Maneuvering the Electronic State and Active Site of Assembled-Gold Nanoclusters through Polyoxometalate Implantation for Heterogeneous Green-Light Photocatalysis DOI

Satya Ranjan Sahoo,

Tarun Kumar Dinda, Sumit Saha

et al.

ACS Applied Materials & Interfaces, Journal Year: 2025, Volume and Issue: unknown

Published: March 25, 2025

Gold nanoclusters (AuNCs) exhibit unique molecule-like optical and electronic properties, making them promising candidates for photocatalysis. However, their application as primary photocatalysts in heterogeneous systems is limited by rapid electron recombination, small size, high solubility. To overcome these limitations, we developed an approach combining AuNCs assemblies with trap centers to enhance charge separation transfer. Using a depletion-driven assembly method, Keggin-type polyoxometalates (POMs), Na10SiW9O34 (SiW9), were uniformly embedded within spherical of glutathione-protected AuNCs, forming gold superclusters (AuSCs). The resulting AuSCs@SiW9 exhibited complete photoluminescence quenching, enhanced metallicity, stabilized photogenerated electrons via SiW9, enabling use photocatalysts. efficiently catalyzed the functionalization terminal aryl alkyne N-bromosuccinimide (NBS), achieving tribromoketones yield 94%, significantly outperforming AuSCs lower or higher metallicity (38 65%, respectively). Mechanistic studies revealed that improved promotes transfer complex formation NBS, while SiW9 stabilizes electrons, enhancing density under light irradiation. strong visible-light absorption, photostability, solvent dispersibility, recyclability up five cycles scalability broader applications. This strategy positions viable photocatalyst, expanding its potential photocatalysis toward synthesizing molecules.

Language: Английский

Stepwise structural evolution toward robust carboranealkynyl-protected copper nanocluster catalysts for nitrate electroreduction DOI Creative Commons
Jie Wang, Jinmeng Cai,

Kaixin Ren

et al.

Science Advances, Journal Year: 2024, Volume and Issue: 10(18)

Published: May 1, 2024

Atomically precise metal nanoclusters (NCs) are emerging as idealized model catalysts for imprecise nanoparticles to unveil their structure-activity relationship. However, the directional synthesis of robust NCs with accessible catalytic active sites remains a great challenge. In this work, we achieved bulky carboranealkynyl-protected copper NCs, monomer

Language: Английский

Citations

23
Planar Core and Macrocyclic Shell Stabilized Atomically Precise Copper Nanocluster Catalyst for Efficient Hydroboration of C–C Multiple Bond DOI Creative Commons
Badriah Alamer, Arunachalam Sagadevan, Mohammad Bodiuzzaman

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(23), P. 16295 - 16305

Published: May 30, 2024

Atomically precise metal nanoclusters (NCs) have become an important class of catalysts due to their catalytic activity, high surface area, and tailored active sites. However, the design development bond-forming reaction based on copper NCs are still in early stages. Herein, we report synthesis atomically nanocluster with a planar core unique shell, [Cu45(TBBT)29(TPP)4(C4H11N)2H14]2+ (Cu45) (TBBT: 4-tert-butylbenzenethiol; TPP: triphenylphosphine), yield via one-pot reduction method. The resulting structurally well-defined Cu45 is highly efficient catalyst for hydroboration alkynes alkenes. Mechanistic studies show that single-electron oxidation situ-formed ate complex enables formation boryl-centered radicals under mild conditions. This work demonstrates promise as C–B heteroatom reactions. compatible wide range alkenes functional groups producing hydroborated products.

Language: Английский

Citations

19
Atomically Precise Silver Clusters Stabilized by Lacunary Polyoxometalates with Photocatalytic CO2 Reduction Activity DOI

Yeqin Feng,

Fangyu Fu,

Linlin Zeng

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(7)

