Atomically Tailored Gold Nanoclusters for Catalytic Application

Abstract

Recent advances in the synthetic chemistry of atomically precise metal nanoclusters (NCs) have significantly broadened the accessible sizes and structures. Such particles are well defined and have intriguing properties, thus, they are attractive for catalysis. Especially, those NCs with identical size but different core (or surface) structure provide unique opportunities that allow the specific role of the core and the surface to be mapped out without complication by the size effect. Herein, we summarize recent work with isomeric Aun NCs protected by ligands and isostructural NCs but with different surface ligands. The highlighted work includes catalysis by spherical and rod‐shaped Au25 (with different ligands), quasi‐isomeric Au28(SR)20 with different R groups, structural isomers of Au38(SR)24 (with identical R) and Au38S2(SR)20 with body‐centred cubic (bcc) structure, and isostructural [Au38L20(PPh3)4]2+ (different L). These isomeric and/or isostructural NCs have provided valuable insights into the respective roles of the kernel, surface staples, and the type of ligands on catalysis. Future studies will lead to fundamental advances and development of tailor‐made catalysts.

Cucurbiturils brighten Au nanoclusters in water

“…In particular, thiolate-protected gold nanoclusters (AuNCs), 19 which have atomically precise compositions (Au x (SR) y , where x and y have exact values, SR ¼ thiolate ligands), have emerged as promising emissive and catalytic materials due to the intriguing optical and photoelectrical properties. [20][21][22][23][24][25][26] Different from common gold nanoparticles, AuNCs don't present a surface plasmon resonance (SPR) effect but show a unique Au(0) kernel-Au(I) shell structure with discrete energy levels, endowing AuNCs with full spectrum photoluminescence emission from blue to NIR as quantum dots and organic dyes. [27][28][29] Besides, the outstanding photo-stability, long carrier lifetime and Stokes shi, and efficient renal clearance properties make AuNCs ideal choices for analysis and bio-imaging.…”

Gold‐Catalyzed Cross‐Coupling Reactions: An Overview of Design Strategies, Mechanistic Studies, and Applications

“…[14][15][16] Many Au-catalyzed reactions are performed in liquid water. [43][44][45] Owing to the localizeds urface plasmon resonance (LSPR)e ffects, [46][47][48] gold nanoparticles (AuNPs) can be used as photocatalysts. [26][27][28][29][30][31] It has been predicted that in the near future, the scope of heterogeneous gold catalysis will be expanded for the large-scale synthesis of bulk and fine chemicals, pharmaceuticals, and polymers, and for pollutant degradation.…”

“…[40][41][42] Also, structurally well-defined and capped gold clusters have been used as tools to design model catalytic systems and to gain amechanistic understanding of the heterogeneous catalysis. [43][44][45] Owing to the localizeds urface plasmon resonance (LSPR)e ffects, [46][47][48] gold nanoparticles (AuNPs) can be used as photocatalysts. [49][50][51][52] In some cases, AuNPs will work as aphotosensitizer,replacing the role of adye in conventional dye-sensitized solarcells.…”

In situstructural kinetics of picosecond laser-induced heating and fragmentation of colloidal gold spheres

“…Their properties change from a quantum regime to a size-scaling regime and may offer a number of unique properties, such as permeability in biological systems 1,2 or higher catalytic activity. 3,4 While LAL has been intensively investigated 5 and up-scaling routines have been defined, 6 the tendency is to add a second process to reduce sizes and achieve a well-defined size definition by laser-induced fragmentation in liquids (LFL). [7][8][9] In LFL, a laser pulse intersects the particle suspension such that the particles preferentially absorb energy and transiently pass through a high energy density state that ends in small fragments.…”