Miscible‐Solvent‐Assisted Two‐Phase Synthesis of Monolayer‐Ligand‐Protected Metal Nanoclusters with Various Sizes

Abstract

Effective yet versatile synthetic strategies for size‐tunable metal nanoclusters (NCs) are scarce. This has hampered the development of this unique class of nanomaterials. Here, a general protocol is reported for the synthesis of high‐quality metal NCs protected by a variety of organic ligands (e.g., selenolate, thiolate, and phosphine) based on a miscible‐solvent‐assisted phase transfer between water and organic solution. This method is demonstrated to be facile, rapid (≤3 h), scalable (gram‐scale), and versatile. The size of the selenolated and thiolated Au NCs can be tuned from Au10 to Au61 by simply varying the miscible solvent in proportions and types. The advantages of this method, such as quick phase separation and no need for purification treatment, enable real‐time monitoring of metal NC growth within the NaBH4 reduction system. The results show that the size of Au NCs gradually increases with increasing valence electron count by a stepwise 2x e‐ hopping mechanism (x = 0–5), i.e., 0 e‐ → 2 e‐ → 4 e‐ → 8 e‐ → 18 e‐ → 22 e‐ → 32 e‐.

In Situ Synthesis of Bismuth Nanoclusters within Carbon Nano‐Bundles from Metal–Organic Framework for Chloride‐Driven Electrochemical Deionization

“…Metal nanoclusters (MNCs for short; <3 nm) as an emerging class of functional nanomaterials, [ 1 ] have attracted enormous attention in fields of catalysis, [ 2 ] energy conversion, [ 3 ] environmental protection, [ 4 ] and biomedicine [ 5 ] due to their intriguing physicochemical properties such as ultrasmall size, [ 1b,6 ] adjustable surface chemistry, [ 7 ] atomic‐precision structure, [ 8 ] ultrahigh surface‐to‐volume ratio, [ 1b ] strong luminescence, [ 8,9 ] intrinsic chirality, [ 10 ] etc. At present, coinage metal NCs (e.g., Au, Ag, and Cu NCs), have gained impressive progress in size tuning, [ 6 ] surface engineering, [ 11 ] structure identification, [ 12 ] as well as property exploration, [ 1b,d,g,2b ] which greatly boosts their diverse applications towards tackling the challenging problems of various fields. [ 1d,2a,3c,4,7 ] By contrast, the same cannot be said in the synthesis of non‐noble MNCs (e.g., Bi, Ni, Mn, and Fe), let alone the wide application of such MNCs.…”

Highly Luminescent AuAg Nanoclusters with Aggregation-Induced Emission for High-Performance White LED Application

“…In the past decade, ultrasmall luminescent metal nanoclusters (MNCs, < 3 nm) composed of several to a few hundred metal atoms have emerged as a new class of functional materials. − Owing to their unique attributes such as strong luminescence, − rich surface chemistry, − large Stokes shift, good biocompatibility, and excellent photothermal stability, MNCs have attracted extensive research interest in the fields of catalysis, − energy conversion, , healthcare, , electronics, and photonics. − Currently, researchers have attempted to solve certain challenging issues in diverse fields by engineering MNCs with specific functionalities, , which has resulted in some interesting achievements and largely promotes advances in such fields.…”

Exploration of Formation and Size‐Evolution Pathways of Thiolate‐Gold Nanoclusters in the CO‐Directed [Au25(SR)18]− Synthesis

“…Very recently, a similar stepwise 2 e − hopping cluster growth was also discovered in the “NaBH 4 reduction” system, [ 46 ] which indicates that the 2 e − hopping is a popular mechanism in the reduction synthesis of thiolate‐gold and selenolate‐gold clusters. As a conceptual extension of the mechanistic studies of the CO‐reduction system, herein a similar intermolecular reaction mechanism is proposed to understand the 2 e − hopping cluster growth in the “NaBH 4 reduction” system.…”