Polyhedral Metal Research Articles

Preparation of rGO/CAU-10 anchored PdPbBi composites and their electrocatalytic ethylene glycol properties

An effective method to improve the catalytic performance of electrocatalytic alcohol oxidation by establishing strong interfacial interactions through novel carrier materials and polymetallic alloys. In this paper, novel polyhedral metal–organic framework Al-based [Al(OH)(mBDC)] (CAU-10) composites with PdPbBi trimetallic particles embedded in folded graphene oxide (rGO) modified by a simple hydrothermal reaction were prepared and applied to the electrocatalytic oxidation reaction of ethylene glycol. The results of electrochemical tests showed that the trimetallic catalysts exhibited excellent electrocatalytic activity compared to commercial Pd/C. In particular, PdPbBi@rGO/CAU-10 has the highest peak current density of 241.82 mA cm−2, which is 8.97 times higher than that of Pd/C (26.92 mA cm−2), and the largest electrochemical active area (ECSA) value of 88.12 mA cm−2, which is 2.40 times higher than that of Pd/C (36.75 mA cm−2). This outstanding electrocatalytic activity is mainly attributed to the polyhedral structure of CAU-10 composite carriers and the abundance of oxygen-containing atoms, which is conducive to the homogeneous loading of metals, at the same time, the strong electronic effect between Pd, Pb and Bi and the abundance of oxygen-containing species provide significant enhancement of electrocatalytic activity and stability, which provides an important reference for the development of electrocatalysts for ethylene glycol fuel cells.

High-Precision Detection Algorithm for Metal Workpiece Defects Based on Deep Learning

Computer vision technology is increasingly being widely applied in automated industrial production. However, the accuracy of workpiece detection is the bottleneck in the field of computer vision detection technology. Herein, a new object detection and classification deep learning algorithm called CSW-Yolov7 is proposed based on the improvement of the Yolov7 deep learning network. Firstly, the CotNet Transformer structure was combined to guide the learning of dynamic attention matrices and enhance visual representation capabilities. Afterwards, the parameter-free attention mechanism SimAM was introduced, effectively enhancing the detection accuracy without increasing computational complexity. Finally, using WIoUv3 as the loss function effectively mitigated many negative influences during training, thereby improving the model’s accuracy faster. The experimental results manifested that the mAP@0.5 of CSW-Yolov7 reached 93.3%, outperforming other models. Further, this study also designed a polyhedral metal workpiece detection system. A large number of experiments were conducted in this system to verify the effectiveness and robustness of the proposed algorithm.

Electrodeposited copper enhanced removal of 2,4-dichlorophenol in batch and flow reaction in Cu@CC-PS-MFC system

Combination of microbial fuel cell (MFC) and advanced oxidation process (AOP) is promising for pollutant removal. In this paper, Cu0-loaded carbon cloth cathode by electrodeposition (Cu@CC-PS-MFC) was applied to enhance 2,4-dichlorophenol (2,4-DCP) degradation based on persulfate (PS) activation in microbial fuel cell. Cu0 exhibited a typical structure of face-centered cubic metal polyhedron on carbon cloth. The removal of 2,4-DCP by Cu@CC-PS-MFC (75.6%) was enhanced by more than 50% compared to CC-PS-MFC (49.2%) after 1 h of reaction. 30 mg/L 2,4-DCP in Cu@CC-PS-MFC was completely removed and achieved a high mineralization (80.6%) after 9 h of reaction under optimized condition with low dissolved copper ion concentration (0.615 mg/L). Meanwhile, more than 90% removal of 2,4-DCP was stably achieved with flow operation condition (hydraulic residence time of 7.2 h). The change of copper valent state Cu0/Cu2O/CuO was the main mechanism of PS activation with main reactive species of O•H and O21. The bioanode of MFC enhanced the in-situ regeneration of ≡Cu+ and ≡Cu0 on the catalyst surface by transporting electrons, which was believed to contribute to good catalyst lifetime and excellent 2,4-DCP removal. Electrodeposited copper contributes to the enhanced degradation of 2,4-DCP with energy recovery at the same time which can further broaden the application MFC.

Coloration in Supraparticles Assembled from Polyhedral Metal-Organic Framework Particles.

