Recent Progress in Synthesis, Mechanism and Applications of Zinc-Based Metal-Organic Frameworks for Fluorescent Sensing

As more and more pollutants threaten human health, it is necessary and essential to develop sensitive, accurate and rapid methods and sensory materials to detect harmful substance. Metal-organic frameworks (MOFs) are inorganic-organic hybrids assembled from inorganic metal ions or clusters and suitable organic ligands. Zinc-based MOFs (Zn-MOFs) have emerged as one of the most promising sensory material of MOFs for practical applications, and attracted significant attention due to structural diversity and incomparable stability properties. However, there are few reviews on systemic summary of synthesis design, mechanism and application of Zn-MOFs. In this review, we summarize the synthesis design methods, structure types and luminescence mechanism of Zn-MOFs sensor recognition in the past ten years and their applications in metal cations, anions, organic compounds and other analytes. Finally, we present a short conclusion, and look forward to the future development direction of Zn-MOFs.

Investigation on Law of Intercalation of Metal-Ammonia into Graphite by a Microstructural Parameter Method

The laws of forming metal- ammonia- graphite biintercalation compound (MAGBC ) undr natural or electrolytic conditions were studied by selecting microstructural parameter functions in accordance with the chemcal bond theory, and function Φ(g) was proposed to characterize the capability of metal-liquid ammonia solutions to be interalated and the relevant laws were thus summed up together with structural paramter diagrams. Results in general agreement with experimental facts, and some expected results without experiment reports as well, were obtained and satisfactorily explained from the view point of energy.

A two-dimensional threshold voltage analytical model for metal-gate/high-k/SiO_2 /Si stacked MOSFETs

In this paper the influences of the metal-gate and high-k/SiO 2 /Si stacked structure on the metal-oxide-semiconductor field-effect transistor（MOSFET） are investigated.The flat-band voltage is revised by considering the influences of stacked structure and metal-semiconductor work function fluctuation.The two-dimensional Poisson＇s equation of potential distribution is presented.A threshold voltage analytical model for metal-gate/high-k/SiO 2 /Si stacked MOSFETs is developed by solving these Poisson＇s equations using the boundary conditions.The model is verified by a two-dimensional device simulator,which provides the basic design guidance for metal-gate/high-k/SiO 2 /Si stacked MOSFETs.

Recent progress in rechargeable alkali metal-air batteries

Rechargeable alkali metal-air batteries are considered as the most promising candidate for the power source of electric vehicles(EVs) due to their high energy density. However, the practical application of metal-air batteries is still challenging. In the past decade, many strategies have been purposed and explored, which promoted the development of metal-air batteries. The reaction mechanisms have been gradually clarified and catalysts have been rationally designed for air cathodes. In this review, we summarize the recent development of alkali metal-air batteries from four parts: metal anodes, electrolytes, air cathodes and reactant gases, wherein we highlight the important achievement in this filed. Finally problems and prospective are discussed towards the future development of alkali metal-air batteries.

Application of ferrate(VI) in the treatment of industrial wastes containing metal-complexed cyanides : A green treatment

Ferrate（VI） was employed for the oxidation of cyanide （CN） and simultaneous removal of copper or nickel in the mixed/complexed systems of CN-Cu, CN-Ni, or CN-Cu-Ni. The degradation of CN （1.00 mmol/L） and removal of Cu （0.095 mmol/L） were investigated as a function of Fe（Ⅵ） doses from 0.3-2.00 mmol/L at pH 10.0. It was found that Fe（Ⅵ） could readily oxidize CN and the reduction of Fe（Ⅵ） into Fe（Ⅲ） might serve efficiently for the removal of free copper ions. The increase in Fe（Ⅵ） dose apparently favoured the CN oxidation as well as Cu removal. Moreover, the pH dependence study （pH 10.0-13.0） revealed that the oxidation of CN was almost unaffected in the studied pH range （10.0-13.0）, however, the maximum removal efficiency of Cu was obtained at pH 13.0. Similarly, treatment was carded out for CN-Ni system having the initial Ni concentration of 0.170 mmol/L and CN concentration of 1.00 mmol with Fe（Ⅵ） dose 2.00 mmol at various pH values （10.0-12.0）. Results showed a partial oxidation of CN and partial removal of Ni. It can be observed that Fe（Ⅵ） can partially degrade the CN-Ni complex in this pH range. Further, Fe（Ⅵ） was applied for the treatment of simulated industrial waste/effluent waters treatment containing CN, Cu, and Ni.

