Programmable kernel structures of atomically precise metal nanoclusters for tailoring catalytic properties

Abstract

The unclear structures and polydispersity of metal nanoparticles (NPs) seriously hamper the identification of the active sites and the construction of structure‐reactivity relationships. Fortunately, ligand‐protected metal nanoclusters (NCs) with atomically precise structures and monodispersity have become an ideal candidate for understanding the well‐defined correlations between structure and catalytic property at an atomic level. The programmable kernel structures of atomically precise metal NCs provide a fantastic chance to modulate their size, shape, atomic arrangement, and electron state by the precise modulating of the number, type, and location of metal atoms. Thus, the special focus of this review highlights the most recent process in tailoring the catalytic activity and selectivity over metal NCs by precisely controlling their kernel structures. This review is expected to shed light on the in‐depth understanding of metal NCs’ kernel structures and reactivity relationships.

Aqueous Zn–CO2 batteries: a route towards sustainable energy storage

“…Compared to the nanoparticle-based catalysts, the single-atom metal active sites distributed on a conductive substrate can achieve maximum atomic utilization. [119][120][121] Importantly, the catalytic activity and selectivity in a specific metal atom can be fine-tuned in a wider range through its coordination environment. [122][123][124][125] Usually, metals are introduced into heteroatom-doped carbon materials by methods such as pyrolysis and electrochemical deposition to adjust the electronic structure of the active center, thereby modifying the CO 2 RR and OER performance of the catalyst.…”

Dynamic Metal Nanoclusters: A Review on Accurate Crystal Structures

“…The DFT calculations were performed using the Perdew–Burke–Ernzerhof (PBE) functional [ 45 ] based on the generalized gradient approximation, the def2-SVP basis set, and empirical dispersion correction. The surface area of the clusters in the solvent was calculated using the default values of r i and r solv in Turbomole 6.5 [ 53 ]. The results showed that both the -CHO and -NO 2 groups of the 4-nitrobenzaldehyde molecule interacted closely with the surface bonds (S-Au-S) of the clusters.…”

An Innovative SbIII–WVI-Cotemplated Antimonotungstate with Potential in Sensing Paroxetine Electrochemically

“…Cluster materials have attracted persistent attention over the last several decades due to their abundant and devisible architectures, atomically accurate assembly, and unique physical and chemical properties. − They have shown great potentials in diverse applications, for example, optical materials, , green catalysis, , energy-related devices, cancer therapy, , reliable sensors, , and so on. Being one of the most classical cluster materials, polyoxometalates (POMs) feature rich chemical compositions, great structural diversities, and unique electronic structures, which make POMs favored in both cluster science and nanoscience. − Hitherto, extensive explorations on POMs possessing both novel architectures and application potentials have been made. , For instance, a series of 3D porous POM frameworks reported in 2019 exhibit an outstanding water vapor adsorption capacity and moderate proton-conductive properties .…”

“…On one hand, the Sb III ion with lone-pair electrons can effectively contribute to lacunary PBBs, which shows great potential in building giant AT aggregates. On the other hand, the Sb III ion can also serve as the inorganic linker between adjacent PBBs. , However, the Sb III ion is easily hydrolyzed in aqueous solution, while lacunary AT PBBs tend to generate sandwich-type structures, , which largely hinders the explorations on synthesizing innovative ATs. In order to avoid the former problem, the reaction solution should maintain a high acidity to inhibit the hydrolysis of the Sb III ion.…”