Supraparticles are spherical colloidal crystals prepared by confined self‐assembly processes. A particularly appealing property of these microscale structures is the structural color arising from interference of light with their building blocks. Here, we assemble supraparticles with high structural order that exhibit coloration from uniform, polyhedral metal–organic framework (MOF) particles. We analyse the structural coloration as a function of the size of these anisotropic building blocks and their internal structure. We attribute the angle‐dependent coloration of the MOF supraparticles to the presence of ordered, onion‐like layers at the outermost regions. Surprisingly, even though different shapes of the MOF particles have different propensities to form these onion layers, all supraparticle dispersions show well‐visible macroscopic coloration, indicating that local ordering is sufficient to generate interference effects.

Coloration in Supraparticles Assembled from Polyhedral Metal‐Organic Framework Particles

AbstractSupraparticles are spherical colloidal crystals prepared by confined self‐assembly processes. A particularly appealing property of these microscale structures is the structural color arising from interference of light with their building blocks. Here, we assemble supraparticles with high structural order that exhibit coloration from uniform, polyhedral metal–organic framework (MOF) particles. We analyse the structural coloration as a function of the size of these anisotropic building blocks and their internal structure. We attribute the angle‐dependent coloration of the MOF supraparticles to the presence of ordered, onion‐like layers at the outermost regions. Surprisingly, even though different shapes of the MOF particles have different propensities to form these onion layers, all supraparticle dispersions show well‐visible macroscopic coloration, indicating that local ordering is sufficient to generate interference effects.

REVIEW OF THE PHYSICAL AND MECHANICAL CHARACTERISTICS OF POLYURETHANE NANOCOMPOSITES

Polyurethane nanocomposites are promising materials in many industries, they have superior physical and mechanical properties compared to the original polyurethane. This paper presents an analysis of the physical and mechanical properties of polyurethane nano-composites with various types of fillers such as organoclays, carbon nanotubes, polyhedral oligomeric silse-squioxanes, graphene, graphene oxide, polytetrafluoroethylene, and metal nanoparticles. The concentration-dependent effects in changing the structure and properties of polyurethane composites under the influence of the added fillers were also considered. It is noted that the values of physical and mechanical properties are influenced by the uniform distribution of nanofiller particles in the composite and their chemical modification. It was found that with a uniform distribution of nanoparticles in the polymer matrix, the physicomechanical properties of the resulting composites increase.

PH-responsive aminotriazole doped metal organic frameworks nanoplatform enables self‐boosting reactive oxygen species generation through regulating the activity of catalase for targeted chemo/chemodynamic combination therapy

The rational integration of chemotherapy and hydroxyl radical (·OH)-mediated chemodynamic therapy (CDT) via functional metal–organic frameworks (MOF) carriers has great potential in cancer therapy. In this work, aminotriazole (3-AT) doped polyhedral metal organic frameworks (denoted as MAF) were prepared by template ligand replacement, where CDT was initiated by Cu2+/Cu+ modulated Fenton reaction and enhanced by effectively regulating the catalase activity with 3-AT. However, a rod-like Cu-MOF with 3-AT served as a ligand was obtained by the hydrothermal method without using template. In contrast to Cu-MOF, pH-responsive MAF was chosen as the carrier for targeted drug delivery due to its higher drug load of 17.6% and relatively uniform size, where doxorubicin (DOX) as a model drug was loaded in its cavity and hyaluronic acid (HA) was coated on its surface via electrostatic interactions (denoted as HA-MAF@DOX). In vitro experiments demonstrated that HA-MAF@DOX had high transport efficiency of DOX, effective regulation of catalase (CAT) activity and enhanced cytotoxicity to HepG2 cells. This work is the first use of enzyme inhibitors as ligands to construct functional MOFs via template ligand replacement for effective regulating enzyme activity, mediating intracellular redox homeostasis and enhancing CDT efficacy, which provides a feasible strategy for the construction the functional MOFs in cancer therapy.

Principles Determining the Structure of Transition Metals.