Hybrid metal-insulator-metal structures on Si nanowires array for surface enhanced Raman scattering

Surface enhanced Raman scattering(SERS)is an efficient technique to detect low concentration molecules.In this work,periodical silicon nanowires(Si NWs)integrated with metal-insulator-metal(MIM)layers are employed as SERS substrates.Laser interference lithography(LIL)combined with reactive ion etching(RIE)is used to fabricate large-area periodic nanostructures,followed by decorating the MIM layers.Compared to MIM disks array on Si surface,the SERS enhancement factor(EF)of the MIM structures on the Si NWs array can be increased up to 5 times,which is attributed to the enhanced electric field at the boundary of the MIM disks.Furthermore,high density of nanoparticles and nanogaps serving as hot spots on sidewall surfaces also contribute to the enhanced SERS signals.Via changing the thickness of the insulator layer,the plasmonic resonance can be tuned,which provides a new localized surface plasmon resonance(LSPR)characteristic for SERS applications.

Hierarchical Metal-Organic Frameworks with Macroporosity:Synthesis, Achievements,and Challenges

Introduction of multiple pore size regimes into metalorganic frameworks(MOFs)to form hierarchical porous structures can lead to improved performance of the material in various applications.In many cases,where interactions with bulky molecules are involved,enlarging the pore size of typically microporous MOF adsorbents or MOF catalysts is crucial for enhancing both mass transfer and molecular accessibility.In this review,we examine the range of synthetic strategies which have been reported thus far to prepare hierarchical MOFs or MOF composites with added macroporosity.These fabrication techniques can be either pre-or post-synthetic and include using hard or soft structural template agents,defect formation,routes involving supercritical CO2,and 3D printing.We also discuss potential applications and some of the challenges involved with current techniques,which must be addressed if any of these approaches are to be taken forward for industrial applications.

Alkali metal cation doping of metal-organic framework for enhancing carbon dioxide adsorption capacity

Metal-organic frameworks （MOFs） have attracted much attention as adsorbents for the separation of CO2 from flue gas or natural gas. Here, a typical metal-organic framework HKUST-I（also named Cu-BTC or MOF-199） was chemically reduced by doping it with alkali metals （Li, Na and K） and they were further used to investigate their CO2 adsorption capacities. The structural information, surface chemistry and thermal behavior of the prepared adsorbent samples were characterized by X-ray powder diffraction （XRD）, thermo-gravimetric analysis （TGA） and nitrogen adsorption-desorption isotherm analysis. The results showed that the CO2 storage capacity of HKUST-1 doped with moderate quantities of Li＋, Na＋ and K＋, individually, was greater than that of unmodified HKUST-1. The highest CO2 adsorption uptake of 8.64 mmol/g was obtained with 1K-HKUST-1, and it was ca. 11% increase in adsorption capacity at 298 K and 18 bar as compared with HKUST- 1. Moreover, adsorption tests showed that HKUST-1 and 1K-HKUST-1 displayed much higher adsorption capacities of CO2 than those of N2. Finally, the adsorption/desorption cycle experiment revealed that the adsorption performance of 1K-HKUST-1 was fairly stable, without obvious deterioration in the adsorption capacity of CO2 after 10 cycles.

Directional solidification of metal-gas eutectic and fabrication of regular porous metals

Directional solidification of metal-gas eutectic (Gasar) is a novel process for making regular porous metals.This process is based on a solid-gas eutectic reaction involving a gaseous medium and a metal or a ceramic phase, andallows an easy control of the porosity, such as its pore size, pore orientation and morphology in a wide range by properlyadjusting its melting and solidification conditions. The latest progress and our research work in this field are reviewed inthis paper.

