Preparation and Reaction of Naked Metal Clusters for Catalysis and Genetic Materials

Metal clusters that contain a small number of atoms usually present unique properties with dramatic dependence on their sizes, geometric structures, and compositions. The studies of naked metal clusters are devoted to develop new catalysts and functional materials of atomic precision, and enable to improve the fundamental theory of structure chemistry and to understand the basic reactions and properties bridging the gap between atoms and bulk materials. In particular, some interesting superatom clusters have received reasonable research interest indicative of materials gene of clusters. Here in this review, we simply summarize the preparation, stability, and reactivity of naked metal clusters with a few examples displayed. Hopefully it serves as a modest spur to stimulate more interest of related investigations in this field.     

Functionalization of polyoxometalates: towards advanced applications in catalysis and materials science

Functionalization via covalent grafting of organic functions allows to tune the redox and acid-base properties, and the solubility of polyoxometalates, to enhance their stability and biological activity and to reduce their toxicity, to facilitate their implementation in extended structures and functional devices. We discuss herein the electronic and binding connections, and the various synthesis methodologies. We emphasize on organonitrogen, organosilyl and organophosphonyl derivatives with special attention to synthesis, characterization and potential applications in catalysis and materials science. We also consider the giant molybdenum oxide-based clusters especially the porous capsule-type clusters (Keplerates) which have high relevance to this context.     

Electronic Structure of EuMo6Se8 Studied by X-Ray Absorption Spectroscopy

The rare-earth based molybdenum chalcogenides, REMo₆Se₈ (RE = rare-earth metals) have been extensively studied because of their unique crystal structure based on Mo₆Se₈ clusters and their outstanding properties involving coexistence of superconductivity and magnetism. Among all these compounds, Ce and Eu based chalcogenides are magnetic and non-superconductors and possess many novel properties. Understanding their electronic structure is likely to provide valuable information about these materials. We employ X-ray absorption near-edge structure (XANES) spectroscopy at Mo and Se K-edges of EuMo₆Se₈ to identify the local environment respectively around Mo and Se ions and XANES spectra at L₃-edge of Eu ion to identify their valence state. Results from this study demonstrate that Se ions in EuMo₆Se₈ are in two inequivalent sites and the valency of Eu is divalent.     

稀土无机发光材料:电子结构、光学性能和生物应用

目前,稀土无机发光材料在激光、光通讯、平板显示、荧光生物标记和纳米光电子器件等领域具有广泛的应用前景.稀土离子(从Ce到Yb)是一类性能优异的结构和光谱探针,其在不同介质材料中的光学性能主要取决于其局域态的电子结构和激发态动力学.对稀土发光材料开展深入的光学和光电子学基础研究有助于发现新颖的光学性能或开辟新的应用领域.依托研制的低温高分辨激光光谱和上转换量子产率等仪器,本课题组致力于稀土无机发光材料电子结构与性能研究,近年来在发光材料的控制合成、电子结构、光学性能及生物应用等方面取得了系列重要结果.这些研究有望加快实现稀土无机发光材料在生物应用的突破,实现稀土资源的高值利用.     

InAs管状团簇及单壁InAs纳米管的结构、稳定性和电子性质

采用密度泛函理论研究了InnAsn (n≤90)管状团簇以及单壁InAs纳米管的几何结构、稳定性和电子性质. 小团簇InnAsn (n=1-3)基态结构和电子性质的计算结果与已有报道相一致. 当n≥4时优化得到了一族稳定的管状团簇, 其结构基元(In原子与As原子交替排列的四元环和六元环结构)满足共同的衍化通式. 团簇的平均结合能表明横截面为八个原子的管状团簇稳定性最好. 管状团簇前线轨道随尺寸的变化规律有效地解释了一维稳定管状团簇的生长原因, 同时也说明了实验上之所以能合成InAs纳米管的微观机理. 此外, 研究结果表明通过管状团簇的有效组装可得到宽带隙的InAs半导体单壁纳米管.     

Geometric, electronic, and bonding properties of AuNM (N = 1-7, M = Ni, Pd, Pt) clusters

Employing first-principles methods, based on density functional theory, we report the ground state geometric and electronic structures of gold clusters doped with platinum group atoms, Au(N)M (N = 1-7, M = Ni, Pd, Pt). The stability and electronic properties of Ni-doped gold clusters are similar to that of pure gold clusters with an enhancement of bond strength. Due to the strong d-d or s-d interplay between impurities and gold atoms originating in the relativistic effects and unique properties of dopant delocalized s-electrons in Pd- and Pt-doped gold clusters, the dopant atoms markedly change the geometric and electronic properties of gold clusters, and stronger bond energies are found in Pt-doped clusters. The Mulliken populations analysis of impurities and detailed decompositions of bond energies as well as a variety of density of states of the most stable dopant gold clusters are given to understand the different effects of individual dopant atom on bonding and electronic properties of dopant gold clusters. From the electronic properties of dopant gold clusters, the different chemical reactivity toward O(2), CO, or NO molecule is predicted in transition metal-doped gold clusters compared to pure gold clusters.     

