Abstract:Ligands are of tremendous importance for colloidal nanoparticles (NPs) in terms of surface protection, size and shape control, tailoring properties, self-assembly, and applications. However, it is very challenging to obtain unambiguous information on the ligands and their interactions and patterning on NPs. The recent advent of atomically precise nanochemistry has opened new horizons. One can now see ligands with atomic resolution and understand their behavior on the surface of ultrasmall NPs (1−3 nm) and also… Show more
“…[32,33] Specifically, the attained atomic level insights reveal that the kernel structure plays decisive roles in the optical properties, [34] while the organic-inorganic interface is decisive to chirality and catalysis, [35,36] and the surface ligand shell is critical to assembly and photoluminescence. [37,38] We foresee that the advances in nanochemistry will be capable of producing atomically precise NC materials that rival, and to some extent exceed, what conventional molecular chemistry has achieved at the molecular scale.Among the appealing physicochemical properties of NPs, the optical properties have long been one of the major topics in nanoscience. [1][2][3][4][5][6][39][40][41] Gold NPs account for the red color of stained glass in church windows, whereas silver NPs are typically yellow.…”
mentioning
confidence: 99%
“…[32,33] Specifically, the attained atomic level insights reveal that the kernel structure plays decisive roles in the optical properties, [34] while the organic-inorganic interface is decisive to chirality and catalysis, [35,36] and the surface ligand shell is critical to assembly and photoluminescence. [37,38] We foresee that the advances in nanochemistry will be capable of producing atomically precise NC materials that rival, and to some extent exceed, what conventional molecular chemistry has achieved at the molecular scale.…”
or cubic array of Fe 50 Pt 50 NPs can be controlled by the length of alkyl ligands. [27] Assembling two different types of NPs into binary superlattices is a versatile way to design nanomaterials in which two components are blended into periodic arrangements, and dozens of binary superlattices of structures of fcc, orthorhombic, cuboctahedral, etc., have been reported. [28][29][30] To sum up, by size/shape control and surface ligand engineering of gold NPs, programmable assembly of NPs into superlattices (e.g., primitive cubic, body-centered cubic (bcc), fcc, and hcp) has been well developed (Scheme 1, left).With the realization of programmable assembly of NPs, it would be highly desirable to achieve similarly exquisite control over the NP itself, such as the structure and functionality. For gold, the atoms typically adopt the fcc packing in both the bulk and nanoparticle forms. [31] In the past decade, significant efforts have been made in achieving atomically precise, ultrasmall gold NPs (often called nanoclusters, NCs, with core sizes of 1-3 nm). More importantly, their total structures have been determined by single-crystal X-ray diffraction (SCXRD). The current atomically precise nanochemistry is indeed moving toward programmable synthesis of NCs with control over the structure, such as the bcc, fcc, hcp, decahedra (D h ), icosahedra (I h ), multi-tetrahedral (T d ) network, etc., (Scheme 1, right). Such successes provide an excellent opportunity to correlate the structure of NCs with their properties such as optical absorption. Besides, recent progress in controlling NCs with atomic precision has opened new horizons, as the quantum-sized NCs exhibit fundamentally different properties from their plasmonic counterparts (5-100 nm). [32,33] Specifically, the attained atomic level insights reveal that the kernel structure plays decisive roles in the optical properties, [34] while the organic-inorganic interface is decisive to chirality and catalysis, [35,36] and the surface ligand shell is critical to assembly and photoluminescence. [37,38] We foresee that the advances in nanochemistry will be capable of producing atomically precise NC materials that rival, and to some extent exceed, what conventional molecular chemistry has achieved at the molecular scale.Among the appealing physicochemical properties of NPs, the optical properties have long been one of the major topics in nanoscience. [1][2][3][4][5][6][39][40][41] Gold NPs account for the red color of stained glass in church windows, whereas silver NPs are typically yellow. Scientific studies on the optical properties of Au NPs date back to Faraday's time. Later, Mie solved the Maxwell's equation for spherical particles and successfully simulated the extinction (i.e., scattering + absorption) spectra. [42][43][44] With the recent establishment of atomically precise nanochemistry, capabilities toward programmable control over the nanoparticle size and structure are being developed. Advances in the synthesis of atomically precise nanoclusters (NCs, 1-3 nm) have...