For the better part of a century researchers across disciplines have sought to explain the crystallography of the elemental transition metals: hexagonal close packed, body centered cubic, and face centered cubic in a form similar to that used to rationalize the structure of organic molecules and inorganic complexes. Pauling himself tried with limited success to address the origins of transition metal stability. These early investigators were handicapped, however, by incomplete knowledge regarding the structure of metallic electron density. Here, we exploit modern approaches to electron density analysis to first comprehensively describe transition metal electron density. Then, we use topological partitioning and quantum mechanically rigorous treatments of kinetic energy to account for the structure of the density as arising from the interactions between metallic polyhedra. We argue that the crystallography of the early transition metals results from charge transfer from the so called “octahedral” to “tetrahedral cages” while the face centered cubic structure of the late transition metals is a consequence of anti-bonding interactions that increase octahedral hole kinetic energy.

Synthesis of Polyhedral Metal-Organic Framework@Mesoporous Silica Hybrid Nanocomposites with Branched Shapes.

The structural modulation of multicompartment porous nanomaterials is one of the major challenges of nanoscience. Herein, by utilizing the polyhedral effects/characteristics of metal-organic frameworks (MOFs), we present a versatile approach to construct MOF-organosilica hybrid branched nanocomposites with MOF cores, SiO2 shells, and periodic mesoporous organosilica (PMO) branches. The morphology, structure, and functions of the obtained hybrid nanocomposites can be facilely modulated by varying particle size, shape, or crystalline structures of the MOF cores. Specifically, these branched multicompartment porous nanoparticles exhibit evasion behaviors in epithelial cells compared with macrophage cells, which may endow them great potential as a vehicle for immunotherapy.

Polyhedral metal–organic framework monolayer colloidal crystals with sharpened and crystal facet-dependent selectivity for organic vapor sensing

Polyhedral metal–organic framework monolayer colloidal crystals demonstrate sharpened and crystal facet-dependent selectivity for organic vapors by eliminating grain boundaries and randomly exposed crystal surfaces.

MWCNT-mesoporous silica nanocomposites inserted in a polyhedral metal–organic framework as an advanced hybrid material for energy storage device

Hybridizing of trimetallic HKUST-1 with mesoporous SBA/CNT is highly desirable fot the improvement of energy and power densities in supercapacitors.

Intermetallic Compounds KnMm (М = Ag, Au, As, Sb, Bi, Ge, Sn, Pb): Geometrical and Topological Analysis, Cluster Precursors, and Self-Assembly of Crystal Structures

A geometrical and topological analysis and simulation of the self-assembly of the crystal structures of intermetallic compounds formed in the K–M (M = Ag, Au, As, Sb, Bi, Ge, Sn, Pb) systems have been performed using computation methods (the ToposPro software). The precursor metal clusters of KnMm crystal structures are determined based on the algorithms of structure-graph decomposition in cluster structures and construction of the basic net of structure in the form of a graph with nodes corresponding to cluster centers. Tetrahedral metal clusters, forming packings in the K3Bi-cF16, K3Bi-hP8, K2As2-oP16, K2Sb2-mP16, and K2Sb2-mP32 crystal structures; tetrahedral metal clusters and spacers for the K(K2As2)2-mC18, K4(Pb4)-tI64, and K2(Au4)-hP12 structures; polyhedral metal clusters KK4Pb12 and spacers for the Pb12K(K4Pb12)-cI58 structure; and dodecahedral metal clusters KGe20 and spacers for the K3Ge3(KGe20)-cP54 structure have been found. The symmetry and topology code of the self-assembly of crystal structures of intermetallic compounds KnMm has been reconstructed from precursors $$S_{3}^{0}$$ in the following form: primary chain $$S_{3}^{1}$$ → microlayer $$S_{3}^{2}$$ → microframework $$S_{3}^{3}$$ .

