61 represents the longest one-dimensional metal nanocluster with resolved structure. Unprecedented electron coupling develops between their constituent units. Theoretical studies disclose stabilities two superclusters are dictated by strong interaction as well ligand effect dpa–Ag motifs. quantum size accounts for significant enhancement metal-related absorptions and red shift at near-infrared region length increases. work sheds light evolution materials an understanding electronic communication clusters.

Language: Английский

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Rod-shaped units based cobalt(II) organic framework as an efficient electrochemical sensor for uric acid detection in serum

Microchemical Journal, Journal Year: 2022, Volume and Issue: 185, P. 108154 - 108154

Published: Nov. 17, 2022

Language: Английский

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Ag₂₂ Nanoclusters with Thermally Activated Delayed Fluorescence Protected by Ag/Cyanurate/Phosphine Metallamacrocyclic Monolayers through In‐Situ Ligand Transesterification

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(45)

Published: Sept. 15, 2022

The composition of protection monolayer exerts great influence on the molecular and electronic structures atomically precise protected metal nanoclusters. Four isostructural Ag/cyanurate/phosphine metallamacrocyclic Ag22 nanoclusters are synthesized by kinetically controlled in-situ ligand formation-driven strategy. These eight-electron superatomic silver feature an unprecedented interfacial bonding structure with diverse E-Ag (E=O/N/P/Ag) interactions between Ag13 core monolayer, displays thermally activated delayed fluorescence (TADF), benefiting from their distinct donor-acceptor type structures. This work not only unmasks a new core-shell interface involving cyanurate but also underlines significance high-electron-affinity N-heterocyclic in synthesizing TADF is first mixed valence Ag0/I nanocluster characteristic.

Language: Английский

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Thiacalix[4]arene Etching of an Anisotropic Cu₇₀H₂₂ Intermediate for Accessing Robust Modularly Assembled Copper Nanoclusters

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(5), P. 3545 - 3552

Published: Jan. 26, 2024

Atom-precise metal nanoclusters (NCs) with large bulk (nuclearity >60) are important species for insight into the embryonic phase of nanoparticles and their top-down etching synthesis. Herein, we report a metastable rod-shaped 70-nuclei copper-hydride NC, [Cl@Cu

Language: Английский

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Bifunctional two-dimensional copper-organic framework for high catalytic performance on cycloaddition of CO2 with epoxides and deacetalization-Knoevenagel condensation

Journal of Molecular Structure, Journal Year: 2024, Volume and Issue: 1306, P. 137849 - 137849

Published: Feb. 22, 2024

Language: Английский

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Directional Doping and Cocrystallizing an Open-Shell Ag₃₉ Superatom via Precursor Engineering

ACS Nano, Journal Year: 2022, Volume and Issue: 16(4), P. 5507 - 5514

Published: March 30, 2022

Metal precursors employed in the bottom-up synthesis of metal nanoclusters (NCs) are great importance directing their composition and geometrical structure. In this work, a silver nanocluster co-protected by phosphine thiolate, namely, [Ag39(PFBT)24(TPP)8]2- (Ag39, PFBT = pentafluorobenzenethiol, TPP triphenylphosphine), was isolated structurally characterized. It adopts three-layered Ag13@Ag18@Ag8S24P8 core-shell The Ag13@Ag18 kernel is unusual multilayer noble NCs. By introducing copper precursor synthesis, bimetallic [Ag37Cu2(PFBT)24(TPP)8]2- (Ag37Cu2) with an identical structure to Ag39 apart from two outer Ag atoms being substituted Cu obtained. Astoundingly, used found be critical determining final alteration led cocrystallization above alloy Ag14 nanocluster, [Ag37Cu2(PFBT)24(TPP)8]2-·[Ag14(PFBT)6(TPP)8] (Ag37Cu2·Ag14). electronic analyzed theoretical calculation reveals that 17-electron open-shell superatom. optical absorption Ag39, Ag37Cu2, Ag37Cu2·Ag14 compared studied detail. This work not only enriches family metallic but also provides NC-based cocrystal platform for in-depth study its crystal growth photophysical property.

Language: Английский

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Disc‐Like Silver Nanocluster Ag₉₃ Built with Bicapped Hexagonal Prismatic Ag₁₅ and Ino Decahedral Ag₁₃ Units

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(29)

Published: May 22, 2023

The reduction of alkynyl-silver and phosphine-silver precursors with a weak reducing reagent Ph2 SiH2 led to the formation novel silver nanocluster [Ag93 (PPh3 )6 (C≡CR)50 ]3+ (R=4-CH3 OC6 H4 ), which is largest structurally characterized cluster clusters. This disc-shaped has Ag69 kernel consisting bicapped hexagonal prismatic Ag15 unit wrapped by six Ino decahedra through edge-sharing. first time that are used as building block assemble Moreover, central atom coordination number 14, highest in metal nanoclusters. work provides diverse packing pattern nanoclusters, helpful for understanding assembling mechanisms.

Language: Английский

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A pillar-layered binuclear 3D cobalt(ii) coordination polymer as an electrocatalyst for overall water splitting and as a chemosensor for Cr(vi) anion detection

CrystEngComm, Journal Year: 2021, Volume and Issue: 23(36), P. 6245 - 6252

Published: Jan. 1, 2021

A 3D pillar-layered cobalt( ii ) CP with a (4,6)-connected {4 4 ·6 10 ·8}{4 2 } fsc net was designed and it showed great potential as an electrocatalyst in the overall water splitting chemosensor for Cr( vi anion detection.

Language: Английский

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