“…[32,33] Specifically, the attained atomic level insights reveal that the kernel structure plays decisive roles in the optical properties, [34] while the organic-inorganic interface is decisive to chirality and catalysis, [35,36] and the surface ligand shell is critical to assembly and photoluminescence. [37,38] We foresee that the advances in nanochemistry will be capable of producing atomically precise NC materials that rival, and to some extent exceed, what conventional molecular chemistry has achieved at the molecular scale.Among the appealing physicochemical properties of NPs, the optical properties have long been one of the major topics in nanoscience. [1][2][3][4][5][6][39][40][41] Gold NPs account for the red color of stained glass in church windows, whereas silver NPs are typically yellow.…”
mentioning
confidence: 99%
“…[32,33] Specifically, the attained atomic level insights reveal that the kernel structure plays decisive roles in the optical properties, [34] while the organic-inorganic interface is decisive to chirality and catalysis, [35,36] and the surface ligand shell is critical to assembly and photoluminescence. [37,38] We foresee that the advances in nanochemistry will be capable of producing atomically precise NC materials that rival, and to some extent exceed, what conventional molecular chemistry has achieved at the molecular scale.…”
or cubic array of Fe 50 Pt 50 NPs can be controlled by the length of alkyl ligands. [27] Assembling two different types of NPs into binary superlattices is a versatile way to design nanomaterials in which two components are blended into periodic arrangements, and dozens of binary superlattices of structures of fcc, orthorhombic, cuboctahedral, etc., have been reported. [28][29][30] To sum up, by size/shape control and surface ligand engineering of gold NPs, programmable assembly of NPs into superlattices (e.g., primitive cubic, body-centered cubic (bcc), fcc, and hcp) has been well developed (Scheme 1, left).With the realization of programmable assembly of NPs, it would be highly desirable to achieve similarly exquisite control over the NP itself, such as the structure and functionality. For gold, the atoms typically adopt the fcc packing in both the bulk and nanoparticle forms. [31] In the past decade, significant efforts have been made in achieving atomically precise, ultrasmall gold NPs (often called nanoclusters, NCs, with core sizes of 1-3 nm). More importantly, their total structures have been determined by single-crystal X-ray diffraction (SCXRD). The current atomically precise nanochemistry is indeed moving toward programmable synthesis of NCs with control over the structure, such as the bcc, fcc, hcp, decahedra (D h ), icosahedra (I h ), multi-tetrahedral (T d ) network, etc., (Scheme 1, right). Such successes provide an excellent opportunity to correlate the structure of NCs with their properties such as optical absorption. Besides, recent progress in controlling NCs with atomic precision has opened new horizons, as the quantum-sized NCs exhibit fundamentally different properties from their plasmonic counterparts (5-100 nm). [32,33] Specifically, the attained atomic level insights reveal that the kernel structure plays decisive roles in the optical properties, [34] while the organic-inorganic interface is decisive to chirality and catalysis, [35,36] and the surface ligand shell is critical to assembly and photoluminescence. [37,38] We foresee that the advances in nanochemistry will be capable of producing atomically precise NC materials that rival, and to some extent exceed, what conventional molecular chemistry has achieved at the molecular scale.Among the appealing physicochemical properties of NPs, the optical properties have long been one of the major topics in nanoscience. [1][2][3][4][5][6][39][40][41] Gold NPs account for the red color of stained glass in church windows, whereas silver NPs are typically yellow. Scientific studies on the optical properties of Au NPs date back to Faraday's time. Later, Mie solved the Maxwell's equation for spherical particles and successfully simulated the extinction (i.e., scattering + absorption) spectra. [42][43][44] With the recent establishment of atomically precise nanochemistry, capabilities toward programmable control over the nanoparticle size and structure are being developed. Advances in the synthesis of atomically precise nanoclusters (NCs, 1-3 nm) have...
“…Unfortunately, owing to the restricted pore size of MOFs, the sizes of NCs that can be produced may be limited. Furthermore, sometimes the pore-confined growth has difficulties in ensuring the atomic accuracy of NCs, as atomically exact NCs generally require kinetic control in the reduction stage, followed by a size-focusing step or separation procedure ( Li and Jin, 2020 ; Liu et al., 2020 ; Chen et al., 2015 ). Figure 2 Schematic representation of the process of Au NCs synthesis in MOFs and the example of Au 11 @ZIF-8 Reproduced with permission from Liu et al.…”
Section: Fabrication Of Ncs/mof Nanostructuresmentioning
Summary
Significant progress has been made in both fields of atomically precise metal nanoclusters (NCs) and metal-organic frameworks (MOFs) in recent years. A promising direction is to integrate these two classes of materials for creating unique composites with improved properties for catalysis and other applications. NCs incorporated with MOFs exhibit an optimized catalytic performance in many catalytic reactions, in which MOFs play a vital supporting role or as cocatalysts. In this Perspective, we first provide a brief summary of the methods that have been developed for the preparation of NCs/MOF composites and the characteristics of these strategies are analyzed. Following that, some recent works are highlighted to demonstrate the crucial role of MOF matrices in the enhancement of NCs catalytic properties. Finally, we outline some potentially important aspects for future work. This Perspective is in hopes of stimulating more interest in the research on the integration of NCs with MOFs toward functional materials.
“…To this end, several strategies have been developed for the systematic organization of nanoclusters. For example, a straightforward method for assembling atomic clusters into assemblies has been pursued, based on the interaction among the ligands stabilizing the nanoclusters [ 20 ]. Similarly, the use of biological molecules such as DNA and proteins as templates for the organization of nanoclusters have also been reported.…”
Metal nanoclusters have gained prominence in nanomaterials sciences, owing to their atomic precision, structural regularity, and unique chemical composition. Additionally, the ligands stabilizing the clusters provide great opportunities for linking the clusters in higher order dimensions, eventually leading to the formation of a repertoire of nanoarchitectures. This makes the chemistry of atomic clusters worth exploring. In this mini review, we aim to focus on the chemistry of nanoclusters. Firstly, we summarize the important strategies developed so far for the synthesis of atomic clusters. For each synthetic strategy, we highlight the chemistry governing the formation of nanoclusters. Next, we discuss the key techniques in the purification and separation of nanoclusters, as the chemical purity of clusters is deemed important for their further chemical processing. Thereafter which we provide an account of the chemical reactions of nanoclusters. Then, we summarize the chemical routes to the spatial organization of atomic clusters, highlighting the importance of assembly formation from an application point of view. Finally, we raise some fundamentally important questions with regard to the chemistry of atomic clusters, which, if addressed, may broaden the scope of research pertaining to atomic clusters.
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