Metal species with different size (single atoms, nanoclusters, and nanoparticles) show different catalytic behavior for various heterogeneous catalytic reactions. It has been shown in the literature that many factors including the particle size, shape, chemical composition, metal–support interaction, and metal–reactant/solvent interaction can have significant influences on the catalytic properties of metal catalysts. The recent developments of well-controlled synthesis methodologies and advanced characterization tools allow one to correlate the relationships at the molecular level. In this Review, the electronic and geometric structures of single atoms, nanoclusters, and nanoparticles will be discussed. Furthermore, we will summarize the catalytic applications of single atoms, nanoclusters, and nanoparticles for different types of reactions, including CO oxidation, selective oxidation, selective hydrogenation, organic reactions, electrocatalytic, and photocatalytic reactions. We will compare the results o...

Metal Catalysts for Heterogeneous Catalysis: From Single Atoms to Nanoclusters and Nanoparticles.

Colloidal nanoparticles are being intensely pursued in current nanoscience research. Nanochemists are often frustrated by the well-known fact that no two nanoparticles are the same, which precludes the deep understanding of many fundamental properties of colloidal nanoparticles in which the total structures (core plus surface) must be known. Therefore, controlling nanoparticles with atomic precision and solving their total structures have long been major dreams for nanochemists. Recently, these goals are partially fulfilled in the case of gold nanoparticles, at least in the ultrasmall size regime (1–3 nm in diameter, often called nanoclusters). This review summarizes the major progress in the field, including the principles that permit atomically precise synthesis, new types of atomic structures, and unique physical and chemical properties of atomically precise nanoparticles, as well as exciting opportunities for nanochemists to understand very fundamental science of colloidal nanoparticles (such as the s...

Atomically Precise Colloidal Metal Nanoclusters and Nanoparticles: Fundamentals and Opportunities

Atomically precise pieces of matter of nanometer dimensions composed of noble metals are new categories of materials with many unusual properties. Over 100 molecules of this kind with formulas such as Au25(SR)18, Au38(SR)24, and Au102(SR)44 as well as Ag25(SR)18, Ag29(S2R)12, and Ag44(SR)30 (often with a few counterions to compensate charges) are known now. They can be made reproducibly with robust synthetic protocols, resulting in colored solutions, yielding powders or diffractable crystals. They are distinctly different from nanoparticles in their spectroscopic properties such as optical absorption and emission, showing well-defined features, just like molecules. They show isotopically resolved molecular ion peaks in mass spectra and provide diverse information when examined through multiple instrumental methods. Most important of these properties is luminescence, often in the visible–near-infrared window, useful in biological applications. Luminescence in the visible region, especially by clusters prot...

Atomically Precise Clusters of Noble Metals: Emerging Link between Atoms and Nanoparticles

Rapidly increasing atmospheric CO2 concentrations threaten human society, the natural environment, and the synergy between the two. In order to ameliorate the CO2 problem, carbon capture and conversion techniques have been proposed. Metal–organic framework (MOF)-based materials, a relatively new class of porous materials with unique structural features, high surface areas, chemical tunability and stability, have been extensively studied with respect to their applicability to such techniques. Recently, it has become apparent that the CO2 capture capabilities of MOF-based materials significantly boost their potential toward CO2 conversion. Furthermore, MOF-based materials’ well-defined structures greatly facilitate the understanding of structure–property relationships and their roles in CO2 capture and conversion. In this review, we provide a comprehensive account of significant progress in the design and synthesis of MOF-based materials, including MOFs, MOF composites and MOF derivatives, and their application to carbon capture and conversion. Special emphases on the relationships between CO2 capture capacities of MOF-based materials and their catalytic CO2 conversion performances are discussed.

Carbon capture and conversion using metal–organic frameworks and MOF-based materials

Metal–organic frameworks (MOFs), established as a relatively new class of crystalline porous materials with high surface area, structural diversity, and tailorability, attract extensive interest and exhibit a variety of applications, especially in catalysis. Their permanent porosity enables their inherent superiority in confining guest species, particularly small metal nanoparticles (MNPs), for improved catalytic performance and/or the expansion of reaction scope. This is a rapidly developing interdisciplinary research field. In this review, we provide an overview of significant progress in the development of MNP/MOF composites, including various preparation strategies and characterization methods as well as catalytic applications. Special emphasis is placed on synergistic effects between the two components that result in an enhanced performance in heterogeneous catalysis. Finally, the prospects of MNP/MOF composites in catalysis and remaining issues in this field have been indicated.

Metal–organic frameworks meet metal nanoparticles: synergistic effect for enhanced catalysis

Improving the knowledge of the relationship between structure and properties is fundamental in catalysis. Recently, researchers have developed a variety of well-controlled methods to synthesize atomically precise metal nanoclusters (NCs). NCs have shown high catalytic activity and unique selectivity in many catalytic reactions, which are related to their ultrasmall size, abundant unsaturated active sites, and unique electronic structure different from that of traditional nanoparticles (NPs). More importantly, because of their definite structure and monodispersity, they are used as model catalysts to reveal the correlation between catalyst performance and structure at the atomic scale. Therefore, this review aims to summarize the recent progress on NCs in catalysis and provide potential theoretical guidance for the rational design of high-performance catalysts. First a brief summary of the synthetic strategies and characterization methods of NCs is provided. Then the primary focus of this review—the model ...