Structures and electronic properties of silicene clusters: a promising material for FET and hydrogen storage

Structures and electronic properties of clusters of an all-Si analogue of graphene, silicene, have been studied through quantum chemical calculations. The structures of the six-membered rings show interesting chair like puckering, which for large sheet-like clusters form ordered ripples. Binding energies, HOMO-LUMO gaps and polarizabilities for the silicene clusters show interesting monotonic trends analogous to polyacenes. Stacking of two silicene layers leads to the formation of closed 3D clusters with high symmetry and strong Si-Si bonds. The heat of hydrogenation of silicene to form silicanes is overwhelmingly exothermic and leads to the opening up of the HOMO-LUMO gaps. Thus, analogous to graphanes, silicanes are predicted to be interesting materials for hydrogen storage and for their band engineering properties.     

Chemical modeling of mixed occupations and site preferences in anisotropic crystal structures: case of complex intermetallic borides

Transition-metal borides show not only promising physical properties but also a rich variety of crystal structures. In this context, quantum-chemical tools can shed light on important facets of the chemistry within such intermetallic borides. Using density-functional theory (DFT), we analyze in detail two phases of significant structural-chemical importance: the recently synthesized Ti(1+x)Os(2-x)RuB(2) and the isotypical Ti(1+x)Os(3-x)B(2). Starting from the observation of different Ti/Os occupations in X-ray crystal structure analysis, we assess suitable computational models and rationalize how the interplay of Ti-Ti, Ti-Os, and Os-Os bonds drives the site preferences. Then, we move on to a systematic investigation of the metal-boron bonds which embed the characteristic, trigonal-planar B(4) units within their metallic surroundings. Remarkably, the different Ti-B bonds in Ti(1+x)Os(2-x)RuB(2) (and also in its ternary derivative) are of vastly different strength, and the strength of these bonds does not correlate with their length. The tools presented in this work are based on simple and insightful chemical arguments together with DFT, and may subsequently be transferred to other intermetallic phases--transition-metal borides and beyond.     

Reductive Activation of Small Molecules by Anionic Coinage Metal Atoms and Clusters in the Gas Phase

Metal atoms and clusters exhibit chemical properties that are significantly different or totally absent in comparison to their bulk counterparts. Such peculiarity makes them potential building units for the generation of novel catalysts. Investigations of the gas‐phase reactions between size‐ and charge‐selected atoms/clusters and small molecules have provided fundamental insights into their intrinsic reactivity, thus leading to a guiding principle for the rational design of the single‐atom and cluster‐based catalysts. Especially, recent gas‐phase studies have elucidated that small molecules such as O₂, CO₂, and CH₃I can be catalytically activated by negatively‐charged atoms/clusters via donation of a partial electronic charge. This Minireview showcases typical examples of such “reductive activation” processes promoted by anions of metal atoms and clusters. Here, we focus on anionic atoms/clusters of coinage metals (Cu, Ag, and Au) owing to the simplicity of their electronic structures. The determination of a correlation between their activation modes and the electronic structures might be helpful for the future development of innovative coinage metal catalysts.     

Insight into the Geometric and Electronic Structures of Gold/Silver Superatomic Clusters Based on Icosahedron M13 Units and Their Alloys

Metal superatomic nanoclusters, with electronic structures similar to those of one certain atom, are an important type of metal clusters. Interestingly, metal clusters with metal cores composed of either icosahedral M₁₃ or icosahedral assemblies always have a greater potential to become superatomic clusters. Furthermore, superatomic clusters with similar electronic compositions could possess various geometric structures, owing to differences in the shells; this provides a deeper understanding of the metal superatomic cluster and the assembly for nanomaterials. Therefore, this review focuses on the geometric and electronic structures of gold/silver superatomic clusters based on icosahedron M₁₃ units and their alloys, which will facilitate the development of various applications of superatomic clusters.     