Published: Dec. 28, 2023

Abstract The syntheses of atomically precise silver (Ag) clusters stabilized by multidentate lacunary polyoxometalate (POM) ligands have been emerging as a promising but challenging research direction, the combination redox‐active POM and will render them unexpected geometric structures catalytic properties. Herein, we report successful construction two structurally‐new POM‐stabilized Ag clusters, TBA 6 H 14 (DPPB) 4 (CH 3 CN) 9 [Ag 24 (Si 2 W 18 O 66 ) ] ⋅ 10CH CN 9H ( {Ag } , TBA=tetra‐ n ‐butylammonium, DPPB=1,4‐Bis(diphenylphosphino)butane) Na (H O) 27 8CH 10H ), using facile one‐pot solvothermal approach. Under otherwise identical synthetic conditions, molecular could be readily tuned addition different organic ligands. In both compounds, central trefoil‐propeller‐shaped 14+ 17+ bearing 10 delocalized valence electrons are three C‐shaped {Si units. femtosecond/nanosecond transient absorption spectroscopy revealed rapid charge transfer between core Both compounds pioneeringly investigated catalysts for photocatalytic CO reduction to HCOOH with high selectivity.

Language: Английский

Citations

37
Advances in Cu nanocluster catalyst design: recent progress and promising applications DOI Creative Commons
Sourav Biswas, Saikat Das, Yuichi Negishi

et al.

Nanoscale Horizons, Journal Year: 2023, Volume and Issue: 8(11), P. 1509 - 1522

Published: Jan. 1, 2023

We present an in-depth study of Cu NC catalysts, encompassing design strategies, atomic-level tuning, and diverse catalytic applications.

Language: Английский

Citations

25
Labile Ligands Protected Cu50 Nanoclusters with Tailorable Optical Limiting Effect DOI
Jing Sun,

Xiongkai Tang,

Zhuang‐Hua Liu

et al.

ACS Materials Letters, Journal Year: 2023, Volume and Issue: 6(1), P. 281 - 289

Published: Dec. 19, 2023

Atomically precise copper nanoclusters have recently attracted tremendous attention, as they often exhibit structures and properties distinct to their gold silver counterparts. Although considerable progress has been made in the preparation structure determination of nanoclusters, introduction those newly created materials more underlying areas such nonlinear optics is its infancy. Herein, we report a new class Cu50 exhibiting tunable optical limiting effect. The facile prototype reported this work allows discovery up four clusters with nearly identical metal framework, namely, Cu50(CF3COO)12(3,5-diMe-PhS)18(PPh3)4H2 (Cu50-1), Cu50(CF3COO)10(4-F-PhS)20(PPh3)6H2 (Cu50-2), Cu50(CF3COO)10(PhS)20(PPh3)6H2 (Cu50-3), Cu50(PhCOO)10(4-F-PhS)20(PPh3)6H2 (Cu50-4). molecular series, revealed by X-ray single crystal analysis, describes stabilization Cu44 core an organometallic shell thiolate-carboxylate-phosphine-copper. combinatorial studies electrospray ionization mass spectroscopy (ESI-MS), nuclear magnetic resonance (NMR), density functional theory (DFT) calculations suggest that contain 18 free valence electrons, making them probably first library superatoms featuring 18e. As nanosecond Z-scan measurements results, typical effects, indicating promising applications field (NLO). More importantly, labile surface motifs on allow us tune NLO properties. This not only reports atomically process, clear structures, but also encourages research exploration exciting areas.

Language: Английский

Citations

24
A Comprehensive Analysis of Luminescent Crystallized Cu Nanoclusters DOI Creative Commons
Sourav Biswas, Yuichi Negishi

The Journal of Physical Chemistry Letters, Journal Year: 2024, Volume and Issue: 15(4), P. 947 - 958

Published: Jan. 22, 2024

Photoluminescence (PL) emission is an intriguing characteristic displayed by atomically precise d10 metal nanoclusters (NCs), renowned for their meticulous atomic arrangements, which have captivated the scientific community. Cu(I) NCs are a focal point in extensive research due to abundance, cost-effectiveness, and unique luminescent attributes. Despite similar core sizes, characteristics vary, influenced multiple factors. Progress hinges on synthesizing new modifying existing ones, with postsynthetic alterations impacting properties. The rapid advancements this field pose challenges discerning essential points excelling amidst competition other NCs. This Perspective explores intricate origins of PL NCs, providing comprehensive review correlated structural architectures. Understanding mechanistic origin each cluster crucial correlating diverse characteristics, contributing deeper comprehension from both fundamental applied perspectives.

