Engineering Functional Metal Materials at the Atomic Level

Abstract

With continuous research efforts devoted into synthesis and characterization chemistry of functional nanomaterials in the past decades, the development of metal materials is stepping into a new era, where atom-by-atom customization of property-dictating structural attributes is expected. Herein, the state-of-the-art modulation of functional metal nanomaterials at the atomic level, by size- and structure-controlled synthesis of thiolate-protected metal (e.g., Au and Ag) nanoclusters (NCs), is exemplified. Metal NCs are ultrasmall (<3 nm) particles with hierarchical primary, secondary, and tertiary structures, reminiscent of natural proteins or enzymes. Given the proven dependence of their physicochemical properties on their size and structure, documented synthetic methodologies delivering NCs with atomic-level monodispersity and tailorable size and structural attributes at individual hierarchical levels are categorized and discussed. Such assured atomic-level modulation could confer metal NCs with novel application opportunities in diverse fields, which are also exemplified by their size- and structure-dictated catalytic and biomedical performance. The precise synthesis and application chemistry developed based on the hierarchical structure scheme of metal NCs could increase the acceptance of metal NCs as a new family of functional materials.

Metal Nanoclusters Stabilized by Selenol Ligands

“…However, an atomic‐level understanding of surface coordination chemistry in large nanoparticles (e.g., >1000 metal atoms) remains challenging, for two natures of nanoparticles—the poly‐disperse sizes (i.e., hard to be prepared uniformly at the atomic level), and the uncertain surface chemistry (e.g., metal–ligand interactions) . In view of this, metal nanoclusters have been served as model nanosystems, and precise molecular tools, for investigating the surface coordination chemistry at the atomic level owing to the monodisperse sizes and accurately characterized structures of these nanomaterials . Thiolates are most frequently used in protecting metallic kernels of nanoclusters; selenols, cognate derivatives of thiols by replacing the sulfur in thiols into selenium, have embodied their superiority in stabilizing metal nanoclusters and shown distinctively surface coordination mode.…”

Atomically Precise Bimetallic Nanoclusters as Photosensitizers in Photoelectrochemical Cells

“…[5][6][7][8][9][10] The well-defined structures of metal NCs enable scientists to study their structure-propertyr elationshipsa tt he atomic level. [11][12][13][14][15][16][17] For example, as ingle Au-Ags ubstitution could greatlyc hange the electronic structure of metal NCs, boosting their photoluminescence quantum yield as high as 200-fold. [18,19] Recently,l igand-protected gold NCs have been successfully used for light energyc onversions, such as in solar cells and water splitting.…”

Controlling magnetism of Au133(TBBT)52 nanoclusters at single electron level and implication for nonmetal to metal transition

“…1 Recent advances in solution-phase synthesis of atomically precise metal nanoclusters and their total structure determination by X-ray crystallography have opened up exciting opportunities for exploring the precise structure-property correlations. [1][2][3][4][5] Signicant progress has been achieved in controlling the size and structure of gold, 6-12 silver, [13][14][15][16][17][18][19][20][21] copper, [22][23][24] and alloy nanoclusters. [25][26][27][28][29][30] Such new materials hold potential in a wide range of applications, such as catalysis, chemical and biological detection, drug delivery, to name a few.…”