High density Al2O3/TaN-based metal-insulatormetal capacitors in application to radio equency integrated circuits

Metal-insulator-metal （MIM） capacitors with atomic-layer-deposited Al2O3 dielectric and reactively sputtered TaN electrodes in application to radio frequency integrated circuits have been characterized electrically. The capacitors exhibit a high density of about 6.05 fF/μm^2, a small leakage current of 4.8 × 10^-8 A/cm^2 at 3 V, a high breakdown electric field of 8.61 MV/cm as well as acceptable voltage coefficients of capacitance （VCCs） of 795 ppm/V2 and 268ppm/V at 1 MHz. The observed properties should be attributed to high-quality Al2O3 film and chemically stable TaN electrodes. Further, a logarithmically linear relationship between quadratic VCC and frequency is observed due to the change of relaxation time with carrier mobility in the dielectric. The conduction mechanism in the high field ranges is dominated by the Poole-Frenkel emission, and the leakage current in the low field ranges is likely to be associated with trap-assisted tunnelling. Meanwhile, the Al2O3 dielectric presents charge trapping under low voltage stresses, and defect generation under high voltage stresses, and it has a hard-breakdown performance.

PARTICULATE SIZE EFFECTS IN THE PARTICLE-REINFORCED METAL-MATRIX COMPOSITES

The influences of I,article size on the mechanical properties of the particulate metal matrix composite;are obviously displayed in the experimental observations. However, the phenomenon can not be predicted directly using the conventional elastic-plastic theory. It is because that no length scale parameters are involved in the conventional theory. In the present research, using the strain gradient plasticity theory, a systematic research of the particle size effect in the particulate metal matrix composite is carried out. The roles of many composite factors, such as: the particle size, the Young's modulus of the particle, the particle aspect ratio and volume fraction, as well as the plastic strain hardening exponent of the matrix material, are studied in detail. In order to obtain a general understanding for the composite behavior, two kinds of particle shapes, ellipsoid and cylinder, are considered to check the strength dependence of the smooth or non-smooth particle surface. Finally, the prediction results will be applied to the several experiments about the ceramic particle-reinforced metal-matrix composites. The material length scale parameter is predicted.

Carbon-based derivatives from metal-organic frameworks as cathode hosts for Li–S batteries

Lithium-sulfur batteries(Li–S batteries) are promising candidates for the next generation high-energy rechargeable Li batteries due to their high theoretical specific capacity(1672 m Ahg-1) and energy density(2500 Wh kg-1). The commercialization of Li–S batteries is impeded by several key challenges at cathode side, e.g. the insulating nature of sulfur and discharged products(Li2S 2 and Li2S), the solubility of long-chain polysulfides and volume variation of sulfur cathode upon cycling. Recently, the carbonbased derivatives from metal-organic frameworks(MOFs) has emerged talent in their utilization as cathode hosts for Li–S batteries. They are not only highly conductive and porous to enable the acceleration of Li +/e-transfer and accommodation of volumetric expansion of sulfur cathode during cycling, but also enriched by controllable chemical active sites to enable the adsorption of polysulfides and promotion of their conversion reaction kinetics. In this review, based on the types of MOFs(e.g. ZIF-8, ZIF-67, Prussian blue, Al-MOF, MOF-5, Cu-MOF, Ni-MOF), the synthetic methods, formation process and morphology, structural superiority of MOFs-derived carbon frameworks along with their electrochemical performance as cathode host in Li–S batteries are summarized and discussed.

Rational design of carbon-based metal-free catalysts for electrochemical carbon dioxide reduction: A review

Electrochemical CO2 reduction to chemicals or fuels presents one of the most promising strategies for managing the global carbon balance, which yet poses a significant challenge due to lack of efficient and durable electrocatalyst as well as the understanding of the CO2 reduction reaction(CO2RR) mechanism.Benefiting from the large surface area, high electrical conductivity, and tunable structure, carbon-based metal-free materials(CMs) have been extensively studied as cost-effective electrocatalysts for CO2RR.The development of CMs with low cost, high activity and durability for CO2RR has been considered as one of the most active and competitive directions in electrochemistry and material science.In this review article,some up-to-date strategies in improving the CO2RR performance on CMs are summarized.Specifically, the approaches to optimize the adsorption of CO2RR intermediates, such as tuning the physical and electronic structure are introduced, which can enhance the electrocatalytic activity of CMs effectively.Finally, some design strategies are proposed to prepare CMs with high activity and selectivity for CO2RR.