RETRACTED ARTICLE: A Heterometallic MOF for Highly Selective Al3+ Ion Detection and Protective Effect Against Periodontitis by Reducing P. gingivalis CFU and Inflammatory Cytokines Levels

By employment of an amide-functionalized tetracarboxylic ligand 5,5′-(carbonylbis(azanediyl))-diisophthalic acid (H4cbab), a new polyhedral metal–organic framework (MOF) with the chemical formula of {[InZn2(cbda)2(H2O)2](NMF)3}n (1, NMF = N-methylformamide) has been synthesized under the solvothermal reaction condition. The structural feature was studied via the single crystal X-ray diffraction along with ultimate analysis. This as-prepared MOF shows excellent luminescence performance which can be able to detect Al3+ ions selectively. In aqueous solutions, the detection limitation for Al3+ ion is 0.56 µM, which is significantly below the highest standard of 7.41 µM for Al3+ ion in drinking water that is defined by the World Health Organization (WHO). The protective effect of compound against periodontitis was further explored. The viable cell counts (CFU) number was counted to evaluate the inhibitory effect of compound on bacterial growth. The enzyme linked immunosorbent assay (ELISA) was carried on in order to measure accurately the proportion of inflammatory cytokines in gingival fluid around the implant. The potential binding modes of the synthesized compounds as well as the targeted protein was explored by calculating docking with high accuracy as well as pose scoring process.

Spectroscopic Characterization of μ-η1:η1-Peroxo Ligands Formed by Reaction of Dioxygen with Electron-Rich Iridium Clusters.

Although oxygen is a common ligand in supported metal catalysts, its coordination has been challenging to elucidate. We now characterize a diiridium complex that has been previously shown by X-ray diffraction crystallography to incorporate a μ-η1:η1-peroxo ligand. We observe markedly enhanced intensity at 788 cm-1 in the Raman spectrum of this complex, which is a consequence of bonding of the peroxo ligand but does not shift upon 18O labeling. Electronic structure calculations at the density functional theory level suggest that this increase in Raman intensity results from bands associated with rocking of CH2 substituents directly attached to P(Ph)2 groups coupling with the O-O band. These results provide part of the foundation for understanding oxygen ligands on a silica-supported tetrairidium carbonyl cluster stabilized with bulky electron-donating phosphine ligands [p-tert-butyl-calix[4]arene(OPr)3(OCH2PPh2) (Ph = phenyl; Pr = propyl)]. Reaction of the cluster with O2 also led to the growing in of a Raman band at 788 cm-1, similar to that in the diiridium complex and also assigned to the bonding of a bridging peroxo ligand. Infrared spectra recorded as the supported cluster reacted in sequential exposures to (i) H2, (ii) O2, (iii) H2, and (iv) CO indicate that two bridging peroxo ligands were bonded irreversibly per tetrairidium cluster, replacing bridging carbonyl ligands without altering either the cluster frame or the phosphine ligands. X-ray absorption near edge and infrared spectra include isosbestic points signifying a stoichiometrically simple reaction of the cluster with O2, and mass spectra of the effluent gas show that CO2 formed by oxidation of one terminal CO ligand per cluster as H2 (and not H2O) formed, evidence that hydride ligands had been present on the cluster following treatment (i). The understanding of how O2 reacts with the metal polyhedron provides a foundation for understanding of how oxidation catalysis may proceed on the surfaces of noble metals.

Polyhedral metal cage for photocatalytic CO2 reduction

Polyhedral metal cage for photocatalytic CO2 reduction

Iron polyphosphate glasses for waste immobilization

AbstractIron polyphosphate glasses resist attack by water, can dissolve large concentrations of species that are otherwise insoluble in borosilicate glass melts, and can be processed at relatively low temperatures (1000‐1200°C), and so are viable hosts for vitrifying hazardous and radioactive wastes. The properties of iron polyphosphate glasses depend on the distributions of phosphate anions and the nature of the bonds between those anions and various metal polyhedra, and quantitative information can be obtained about those structures using a variety of spectroscopic, diffraction, and chromatographic techniques. This structural information helps explain compositional trends in properties, including dissolution rates, electrical conductivity, thermal properties and crystallization tendency. Studies of waste forms made with low activity and high level wastes are reviewed and related back to an understanding of the structures and properties of simpler iron polyphosphate glasses.

