The Hidden Mechanism: Excited‐State Proton‐Electron Pair Transfer in Metal Nanocluster Emission DOI Open Access
Kai‐Yuan Huang, Yanyan Chen,

Wen‐Lu Wang

и другие.

Angewandte Chemie, Год журнала: 2024, Номер unknown

Опубликована: Окт. 25, 2024

Abstract Comprehending the underlying factors that govern photoluminescence (PL) in metal nanoclusters (NCs) under physiological conditions remains a highly intriguing and unresolved challenge, particularly for their biomedical applications. In this study, we evaluate critical role of excited‐state proton‐coupled electron transfer emission NCs. Our findings demonstrate hydronium ion (H 3 O + ) binding can trigger nonlinear, pH‐dependent concerted proton (CEPT) reaction. This involves simultaneous from Au(0) core to Au(I)−ATT (ATT denotes 6‐aza‐2‐thiothymidine) surface H ATT ligand single step, greatly promoting vibrations rotations surface, resulting substantial PL quenching Au 10 (ATT) 6 Further analyses show unique CEPT dynamics are strongly influenced by opposing effects increased reorganization energy larger pre‐exponential factor on rate. Moreover, proposed process is found be prevalent core–shell relaxation NCs, such as 25 (SR) 18 (SR thiolate) serves an important limiting emission. By simply controlling p K ligands, performance easily regulated environments.

Язык: Английский

Symmetrical and asymmetrical surface structure expansions of silver nanoclusters with atomic precision DOI Creative Commons

Honglei Shen,

Pu Wang, Jiawei Xu

и другие.

Chemical Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

The controlled symmetrical or asymmetrical surface structure expansion of metal nanoclusters has been accomplished at the atomic level.

Язык: Английский

Процитировано

2
O‐Bridged Co‐Cu Dual‐Atom Catalyst Synergistically Triggers Interfacial Proton‐Coupled Electron Transfer: A New Approach to Sustainable Decontamination DOI Open Access
Qin Dai, Xin Li, Jieyuan Li

и другие.

Advanced Functional Materials, Год журнала: 2025, Номер unknown

Опубликована: Янв. 28, 2025

Abstract Heteroatom‐bridged dual‐atom catalysts (DACs), featuring more flexible active sites and intermetallic interaction, provide an opportunity for sustainable environmental remediation. Herein, innovative oxygen‐bridged Co‐Cu DAC supported on nano‐alumina (CoOCu‐DAC) is fabricated using a straightforward two‐step process. The as‐prepared catalyst significantly enhances both decontamination kinetics peroxymonosulfate (PMS) utilization efficiency by 1–3 orders of magnitude toward monoethanolamine (MEA, p K = 9.5) compared to Co single‐atom (Co‐SAC) bulk metal catalysts, largely outperforms previously reported systems. In‐situ ATR‐FTIR theoretical investigations reveal that the secondary introduction Cu plays multiple important roles: it activates lattice oxygen trigger key proton transfer (PT) MEAH + via nucleophilic attack at interface subsequently favors deprotonated MEA as efficient electron donor accelerate (ET) enhancing orbital overlaps co‐activation O 2 PMS. Such stepwise proton‐coupled (PCET)‐enhanced catalytic pathway mediated CoOCu‐DAC fundamentally different from common route identified in Co‐SAC‐involved Fenton‐like system. established binary QSAR further substantiates universality PCET‐enhanced strategy versatile nitrogen‐containing organic compounds. This study offers new perspective water other related areas catalysis based rationalized design multifunctional atomic level.

Язык: Английский

Процитировано

2
Rational Design of Highly Phosphorescent Nanoclusters for Efficient Photocatalytic Oxidation DOI
Zhu Chen,

Ze‐Le Chen,

Hao Li

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(33), С. 23212 - 23220

Опубликована: Июль 31, 2024

Analyzing the molecular structure-photophysical property correlations of metal nanoclusters to accomplish function-oriented photocatalysis could be challenging. Here, selective heteroatom alloying has been exploited a

Язык: Английский

Процитировано

5
Structure search for molecular clusters. Towards a rational understanding of their size-dependent properties DOI
Peter L. Rodríguez‐Kessler, Alvaro Muñoz‐Castro

Inorganica Chimica Acta, Год журнала: 2024, Номер unknown, С. 122376 - 122376

Опубликована: Сен. 1, 2024

Язык: Английский

Процитировано

4
Dual-Function Strategy for Enhanced Quercetin Detection Using Terbium(III) Ion-Bound Gold Nanoclusters DOI
Kai‐Yuan Huang, Yanyan Chen, Zhiqiang Yang

и другие.