Theoretical Studies on the Electronic Properties of R_2M_(14)B (R = Lanthanides from La to Lu;M = Mn,Fe, Co,and Ni)

To search for an alternative for Nd₂Fe₁₄B,we have studied the electronic structures of R₂M₁₄B compounds,where R stands for rare-earth element and M for Mn,Fe,Co and Ni.By density functional theory(DFT),we discuss the atomic coordination environment and partial density of states(PDOS)in detail,with the emphasis on the interaction between the six kinds of M sites and the R atoms.We systemically calculated the electronic structures of sixty R₂M₁₄B compounds to provide systematic and reliable results for explaining the origination of magnetism,which is important for further development of Nd₂Fe₁₄B based magnet materials.     

Sub-nanometre sized metal clusters: from synthetic challenges to the unique property discoveries

Sub-nanometre sized metal clusters, with dimensions between metal atoms and nanoparticles, have attracted more and more attention due to their unique electronic structures and the subsequent unusual physical and chemical properties. However, the tiny size of the metal clusters brings the difficulty of their synthesis compared to the easier preparation of large nanoparticles. Up to now various synthetic techniques and routes have been successfully applied to the preparation of sub-nanometre clusters. Among the metals, gold clusters, especially the alkanethiolate monolayer protected clusters (MPCs), have been extensively investigated during the past decades. In recent years, silver and copper nanoclusters have also attracted enormous interest mainly due to their excellent photoluminescent properties. Meanwhile, more structural characteristics, particular optical, catalytic, electronic and magnetic properties and the related technical applications of the metal nanoclusters have been discovered in recent years. In this critical review, recent advances in sub-nanometre sized metal clusters (Au, Ag, Cu, etc.) including the synthetic techniques, structural characterizations, novel physical, chemical and optical properties and their potential applications are discussed in detail. We finally give a brief outlook on the future development of metal nanoclusters from the viewpoint of controlled synthesis and their potential applications.     

Rare-earth quinolinates: infrared-emitting molecular materials with a rich structural chemistry

Near-infrared-emitting rare-earth chelates based on 8-hydroxyquinoline have appeared frequently in recent literature, because they are promising candidates for active components in near-infrared-luminescent optical devices, such as optical amplifiers, organic light-emitting diodes, .... Unfortunately, the absence of a full structural investigation of these rare-earth quinolinates is hampering the further development of rare-earth quinolinate based materials, because the luminescence output cannot be related to the structural properties. After an elaborate structural elucidation of the rare-earth quinolinate chemistry we can conclude that basically three types of structures can be formed, depending on the reaction conditions: tris complexes, corresponding to a 1:3 metal-to-ligand ratio, tetrakis complexes, corresponding to a 1:4 metal-to-ligand ratio, and trimeric complexes, with a 3:8 metal-to-ligand ratio. The intensity of the emitted near-infrared luminescence of the erbium(III) complexes is highest for the tetrakis complexes of the dihalogenated 8-hydroxyquinolinates.     

Structure and function of oxide nanostructures: catalytic consequences of size and composition

Redox and acid-base properties of dispersed oxide nanostructures change markedly as their local structure and electronic properties vary with domain size. These changes give rise to catalytic behavior, site structures, and reaction chemistries often unavailable on bulk crystalline oxides. Turnover rates for redox and acid catalysis vary as oxide domains evolve from isolated monomers to two-dimensional oligomers, and ultimately into clusters with bulk-like properties. These reactivity changes reflect the ability of oxide domains to accept or redistribute electron density in kinetically-relevant reduction steps, in the formation of temporary acid sites via reductive processes, and in the stabilization of cationic transition states. Reduction steps are favored by low-lying empty orbitals prevalent in larger clusters, which also favor electron delocalization, stable anions, and strong Br?nsted acidity. Isomerization of xylenes and alkanes, elimination reactions of alkanols, and oxidation of alkanes to alkenes on V, Mo, Nb, and W oxide domains are used here to demonstrate the remarkable catalytic diversity made available by changes in domain size. The reactive and disordered nature of small catalytic domains introduces significant challenges in their synthesis and their structural and mechanistic characterization, which require in situ probes and detailed kinetic analysis. The local structure and electronic properties of these materials must be probed during catalysis and their catalytic function be related to specific kinetically-relevant steps. Structural uniformity can be imposed on oxide clusters by the use of polyoxometalate clusters with thermodynamically stable and well-defined size and connectivity. These clusters provide the compositional diversity and the structural fidelity required to develop composition-function relations from synergistic use of experiments and theory. In these clusters, the valence and electronegativity of the central atom affects the acid strength of the polyoxometalate clusters and the rate constants for acid catalyzed elementary steps via the specific stabilization of cationic transition states in isomerization and elimination reactions.     