Crystal Chemistry of Lithium Intermetallic Compounds: A Survey

The structural chemistry of lithium intermetallic compounds that are formed in Li–М binary systems where М = Ca, Sr, Ba, Mg, Zn, Cd, and Hg is surveyed. It is for the first time that the crystal structures of intermetallic compounds are classified in terms of polyhedral precursor metal clusters (in the program package ToposPro). The precursor metal clusters of crystal structures are identified using the algorithms of partitioning structural graphs into cluster structures and via the design of the basal 3D network of the structure in the form of a graph whose nodes correspond to the positions of the centers of precursor clusters. Tetrahedral precursor metal clusters M4 are identified for the crystal structures LiZn3-oC4, LiMg3-hP2, LiCd3-hP2, LiHg3-hP8, (LiMg3)(Li2Mg2)-tI16, Li2Zn2-cF16, Li2Cd2-cF16, Li2Hg2-cP2, Li3Cd-cF4, and Li3Hg-cF16; tetrahedral metal clusters M4 are found for the framework structures with spacer atoms Sr(Li2Sr2)-tP20, Ca2(Li4)-cF24, and Ca2(Li4)-cP12; tetrahedral metal clusters M4 and rings M6, for framework structures Ba3Li2(Li10)-hP30 and Ba3Li2(Li4In6)-hP30; icosahedral metal clusters M13 for the framework structure Li(Zn13)-cF112; bilayer tetrahedral metal clusters 0@М4@M22 for the framework structure Li23Sr6-cF116; and deltahedra М17 and deltahedra М30, for framework structures Sr4Li14 [Sr(Sr4Li12)] [(Sr2 (Sr8Li18)]-tI252 and Ba4Li14 [Ba(Ba4Li12)][(Ba2 (Ba8Li18)]-tI252. The scenario of crystal structure self-assembly from precursor metal clusters S30 in intermetallic compounds is reconstituted as: primary chain S31→ microlayer S32→ microframework S33.

A polyhedral metal-organic framework based on rigid precursor for photocatalytic properties

A 3D polyhedral metal organic framework, [Cu4(L)2(H2O)4∙5DMF]n (1) (H4L = 3,5‑di(3,5‑dicarboxyphenyl)nitrobenzene), has been designed and successfully synthesized. 1 shows a 3D mfj topological framework with 1D triangular channels. The UV diffuse reflectance spectroscopy of the MOF indicates its semiconducting nature which induces photocatalytic property in the MOF. The photocatalytic property of 1 in photo-degradation of organic dyes viz. methyl violet and Rhodamine B have been investigated. The possible mechanism for the photocatalytic activity of 1 against organic dyes has been addressed using density of states (DOS) and partial DOS (pDOS) calculations.

Correlation of Low-Index Facets to Active Sites in Micrometer-Sized Polyhedral Pyrochlore Electrocatalyst

Polyhedral structure has attracted attention as a promising morphology of bifunctional electrocatalysts, which is suitable for providing catalytic active facets. However, polyhedral metal oxides have been suffering from control of their morphology. Herein, we develop micrometer-sized polyhedral bismuth ruthenate pyrochlore (P-BRO) for Zn–air batteries, which achieve highly improved catalytic activity by development of (100), (110), and (111) planes regardless of particle size. To clarify the formation mechanism of polyhedral structure, in situ transmission electron microscopy analysis is performed at 1050 °C, resulting in observation of Ostwald ripening and facets formation. Furthermore, we reveal that A- and B-site cations on low-index facets of the P-BRO could mainly contribute to catalytic activity by first-principle calculations. For practical application, we performed Zn–air flow batteries, which could effectively remove precipitated zinc oxide particles on the surface of air electrode, resulting in ...

Switching of Current Rectification Ratios within a Single Nanocrystal by Facet-Resolved Electrical Wiring.

Here we show that within a single polyhedral metal oxide nanoparticle a nanometer-scale lateral or vertical sliding of a small metal top contact ( e. g., <50 nm) leads to a 10-fold change in current rectification ratios. Electron tunneling imaging and constant-force current-potential analysis in atomic force microscopy demonstrate that within an individual p-n rectifier (a Cu2O nanocrystal on silicon) the degree of current asymmetry can be modulated predictably by a set of geometric considerations. We demonstrate the concept of a single nanoscale entity displaying an in-built range of discrete electrical signatures and address fundamental questions in the direction of "landing" contacts in single-particle diodes. This concept is scalable to large 2D arrays, up to millimeters in size, with implications in the design and understanding of nanoparticle circuitry.