Exploring the Capacity Limit: A Layered Hexacarboxylate-Based Metal-Organic Framework for Advanced Lithium Storage.

Our previous work suggested that more carboxylate groups might lead to higher energy density for metal-organic frameworks. In this study, we synthesized a layered metal-organic framework (MOF) Ni-BHC by use of 1,2,3,4,5,6-benzenehexacarboxylic acid. After evacuation by thermal treatment, this MOF was employed as an anode for lithium storage. For its rich lithiation sites as well as layered fast-kinetics structure, it delivers a superior reversible capacity of 1261.3 mA h g-1 at 100 mA g-1, far exceeding the performance of previously reported MOF-based anode materials. Density functional theory calculation and O soft X-ray absorption spectroscopy suggest that the luxuriant carboxylate-metal units play an important part in the electrochemical process.

Ultrathin Cobalt-Based Metal-Organic Framework Nanosheets with Both Metal and Ligand Redox Activities for Superior Lithium Storage.

The controllable synthesis and structural tailoring of nanostructured metal-organic frameworks (MOFs) is of huge significance in boosting their potential for rechargeable batteries. We herein present the facile synthesis of cobalt-based ultrathin metal-organic framework nanosheets (referred to as "u-CoTDA") by using 2,5-thiophenedicarboxylic (H2 TDA) as the organic building block through a one-pot ultrasonic method for the first time. The obtained u-CoTDA exhibits high reversible capacity (790 mAh g-1 after 400 cycles at 1 A g-1 ) and excellent rate capability (694 mAh g-1 at 2 A g-1 ), which outperforms its bulk counterpart. Moreover, the detailed lithiation/delithiation processes of u-CoTDA were studied by the combination of Co K-edge X-ray absorption near edge structure (XANES), O K-edge soft X-ray spectroscopy (sXAS) and electron paramagnetic resonance (EPR) techniques, which demonstrate that both the CoII centers and organic ligands of u-CoTDA are involved in the reduction/oxidation processes.

Bubble-Mediated Production of Few-Layer Graphene via Vapor-Liquid Reaction between Carbon Dioxide and Magnesium Melt.

It is urgent to develop novel technologies to convert carbon dioxide to graphene. In this work, a bubble-mediated approach via a chemical reaction between carbon dioxide gas and magnesium melt to fabricate a few-layer graphene was illustrated. The morphology and defects of graphene can be regulated by manipulating the melt temperature. The preparation of graphene at 720 °C exhibited an excellent quality of surface and graphitization degree. The high-quality few-layer graphene can be grown under the combined effect of carbon dioxide bubbles and in-situ grown MgO. This preparation method possesses the advantages of high efficiency, low cost, and environmental protection, which may provide a new strategy for the recovery and reuse of greenhouse gases.

In Situ Flash Synthesis of Ultra-High-Performance Metal Oxide Anode through Shunting Current-Based Electrothermal Shock.

The synthesis of anode materials plays an important role in determining the production efficiency, cost, and performance of lithium-ion batteries (LIBs). However, a low-cost, high-speed, scalable manufacturing process of the anode with the desired structural feature for practical technology adoption remains elusive. In this study, we propose a novel method called in situ flash shunt-electrothermal shock (SETS) which is controllable, fast, and energy-saving for synthesizing metal oxide-based materials. By using the example of direct electrothermal decomposition of ZIF-67 precursor loaded onto copper foil support, we achieve rapid (0.1-0.3 s) pyrolysis and generate porous hollow cubic structure material consisting of carbon-coated ultrasmall (10-15 nm) subcrystalline CoO/Co nanoparticles with controllable morphology. It was shown that CoO/Co@N-C exhibits prominent electrochemical performance with a high reversible capacity up to 1503.7 mA h g-1 after 150 cycles at 0.2 A g-1and stable capacities up to 434.1 mA h g-1 after 400 cycles at a high current density of 6 A g-1. This fabrication technique integrates the synthesis of active materials and the formation of electrode sheets into one process, thus simplifying the preparation of electrodes. Due to the simplicity and scalability of this process, it can be envisaged to apply it to the synthesis of metal oxide-based materials and to achieve large-scale production in a nanomanufacturing process.

Thin-Copper-Layer-Induced Early Fracture in Graphene-Nanosheets (GNSs)-Reinforced Copper-Matrix-Laminated Composites.