Silica nanoarchitectures with tailored pores based on the hybrid three- and four-membered rings

Inspired by the recent developments in the controlled synthesis of porous materials, we present herein the structural prediction of silica nanoarchitectures by using the three- (3MRs) and four-membered rings (4MRs), which are more frequently found in the nanometer-sized particles than in the bulk form, as building blocks. The proposed models include the active molecular rings, thin nanowires, hollow nanotubes, discrete fullerene-like cages, and porous zeolite-like three-dimensional networks. Their geometrical and electronic structures and properties were studied by performing density functional calculations. These silica nanostructures were proved, using molecular dynamics simulations, to possess intrinsic structural stabilities with highly symmetrical geometries and regular nanochannels. These atomically well-defined clusters, (SiO)(n), are chemically more reactive than those proposed earlier and are energetically more favorable for n > 20 in high-level density functional calculations over the corresponding two-membered ring (2MR) chains and rings as well as the pure 3MR networks. The nanoparticles and nanodevices based on them are expected to have potential technological applications that mainly make use of their characteristic geometrical structures (nanosized pores) and novel electronic properties.     

Size dependence of the structures and energetic and electronic properties of gold clusters

The structures and stabilities of gold clusters with up to 14 atoms have been determined by density-functional theory. The structure optimizations and frequency analysis are performed with the Perdew-Wang 1991 gradient-corrected functional combined with the effective core potential and corresponding valence basis set (LANL2DZ). The turnover point from two-dimensional to three-dimensional geometry for gold clusters occurs at Au12. The energetic and electronic properties of the small gold clusters are strongly dependent on sizes and structures, which are in good agreement with experiment and other theoretical calculations. The even-odd oscillation in cluster stability and electronic properties predicted that the clusters with even numbers of atoms were more stable than the neighboring clusters with odd numbers of atoms. The stability and electronic structure properties of gold clusters are also characterized by the maximum hardness principle of chemical reactivity and minimum polarizability principle.     

Design of sodium lanthanide fluoride nanocrystals for NIR imaging and targeted therapy

Since the 18th century, rare-earth ions have been widely used as active dopants in inorganic lattices due to their unique optical properties. Rare-earth doping can control the crystal phase, morphology and size of nanomaterials, resulting in adjustable optical response of doped nanomaterials. The substrate of nanostructures can greatly affect the physical and chemical behavior of rare-earth ions. Therefore, it is also important to find suitable host materials. Among various new host materials, sodium lanthanide fluoride (NaLnF₄) nanoparticles are known for their photoluminescence properties and stability. This paper emphasizes the latest progress of NaLnF₄ and its derivatives nanoparticles and their related applications in various biological fields. This review covers the key criteria of NaLnF₄ and its derivatives, including basic electronic structure, lattice environment, doping strategy, surface functionalization and basic design principles for biological applications. At the same time, this paper also discusses the obstacles encountered in the development process and the research directions and challenges of future new applications.     

Molecular engineering of CxNy: Topologies,electronic structures and multidisciplinary applications

As a class of metal-free two-dimensional (2D) semiconductor materials, polymeric carbon nitrides have attracted wide attention recently due to its facile regulation of the molecular and electronic structures, availability in abundance and high stability. According to the different ratios of C and N atoms in the framework, a series of C_xN_y materials have been successfully synthesized by virtue of various precursors, which further triggers extensive investigations of broad applications ranging from sustainable photocatalytic reactions and highly sensitive optoelectronic biosensing. In view of topological structures on their electronic structures and material properties, the as-reported C_xN_y could be generally classified into two main categories with three- or six-bond-extending frameworks. Owing to the effective n→π^* transition in most C_xN_y materials, the relative energy level of the lone-pair electrons on N atoms is high, which thus endows the materials with the capability of visible light absorption. Meanwhile, the different repeating units, bridging groups and defect sites of these two kinds of C_xN_y allow them to effectively drive a diverse of promising applications that require specific electronic, interfacial and geometric properties. This review paper aims to summarize the recent progress in topological structure design and the relevant electronic band structures and striking properties of C_xN_y materials. In the final part, we also discuss the existing challenges of C_xN_y and outlook the prospect possibilities.     

Atomic and electronic structure of gold clusters: understanding flakes, cages and superatoms from simple concepts

Atomic structure and electronic structure are intimately interrelated properties of nanoclusters and nanoparticles, defining their stability, electronic, optical and chemical properties, in other words, their usability as potential components for nanoscale devices. This tutorial review attempts to describe the development in understanding the structures of bare and ligand-protected gold clusters over the past decade, based on selected density-functional-theory calculations. This review should be of interest both to newcomers in the field and to an interdisciplinary community of researchers working in synthesis, characterization and utilization of ligand-protected gold clusters.