Atomically Precise Noble Metal Nanoclusters as Efficient Catalysts: A Bridge between Structure and Properties.

Due to their atomically precise structures and intriguing chemical/physical properties, metal nanoclusters are an emerging class of modular nanomaterials. Photo-luminescence (PL) is one of their most fascinating properties, due to the plethora of promising PL-based applications, such as chemical sensing, bio-imaging, cell labeling, phototherapy, drug delivery, and so on. However, the PL of most current nanoclusters is still unsatisfactory-the PL quantum yield (QY) is relatively low (generally lower than 20%), the emission lifetimes are generally in the nanosecond range, and the emitted color is always red (emission wavelengths of above 630 nm). To address these shortcomings, several strategies have been adopted, and are reviewed herein: capped-ligand engineering, metallic kernel alloying, aggregation-induced emission, self-assembly of nanocluster building blocks into cluster-based networks, and adjustments on external environment factors. We further review promising applications of these fluorescent nanoclusters, with particular focus on their potential to impact the fields of chemical sensing, bio-imaging, and bio-labeling. Finally, scope for improvements and future perspectives of these novel nanomaterials are highlighted as well. Our intended audience is the broader scientific community interested in the fluorescence of metal nanoclusters, and our review hopefully opens up new horizons for these scientists to manipulate PL properties of nanoclusters. This review is based on publications available up to December 2018.

Tailoring the photoluminescence of atomically precise nanoclusters.

The rod-shaped Au25 nanocluster possesses a low photoluminescence quantum yield (QY=0.1 %) and hence is not of practical use in bioimaging and related applications. Herein, we show that substituting silver atoms for gold in the 25-atom matrix can drastically enhance the photoluminescence. The obtained AgxAu25−x (x=1–13) nanoclusters exhibit high quantum yield (QY=40.1 %), which is in striking contrast with the normally weakly luminescent AgxAu25−x species (x=1–12, QY=0.21 %). X-ray crystallography further determines the substitution sites of Ag atoms in the AgxAu25−x cluster through partial occupancy analysis, which provides further insight into the mechanism of photoluminescence enhancement.

A 200-fold quantum yield boost in the photoluminescence of silver-doped Ag(x)Au(25-x) nanoclusters: the 13th silver atom matters.

Metal nanoclusters fill the gap between discrete atoms and plasmonic nanoparticles, providing unique opportunities for investigating the quantum effects and precise structure–property correlations at the atomic level. As a versatile strategy, alloying can largely improve the physicochemical performances compared to the corresponding homo-metal nanoclusters, and thus benefit the applications of such nanomaterials. In this review, we highlight the achievements of atomically precise alloy nanoclusters, and summarize the alloying principles and fundamentals, including the synthetic methods, site-preferences for different heteroatoms in the templates, and alloying-induced structure and property changes. First, based on various Au or Ag nanocluster templates, heteroatom doping modes are presented. The templates with electronic shell-closing configurations tend to maintain their structures during doping, while the others may undergo transformation and give rise to alloy nanoclusters with new structures. Second, alloy nanoclusters of specific magic sizes are reviewed. The arrangement of different atoms is related to the symmetry of the structures; that is, different atoms are symmetrically located in the nanoclusters of smaller sizes, and evolve into shell-by-shell structures at larger sizes. Then, we elaborate on the alloying effects in terms of optical, electrochemical, electroluminescent, magnetic and chiral properties, as well as the stability and reactivity via comparisons between the doped nanoclusters and their homo-metal counterparts. For example, central heteroatom-induced photoluminescence enhancement is emphasized. The applications of alloy nanoclusters in catalysis, chemical sensing, bio-labeling, and other fields are further discussed. Finally, we provide perspectives on existing issues and future efforts. Overall, this review provides a comprehensive synthetic toolbox and controllable doping modes so as to achieve more alloy nanoclusters with customized compositions, structures, and properties for applications. This review is based on publications available up to February 2020.

Atomically precise alloy nanoclusters: syntheses, structures, and properties.

A metal exchange method based upon atomically precise gold nanoclusters (NCs) as templates is devised to obtain alloy NCs including CuxAu25-x(SR)18, AgxAu25-x(SR)18, Cd1Au24(SR)18, and Hg1Au24(SR)18 via reaction of the template with metal thiolate complexes of Cu(II), Ag(I), Cd(II), and Hg(II) (as opposed to common salt precursors such as CuCl2, AgNO3, etc) Experimental results imply that the exchange between gold atoms in NCs and those of the second metal in the thiolated complex does not necessarily follow the order of metal activity (ie, galvanic sequence) In addition, the crystal structure of the exchange product (Cd1Au24(SR)18) is successfully determined, indicating that the Cd is in the center of the 13-atom icosahedral core This metal exchange method is expected to become a versatile new approach for synthesizing alloy NCs that contain both high- and low-activity metal atoms

Manzhou Zhu

Papers

Atomically Precise Noble Metal Nanoclusters as Efficient Catalysts: A Bridge between Structure and Properties.

Tailoring the photoluminescence of atomically precise nanoclusters.

A 200-fold quantum yield boost in the photoluminescence of silver-doped Ag(x)Au(25-x) nanoclusters: the 13th silver atom matters.

Atomically precise alloy nanoclusters: syntheses, structures, and properties.

Metal Exchange Method Using Au25 Nanoclusters as Templates for Alloy Nanoclusters with Atomic Precision