The strength-ductility trade-off has been a long-standing challenge when designing and fabricating a novel metal matrix composite. In this study, graphene-nanosheets (GNSs)-reinforced copper (Cu)-matrix-laminated composites were fabricated through two methods, i.e., the alternating electrodeposition technique followed by spark plasma sintering (SPS) and direct electrodeposition followed by hot-press sintering. As a result, a Cu-GNS-Cu layered structure formed in the composites with various Cu layer thicknesses. Compared with the pure Cu, the yield strength of the GNS/Cu composites increased. However, the mechanical performance of the GNS/Cu composites was strongly Cu-layer-thickness-dependent, and the GNS/Cu composite possessed a brittle fracture mode when the Cu layer was thin (≤10 µm). The fracture mechanism of the GNS/Cu composites was thoroughly investigated and the results showed that the premature failure of the GNS/Cu composites with a thin Cu layer may be due to the lack of Cu matrix, which can relax the excessive stress intensity triggered by GNSs and delay the crack connection between neighboring GNS layers. This study highlights the soft Cu matrix in balancing the strength and ductility of the GNS/Cu-laminated composites and provides new technical and theoretical support for the preparation and optimization of other laminated metal matrix composites.

Synergistic Strengthening of Mechanical Properties and Electromagnetic Interference Shielding Performance of Carbon Nanotubes (CNTs) Reinforced Magnesium Matrix Composites by CNTs Induced Laminated Structure.

In this study, we reported a laminated CNTs/Mg composite fabricated by spray-deposition and subsequent hot-press sintering, which realized simultaneous enhancement effects on strength and electromagnetic interference (EMI) shielding effectiveness (SE) by the introduced CNTs and CNT induced laminated 'Mg-CNT-Mg' structure. It was found that the CNTs/Mg composite with 0.5 wt.% CNTs not only exhibited excellent strength-toughness combination but also achieved a high EMI SE of 58 dB. The CNTs increased the strength of the composites mainly by the thermal expansion mismatch strengthening and blocking dislocation movements. As for toughness enhancement, CNTs induced laminated structure redistributes the local strain effectively and alleviates the strain localization during the deformation process. Moreover, it could also hinder the crack propagation and cause crack deflection, which resulted in an increment of the required energy for the failure of CNTs/Mg composites. Surprisingly, because of the laminated structure induced by introducing CNTs, the composite also exhibited an outperforming EMI SE in the X band (8.2-12.4 GHz). The strong interactions between the laminated 'Mg-CNT-Mg' structure and the incident electromagnetic waves are responsible for the increased absorption of the electromagnetic radiation. The lightweight CNTs/Mg composite with outstanding mechanical properties and simultaneously increased EMI performance could be employed as shell materials for electronic packaging components or electromagnetic absorbers.

Low-temperature pseudomorphic transformation of polyhedral MIL-88A to lithium ferrite (LiFe3O5) in aqueous LiOH medium toward high Li storage.

The ability to develop novel nanomaterials, and to precisely manufacture their functional structures at the nano- and microscales would benefit many emerging device applications. Herein, as a first example, we describe the exploration of feasibility for the morphological replacement of an iron-based MOF bearing trimeric FeIII-O clusters, MIL-88A preform, with a polyhedral architecture of around 0.4 × 1.2 µm by a lithium ferrite (LiFe3O5) phase via solid-liquid pseudomorphic transformation reactions in biologically and environmentally favourable aqueous lithium hydroxide (LiOH). The reaction proceeds at 170 °C, and the overall reaction can be described as Fe3O(H2O)2(FMA)3(OH)·nH2O (MIL-88A) + 7OH- + Li+ → LiFe3O5 + 3FMA2- + (n + 6) H2O (FMA = fumarate). It was proposed that through the coordination substitution of a MOF ligand by OH-, follow-up dehydration and dehydroxylation, and final H+/Li+ ionic exchange, the monolithiated iron oxides formed thermodynamically at comparatively low temperatures, which transcribe the global nanostructure morphologies of the polyhedral MOF preforms with the hexagonal symmetry, but were composed of interconnected LiFe3O5 particles (about 16 nm) that crystallize in a typical magnetite-type cubic (Fd3[combining macron]m) structure. Given the characteristic texture and structure of the Li-Fe oxide replica, cubic LiFe3O5 was preferentially employed as a new type of electrode material in rechargeable lithium cells. Notably, from the electrochemical evaluation, this metal oxide system exhibits decent anodic performances by undergoing a nine-electron conversion reaction, showing a substantially high specific capacity with an average potential of 0.8 V versus lithium metal, a long service life (700 cycles), and exceptional high-rate capability (up to 2.0 A g-1). The synthetic paradigms demonstrated that the MIL-88A to LiFe3O5 conversion may be transferable to other advanced inorganic-based electrodes from the parent metal compound such as LiFeO2, LiMn2O4 or LiCoO2 toward sustainable energy fields.