Synthesis and Crystal Structure of a Novel Chiral 3D Metal-organic Framework Based on an N-methyl Substituted Salan Ligand

A chiral 3D metal-organic framework [CdL].DMSO＇H20 （1） was constructed by an N-methyl substituted salan ligand （H2L）, and characterized by elemental analyses, IR, TGA, powder XRD and single-crystal X-ray crystallography. 1 crystallizes in the chiral hexagonal space group P6522 with a = b = 12.2175（3）, c = 51.450（3） A, V= 6650.9（4） A3, Z = 6, Mr = 883.45, Dc = 1.323 g.cm-3, F（000） = 2760, 2（CuKa） = 1.54178 A,β = 4.771 mm-1, GOOF = 1.041, R = 0.0313 for 3901 observed reflections with I 〉 20（/） and wR = 0.0773.1 consists of three identical sets of independent 3D frameworks interpenetrated with each other. In each set of such 3D frameworks, one half of the monomer （CdL）1/2 as the building unit forms double antiparrel helical chains which are further bridged together by other （CdL）1/2 units from adjacent helical chains. All CdL units in 1 adopt A geometry. DMSO and water guest molecules are found in the gap of the interpenetrated frameworks.

Direct Growth of Graphene on Silicon by Metal-Free Chemical Vapor Deposition

The metal-free synthesis of graphene on singlecrystal silicon substrates, the most common commercial semiconductor, is of paramount significance for many technological applications. In this work, we report the growth of graphene directly on an upside-down placed,single-crystal silicon substrate using metal-free, ambientpressure chemical vapor deposition. By controlling the growth temperature, in-plane propagation, edge-propagation, and core-propagation, the process of graphene growth on silicon can be identified. This process produces atomically flat monolayer or bilayer graphene domains, concave bilayer graphene domains, and bulging few-layer graphene domains. This work would be a significant step toward the synthesis of large-area and layer-controlled, high-quality graphene on single-crystal silicon substrates.

Metallic debris from metal-on-metal total hip arthroplasty regulates periprosthetic tissues

The era of metal-on-metal(MoM) total hip arthroplasty has left the orthopaedic community with valuable insights and lessons on periprosthetic tissue reactions to metallic debris. Various terms have been used to describe the tissue reactions. Sometimes the nomenclature can be confusing. We present a review of the concepts introduced by Willert and Semlitsch in 1977,along with further developments made in the understanding of periprosthetic tissue reactions to metallic debris. We propose that periprosthetic tissue reactions be thought of as(1) gross(metallosis, necrosis, cyst formation and pseudotumour);(2) histological(macrophage-dominated, lymphocyte-dominated or mixed);and(3) molecular(expression of inflammatory mediators and cytokines such as interleukin-6 and tumor necrosis factor-alpha). Taper corrosion and modularity are discussed, along with future research directions to elucidate the antigen-presenting pathways and materi-al-specific biomarkers which may allow early detection and intervention in a patient with adverse periprosthetic tissue reactions to metal wear debris.

Plasmonically induced reflection in metal-insulator-metal waveguides with two silver baffles coupled square ring resonator

A plasmonic waveguide coupled system that is composed of a square ring cavity and a metal-insulator-metal （MIM） waveguide with two silver baffles is proposed. The transmission and reflection properties of the proposed plasmonic system are investigated numerically using the finite element method. The normalized Hz field distributions are calculated to analyze the transmission mode in the plasmonic system. The extreme destructive interference between light mode and dark mode causes plasmonically induced reflection （PIR） window in the transmission spectrum. The PIR window is fitted using the coupled mode theory. The analytical result agrees with the simulation result approximately. In addition, the PIR window can be controlled by adjusting structural parameters and filling different dielectric into the MIM waveguide and the square ring cavity. The results provide a new approach to designing plasmonic devices.