Analytical Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Фев. 25, 2025

The engineering of metal nanoclusters (NCs) that exhibit bright emissions and high sensing performance under physiological conditions is still a formidable challenge. In this study, we report novel design strategy for realizing excellent NC-based probes by leveraging both concerted proton-coupled electron transfer (PCET) photoinduced (PET) mechanisms, with terbium(III) (Tb3+) ions serving as key modulator. Our findings indicate the binding Tb3+ to 6-aza-2-thiothymidine (ATT) ligand effectively inhibits proton-transfer step in PCET pathway Au10(ATT)6 NCs, giving rise over 10-fold enhancement fluorescence quantum yield 7.2%. Moreover, capped on surface NCs can act bridge facilitate an efficient donor-linker-acceptor type PET reaction from quercetin (Que) excited Au10 core specifically interacting bare 3-OH group. These advancements enable Tb3+/Au10(ATT)6 probe achieve significantly lower limit detection Que, reduced nearly 3 orders magnitude 2.6 nM, while also addressing critical difficulty selectively detecting Que presence its glycosylated analogues. This work opens new opportunities precise control photoluminescence NC at molecular level, potentially promoting development next-generation technologies.

Язык: Английский

Процитировано

0
Lighting up metal nanoclusters by the H2O-dictated electron relaxation dynamics DOI Creative Commons
Yuan Zhong,

Xue Wang,

Zhou Huang

и другие.

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Март 7, 2025

Abstract The modulation of traps has found attractive attention to optimize the performance luminescent materials, while understanding trap-involved photoluminescence management metal nanoclusters greatly lags behind, thus extensively impeding their increasing acceptance as promising chromophores. Here, we report an efficient passivation structural oxygen vacancies in AuAg by leveraging H 2 O molecules, achieving a sensitive color tuning from 536 480 nm and remarkably boosting quantum yield 5.3% (trap-state emission) 91.6% (native-state emission). In detail, favored electron transfer relevant contributes weak trap-state emission, which is capable being restrained molecules taking Au-O Ag-O bonds. This scenario allows dominated native-state emission with faster radiative rate. parallel, can rigidify landscape on hydrogen bonding, enabling suppression electron-optical phonon coupling decelerated non-radiative presented study deepens tailoring properties manipulating surface trap chemistry relaxation dynamics, would shed new light customizable performance.

Язык: Английский

Процитировано

0
Assessing the photoluminescence of metal nanoclusters: The Individual versus the collective DOI

Xiaoqin Du,

Peiyao Pan,

Haoqi Li

и другие.

Chinese Chemical Letters, Год журнала: 2025, Номер unknown, С. 111155 - 111155

Опубликована: Март 1, 2025

Язык: Английский

Процитировано

0
Plasmon-enhanced fluorescence sensor based on Au nanocages for sensitive detection of norepinephrine DOI
Chenye Xu, Shilin Chen, Wen Sun

и другие.

Analytica Chimica Acta, Год журнала: 2025, Номер unknown, С. 343995 - 343995

Опубликована: Апрель 1, 2025

Язык: Английский

Процитировано

0
Surface Structural Symmetry Breaking of Highly Symmetrical Ag29 Nanoclusters DOI
Wenqiang Duan,

Chen Zhu,

Xi Kang

и другие.

The Journal of Physical Chemistry Letters, Год журнала: 2025, Номер unknown, С. 4090 - 4096

Опубликована: Апрель 17, 2025

An in-depth understanding of the structural symmetry nanoclusters benefits investigation structure-property correlations. In this study, we accomplished breaking surface structures a highly symmetrical Ag29 nanocluster. The nanocluster exhibited C3 axisymmetry, while underwent in presence large-sized counterions as an asymmetric factor, giving rise to Ag28 with bare and C1 symmetric overall structure. Despite both exhibiting comparably electronic structures, displayed significantly higher photoluminescence intensity compared asymmetrical nanocluster, which has been rationalized from perspective their symmetry. Overall, study presents novel silver cluster pair controllably or allowing for atomic-level how influences metal nanoclusters.

Язык: Английский

Процитировано

0
Building Fast Proton‐Coupled Electron Transport Paths for Accelerating Reduction Reactions in Solar Cells Under Sunlight and Indoor Lighting: Modulating Energy Band Structure and Surface Reactions DOI
Guangping Yang, Sining Yun, Qing Pang

и другие.

Advanced Functional Materials, Год журнала: 2025, Номер unknown

Опубликована: Июнь 3, 2025

Abstract The photovoltaic conversion efficiency of solar cells critically depends on electron transport and mass diffusion at electrode‐electrolyte interfaces. In this study, innovative BCN@Fe 3 C PCN@Fe heterojunction catalysts are developed through tuning their energy band structure surface reactions. designed configurations utilize the metallic state Fe to generate a unique localized electric field interface, established proton‐coupled channel significantly improves kinetics for triiodide reduction (IRR) copper redox reactions (CRR). Under standard AM 1.5G sunlight, cell using counter electrode in N719‐I − /I system achieves power (PCE) 9.03%. Even under indoor lighting conditions 500 lux, maintained Voc 0.76 V PCE 18.99%. also 4.79% D35‐Cu 2+ /Cu + system. Theoretical calculations demonstrate that Schottky junction‐induced space charge regions facilitate selective adsorption Cu I protons, while interfacial built‐in promotes directional migration. This study first reveals mechanism electrons systems highlights advantages modulation optimizing IRR CRR kinetics.

Язык: Английский

Процитировано

0