One-Pot Synthesis of Co-Based Coordination Polymer Nanowire for Li-Ion Batteries with Great Capacity and Stable Cycling Stability.

Nanowire coordination polymer cobalt-terephthalonitrile (Co-BDCN) was successfully synthesized using a simple solvothermal method and applied as anode material for lithium-ion batteries (LIBs). A reversible capacity of 1132 mAh g-1 was retained after 100 cycles at a rate of 100 mA g-1, which should be one of the best LIBs performances among metal organic frameworks and coordination polymers-based anode materials at such a rate. On the basis of the comprehensive structural and morphology characterizations including fourier transform infrared spectroscopy, 1H NMR, 13C NMR, and scanning electron microscopy, we demonstrated that the great electrochemical performance of the as-synthesized Co-BDCN coordination polymer can be attributed to the synergistic effect of metal centers and organic ligands, as well as the stability of the nanowire morphology during cycling.

Green and Rational Design of 3D Layer-by-Layer MnO x Hierarchically Mesoporous Microcuboids from MOF Templates for High-Rate and Long-Life Li-Ion Batteries.

Rational design and delicate control on the textural properties of metal-oxide materials for diverse structure-dependent applications still remain formidable challenges. Here, we present an eco-friendly and facile approach to smartly fabricate three-dimensional (3D) layer-by-layer manganese oxide (MnO x) hierarchical mesoporous microcuboids from a Mn-MOF-74-based template, using a one-step solution-phase reaction scheme at room temperature. Through the controlled exchange of metal-organic framework (MOF) ligand with OH- in alkaline aqueous solution and in situ oxidation of manganese hydroxide intermediate, the Mn-MOF-74 template/precursor was readily converted to Mn3O4 or δ-MnO2 counterpart consisting of primary nanoparticle and nanosheet building blocks, respectively, with well-retained morphology. By X-ray diffraction, transmission electron microscopy (TEM), scanning electron microscopy, high-resolution TEM, N2 adsorption-desorption analysis and other techniques, their crystal structure, detailed morphology, and microstructure features were unambiguously revealed. Specifically, their electrochemical Li-ion insertion/extraction properties were well evaluated, and it turns out that these unique 3D microcuboids could achieve a sustained superior lithium-storage performance especially at high rates benefited from the well-orchestrated structural characteristics (Mn3O4 microcuboids: 890.7, 767.4, 560.1, and 437.1 mAh g-1 after 400 cycles at 0.2, 0.5, 1, and 2 A g-1, respectively; δ-MnO2 microcuboids: 991.5, 660.8, 504.4, and 362.1 mAh g-1 after 400 cycles at 0.2, 0.5, 1, and 2 A g-1, respectively). To our knowledge, this is the most durable high-rate capability as well as the highest reversible capacity ever reported for pure MnO x anodes, which even surpass most of their hybrids. This facile, green, and economical strategy renews the traditional MOF-derived synthesis for highly tailorable functional materials and opens up new opportunities for metal-oxide electrodes with high performance.

Ultrathin Manganese-Based Metal-Organic Framework Nanosheets: Low-Cost and Energy-Dense Lithium Storage Anodes with the Coexistence of Metal and Ligand Redox Activities.

We herein demonstrate the fabrication of Mn- and Ni-based ultrathin metal-organic framework nanosheets with the same coordination mode (termed "Mn-UMOFNs" and "Ni-UMOFNs", respectively) through an expedient and versatile ultrasonic approach and scrutinize their electrochemical properties as anode materials for rechargeable lithium batteries for the first time. The obtained Mn-UMOFNs with structure advantages over Ni-UMOFNs (thinner nanosheets, smaller metal-ion radius, higher specific surface area) exhibit high reversible capacity (1187 mAh g-1 at 100 mA g-1 for 100 cycles), excellent rate capability (701 mAh g-1 even at 2 A g-1), rapid Li+ diffusion coefficient (2.48 × 10-9 cm2 s-1), and a reasonable charge-discharge profile with low average operating potential at 0.4 V. On the grounds of the low-cost and environmental benignity of Mn metals and terephthalic acid linkers, our Mn-UMOFNs show alluring promise as a low-cost high-energy anode material for future LIBs. Furthermore, the lithiation-delithiation chemistry of Mn-UMOFNs was unequivocally studied by a combination of magnetic measurements, electron paramagnetic resonance, and synchrotron-based soft X-ray spectroscopy (O K-edge and Mn L-edge) experiments, the results of which substantiate that both the aromatic chelating ligands and the Mn2+ centers participate in lithium storage.