Theoretical investigation of lithium ions’ nucleation performance on metal-doped Cu surfaces

Lithium metal batteries(LMBs)of an ultrahigh theoretical energy density have attracted lots of attentions for a wide range of practical applications.However,there are still numerous challenges in LMBs system,such as poor cycling performance,complicated interfacial reactions,low Coulombic efficiency,and uncontrollable lithium dendrites.Understanding Li^+ions’nucleation mechanism is essential to tackle the uncontrolled growth of lithium dendrites.However,the nucleation behavior of Li+ions is interfered by the structural complexities of existing substrates during the reduplicative plating/stripping process and the rational mechanism of uniform nucleation of Li^+ions has not been clearly understood from the theoretical point of view.In our work,first-principles theoretical calculations are carried out to investigate the Li^+ions nucleation performance on metal-doped Cu surfaces(MDCSs)and the key descriptors that determines the properties of various MDCSs are systematically summarized.It is found that the introduction of heterogeneous doping Ag and Zn atoms will induce a gradient adsorption energy on MDCSs,and such gradient deposition sites can reduce the diffusion barriers and accelerate the diffusion rates of Li+ions dynamically.By maneuvering the Li+ions nucleation on MDCSs,a dendrite-free lithium metal anode can be achieved without the use of porous matrixes and complex synthesis process,which can be attributed to suppress the uncontrollable lithium dendrites for realizing the high-efficiency LMBs.

Metal-ceramic Bond Mechanism of the Co-Cr Alloy Denture with Original Rough Surface Produced by Selective Laser Melting

The porcelain fracture caused by low metal-ceramic bond strength is a critical issue in porcelain fused to metal（PFM） restorations. Surface roughening methods, such as sand blasting, acid etching and alkaline degreasing for the metal matrix are used to increase bond strength. However, the metal matrix of PFM processed by selective laser melting（SLM） has natural rough surface. To explore the effect of the original roughness on metal-ceramic bond strength, two groups of specimen are fabricated by SLM. One group of specimen surface is polished smooth while another group remains the original rough surface. The dental porcelain is fused to the specimens＇ surfaces according to the ISO 9693：1999 standard. To gain the bond strength, a three-point bending test is carried out and X ray energy spectrum analysis（EDS）, scanning electron microscope（SEM） are used to show fracture mode. The results show that the mean bond strength is 116.5 16 MPa of the group with rough surface（Ra= 17.2）, and the fracture mode is cohesive. However, when the surface is smooth （Ra =3.8）, the mean bond strength is 74.5 MPa _＋ 5 MPa and the fracture mode is mixed. The original surface with prominent structures formed by the partly melted powder particles, not only increases surface roughness but also significantly improves the bond strength by forming strong mechanical lock effect. Statistical analysis （Student＇s t-test） demonstrates a significant difference （p〈0.05） of the mean value of bond strength between the two groups. The experiments indicate the natural rough surface can enhance the metal-ceramic bond strength to over four times the minimum value （25 MPa） of the ISO 9693：1999 standard. It is found that the natural rough surface of SLM-made PFM can eliminate the porcelain collapse defect produced by traditional casting method in PFM restorations.

Adsorptive removal of nitrogen-containing compounds from fuel by metal-organic frameworks

The adsorptive denitrogenation from fuels over three metal-organic frameworks(MIL-96(Al),MIL-53(Al)and MIL-101(Cr))was studied by batch adsorption experiments.Four nitrogen-containing compounds(NCCs)pyridine,pyrrole,quinoline and indole were used as model NCCs in fuels to study the adsorption mechanism.The physicochemical properties of the adsorbents were characterized by XRD,N2physical adsorption,FT-IR spectrum and Hammett indicator method.The metal-organic frameworks(MOFs),especially the MIL-101(Cr)containing Lewis acid sites as well as high specific surface area,can adsorb large quantities of NCCs from fuels.In addition,the adsorptive capacity over MIL-101(Cr)will be different for NCCs with different basicity.The stronger basicity of the NCC is,the more it can be absorbed over MIL-101(Cr).Furthermore,pore size and shape also affect the adsorption capacity for a given adsorbate,which can be proved by the adsorption over MIL-53(Al)and MIL-96(Al).The pseudo-second-order kinetic model and Langmuir equation can be used to describe kinetics and thermodynamics of the adsorption process,respectively.Finally,the regeneration of the used adsorbent has been conducted successfully by just washing it with ethanol.