Language: Английский

Citations

18
Carboxylate-Protected “Isostructural” Cu20 Nanoclusters as a Model System: Carboxylate Effect on Controlling Catalysis DOI
Yanru Yin,

Xuexin You,

Xiongkai Tang

et al.

Chemistry of Materials, Journal Year: 2024, Volume and Issue: 36(2), P. 1004 - 1012

Published: Jan. 10, 2024

Several recent studies have demonstrated the great promise of ligand-protected atomically precise copper nanoclusters in driving various chemical transformation processes. The insights into key factors controlling catalytic performance clusters at molecular level are highly desirable but difficult to gain. Herein, we report synthesis and comprehensive characterization two novel Cu20 nanoclusters, with formulae Se@Cu20(PhSe)12(PPh3)2(C6H5COO)6 (Cu20-1) Se@Cu20(PhSe)12(PPh3)2(CF3COO)6 (Cu20-2), which proved be candidates clarifying structure property relationship catalysis. As revealed by single-crystal X-ray analysis, structures share an identical metal skeleton similar ligand distributions only difference being carboxylate ligands on surface: C6H5COO for Cu20-1 while CF3COO Cu20-2. Surprisingly, such small distinctions cause a 16-fold activity leap reduction 4-nitrophenol 4-aminophenol. electronic resulting distinct, accounts their distinct performances. This work not provides model system highlight importance catalysis but, more importantly, is also expected simulate research attention engineering modulate physicochemical properties carboxylate-functionalized beyond

Language: Английский

Citations

17
Promoting CO2 Electroreduction to Hydrocarbon Products via Sulfur‐Enhanced Proton Feeding in Atomically Precise Thiolate‐Protected Cu Clusters DOI

Jun-Kang Li,

Jian‐Peng Dong,

Shuangshuang Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(48)

Published: Aug. 22, 2024

Abstract Thiolate‐protected Cu clusters with well‐defined structures and stable low‐coordinated + species exhibit remarkable potential for the CO 2 RR are ideal model catalysts establishing structure‐electrocatalytic property relationships at atomic level. However, extant employed in predominantly yield 2e − products. Herein, two 4 (MMI) 8 ( t BuS) (MMI=2‐mercapto‐1‐methylimidazole) prepared to investigate synergistic effect of adjacent S sites on RR. can reduce deep‐reduced products a 91.0 % Faradaic efficiency (including 53.7 CH ) while maintaining stability. Conversely, shows preference C 2+ products, achieving maximum FE 58.5 current density 152.1 mA⋅cm −2 . In situ XAS ex XPS spectra reveal preservation during RR, extensively enhancing adsorption capacity *CO intermediate. Moreover, kinetic analysis theoretical calculations confirm that facilitate H O dissociation into *H species, which directly participate protonation process *CHO. This study highlights important role Cu−S dual provides mechanistic insights pathway

Language: Английский

Citations

15
A thiolated copper-hydride nanocluster with chloride bridging as a catalyst for carbonylative C–N coupling of aryl amines under mild conditions: a combined experimental and theoretical study DOI Creative Commons
Anish Kumar Das, Sourav Biswas, Amit Pal

et al.

Nanoscale, Journal Year: 2024, Volume and Issue: 16(7), P. 3583 - 3590

Published: Jan. 1, 2024

A Cu( i ) nanocluster, with its precisely defined core and shell components, plays a pivotal role in mediating carbonylative C–N coupling reactions.

Language: Английский

Citations

13
Multiple neighboring active sites of an atomically precise copper nanocluster catalyst for efficient bond-forming reactions DOI Creative Commons
Atanu Ghosh, Arunachalam Sagadevan, Kathiravan Murugesan

et al.

Materials Horizons, Journal Year: 2024, Volume and Issue: 11(10), P. 2494 - 2505

Published: Jan. 1, 2024

We present a new type of core–shell copper nanocluster, [Cu 29 (S t Bu) 13 Cl 5 (PPh 3 ) 4 H 10 ] BuSO , that has multiple active sites on its surface. This nanocluster serves as versatile heterogeneous catalyst for various C-heteroatom (C–O, C–N and C–S) bond-forming reactions.

Language: Английский

Citations

12