Highly efficient complexation of sanguinarine alkaloid by carboxylatopillar[6]arene: pKa shift, increased solubility and enhanced antibacterial activity.

Encapsulation of a physiologically active substance, sanguinarine (SA), by a water soluble carboxylatopillar[6]arene (CP6A), is described. The efficient complexation by CP6A, giving a Ka value of (2.4 ± 0.3) × 105 M-1 in pH 7.4, served to increase the water solubility by 4.3-fold, cause a 2.02 shift in pKa, and enhance the antibacterial activity of SA.

Bimetallic coordination polymer as a promising anode material for lithium-ion batteries.

Bimetallic coordination polymers (BiCPs) with Zn and Co were synthesized and applied as anode materials. When the rate was increased to 2 A g(-1), a capacity of 622 mA h g(-1) after 500 cycles could still be maintained.

Graphene nanoplatelets induced heterogeneous bimodal structural magnesium matrix composites with enhanced mechanical properties.

In this work, graphene nanoplatelets (GNPs) reinforced magnesium (Mg) matrix composites were synthesised using the multi-step dispersion route. Well-dispersed but inhomogeneously distributed GNPs were obtained in the matrix. Compared with the monolithic alloy, the nanocomposites exhibited dramatically enhanced Young's modulus, yield strength and ultimate tensile strength and relatively high plasticity, which mainly attributed to the significant heterogeneous laminated microstructure induced by the addition of GNPs. With increasing of the concentration of GNPs, mechanical properties of the composites were gradually improved. Especially, the strengthening efficiency of all the composites exceeded 100%, which was significantly higher than that of carbon nanotubes reinforced Mg matrix composites. The grain refinement and load transfer provided by the two-dimensional and wrinkled surface structure of GNPs were the dominated strengthening mechanisms of the composites. This investigation develops a new method for incorporating GNPs in metals for fabricating high-performance composites.

High Anodic Performance of Co 1,3,5-Benzenetricarboxylate Coordination Polymers for Li-Ion Battery.

We report the designed synthesis of Co 1,3,5-benzenetricarboxylate coordination polymers (CPs) via a straightforward hydrothermal method, in which three kinds of reaction solvents are selected to form CPs with various morphologies and dimensions. When tested as anode materials in Li-ion battery, the cycling stabilities of the three CoBTC CPs at a current density of 100 mA g(-1) have not evident difference; however, the reversible capacities are widely divergent when the current density is increased to 2 A g(-1). The optimized product CoBTC-EtOH maintains a reversible capacity of 473 mAh g(-1) at a rate of 2 A g(-1) after 500 galvanostatic charging/discharging cycles while retaining a nearly 100% Coulombic efficiency. The hollow microspherical morphology, accessible specific area, and the absence of coordination solvent of CoBTC-EtOH might be responsible for such difference. Furthermore, the ex situ soft X-ray absorption spectroscopy studies of CoBTC-EtOH under different states-of-charge suggest that the Co ions remain in the Co(2+) state during the charging/discharging process. Therefore, Li ions are inserted to the organic moiety (including the carboxylate groups and the benzene ring) of CoBTC without the direct engagement of Co ions during electrochemical cycling.

Synthesis of a Water-Soluble Carboxylatobiphen[4]arene and Its Selective Complexation toward Acetylcholine.

The first water-soluble biphen[4]arene containing eight carboxylato moieties (carboxylatobiphen[4]arene, CBP4) has been synthesized. Selective molecular recognition of acetylcholine (ACh) against choline (Ch) and betaine (Bt) and pH-responsive host-guest complexation in aqueous media are described.

Biphen[n]arenes.

To design and exploit novel macrocyclic synthetic receptors is a permanent and challenging topic in supramolecular chemistry. Here we describe the one-pot synthesis, unique geometries and intriguing host-guest properties of a new class of supramolecular macrocycles - biphen[n]arenes (n = 3, 4), which are made up of 4,4'-biphenol or 4,4'-biphenol ether units linked by methylene bridges at the 3- and 3'- positions. The biphenarene macrocycles are conveniently accessible/modifiable and extremely guest-friendly. Particularly, biphen[4]arene is capable of forming inclusion complexes with not only organic cationic guests but also neutral π-electron deficient molecules. Compared with calixarenes, resorcinarenes, cyclotriveratrylenes and pillararenes with substituted mono-benzene units, the biphen[n]arenes reported here possess significantly different characteristics in both their topologic structures and their recognition properties, and thus can find broad applications in supramolecular chemistry and other areas.