尺寸与结构对金纳米团簇金属性演化的协同调控

Synergistic Regulation of Size and Structure on the Metallicity Evolution of Gold Nanoclusters

摘要

金纳米团簇(Au NCs)具有原子级精确的结构, 核心尺寸在1~3 nm范围内, 是连接有机金属分子与传统金纳米颗粒的独特体系, 兼具类分子特性与纳米材料优势, 其从分子态到金属态的转变是纳米科学领域的核心问题之一. 大尺寸(>100个金原子)金纳米团簇随尺寸增大, 能级逐渐从离散向连续转变, 呈现金属特性. 然而, 这一转变并非仅由尺寸决定, 在特定的临界尺寸区域内, 团簇的金属性还受到晶体结构、 几何形貌等多重因素的协同调控. 在临界尺寸区域内, 团簇呈现出兼具分子性与金属性的双重特性, 该特性受晶体结构、 几何形貌等多重因素协同调控, 针对这一区域的研究已广泛且深入地开展. 本文综合评述了大尺寸金纳米团簇金属性演化的研究进展, 概述了非金属性、 金属性及临界区域团簇的尺寸、 结构与金属性间的构效关系, 梳理了金属性的测定判据与关键研究技术. 最后, 讨论了该领域未来的挑战和发展方向.

Abstract

Gold nanoclusters（Au NCs） feature atomically precise structures with core sizes ranging from 1 to 3 nm， serving as a unique system that bridges organometallic molecules and conventional gold nanoparticles； combining molecular-like properties with the advantages of nanomaterials， their transition from a molecular state to a metallic state is one of the core issues in the field of nanoscience. As large-sized gold nanoclusters（containing >100 gold atoms） increase in size， their energy levels gradually shift from discrete to continuous， exhibiting metallic properties. However， this transition is not solely determined by size， and a critical size regime exists. Within this critical size regime， the clusters exhibit dual molecular and metallic properties， which are synergistically regulated by multiple factors including crystal structure and geometric morphology， and this phenomenon has been extensively and intensively investigated. This review summarizes the research progress on the metallicity evolution of large-sized gold nanoclusters， outlines the structure-activity relationships among size， structure， and metallicity for non-metallic， metallic， and critical-regime clusters， and clarifies the determination criteria and key research techniques for metallicity.

关键词

金纳米团簇 / 金属性 / 尺寸演化 / 飞秒瞬态吸收光谱

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基金资助

国家重点研发计划项目(2023YFC3404200)