Elastic films of single-crystal two-dimensional covalent organic frameworks.

The properties of polycrystalline materials are often dominated by defects, and two-dimensional (2D) crystals can even be divided and disrupted by a line defect1-3. In contrast, 2D crystals are often required to be processed into films, which are inevitably polycrystalline and contain numerous grain boundaries, and therefore are brittle and fragile, hindering application in flexible electronics, optoelectronics and separation1-4. Moreover, similar to glass, wood, and plastics, they suffer from trade-off effects between mechanical strength and toughness.5, 6 Here, we report a method to produce highly strong, tough and elastic films of an emerging class of 2D crystals - 2D covalent organic frameworks (COFs) composed of single-crystal domains connected by interwoven grain boundary on water surface using an aliphatic bi-amine as a sacrificial go-between. Films of two 2DCOFs were demonstrated, which showed Young's moduli and breaking strength of 56.7 ± 7.4 GPa and 73.4 ± 11.6 GPa, and 82.2 ± 9.1 N/m and 29.5 ± 7.2 N/m, respectively. We envisage the sacrificial go-between guided synthesis method and the interwoven grain boundary will inspire grain boundary enigineering of various polycrystalline materials, endowing them with new properties, enhancing their current applications and paving the way for new applications.

Growth and Local Structures of Single Crystalline Flakes of Three-Dimensional Covalent Organic Frameworks in Water.

Due to the enormous chemical and structural diversities and designable properties and functionalities, covalent organic frameworks (COFs) hold great promise as tailored materials for industrial applications in electronics, biology, and energy technologies. They were typically obtained as partially crystalline materials, although a few single-crystal three-dimensional (3D) COFs have been obtained recently with structures probed by diffraction techniques. However, it remains challenging to grow single-crystal COFs with controlled morphology and to elucidate the local structures of 3D COFs, imposing severe limitations on the applications and understanding of the local structure-property correlations. Herein, we develop a method for designed growth of five types of single crystalline flakes of 3D COFs with controlled morphology, front crystal facets, and defined edge structures as well as surface chemistry using surfactants that can be self-assembled into layered structures to confine crystal growth in water. The flakes enable direct observation of local structures including monomer units, pore structure, edge structure, grain boundary, and lattice distortion of 3D COFs as well as gradually curved surfaces in kinked but single crystalline 3D COFs with a resolution of up to ∼1.7 Å. In comparison with flakes of two-dimensional crystals, the synthesized flakes show much higher chemical, mechanical, and thermal stability.

Dual-mobility cup total hip arthroplasty improves the quality of life compared to internal fixation in femoral neck fractures patients with severe neuromuscular disease in the lower extremity after stroke: a retrospective study.

Background: This study aimed to demonstrate that dual-mobility cup total hip arthroplasty (DMC-THA) can significantly improve the quality of life (QOL) of elderly femoral neck fracture patients with severe neuromuscular disease in unilateral lower extremities due to stroke hemiplegia compared to internal fixation (IF). Methods: Fifty-eight cases of severe neuromuscular disease in the unilateral lower extremities with muscle strength < grade 3/5 due to stroke were retrospectively examined From January 2015 to December 2020. Then, patients were divided into DMC and IF groups. The QOL was examined using the EQ-5D and SF-36 outcome measures. The physical and mental statuses were assessed using the Barthel Index (BI) and e Fall Efficacy Scale-International (FES-I), respectively. Results: Patients in the DMC group had higher BI scores than those in the IF group at different time point. Regarding mental status, the FES-I mean score was 42.1 ± 5.3 in the DMC group and 47.3 ± 5.6 in the IF group (p = 0.002). For the QOL, the mean SF-36 score was 46.1 ± 18.3 for the health component and 59.5 ± 15.0 for the mental component in the DMC group compared to 35.3 ± 16.2 (p = 0.035), and 46.6 ± 17.4 (p = 0.006) compared to the IF group. The mean EQ-5D-5L values were 0.733 ± 0.190 and 0.303 ± 0.227 in the DMC and IF groups (p = 0.035), respectively. Conclusion: DMC-THA significantly improved postoperative QOL compared to IF in elderly patients with femoral neck fractures and severe neuromuscular dysfunction in the lower extremity after stroke. The improved outcomes were related to the enhanced early, rudimentary motor function of patients.

Nanoporous and Highly Thermal Conductive Thin Film of Single-Crystal Covalent Organic Frameworks Ribbons.

Nanoporous materials are widely explored as efficient adsorbents for the storage of gases and liquids as well as for effective low-dielectric materials in large-scale integrated circuits. These applications require fast heat transfer, while most nanoporous substances are thermal insulators. Here, the oriented growth of micrometer-sized single-crystal covalent organic frameworks (COFs) ribbons with nanoporous structures at an air-water interface is presented. The obtained COFs ribbons are interconnected into a continuous and purely crystalline thin film. Due to the robust connectivity among the COFs ribbons, the entire film can be easily transferred and reliably contacted with target supports. The measured thermal conductivity amounts to ∼5.31 ± 0.37 W m-1 K-1 at 305 K, which is so far the highest value for nanoporous materials. These findings provide a methodology to grow and assemble single-crystal COFs into large area ensembles for the exploration of functional properties and potentially lead to new devices with COFs thin films where both porosity and thermal conductivity are desired.

A High-Rate Two-Dimensional Polyarylimide Covalent Organic Framework Anode for Aqueous Zn-Ion Energy Storage Devices.

Rechargeable aqueous Zn-ion energy storage devices are promising candidates for next-generation energy storage technologies. However, the lack of highly reversible Zn2+-storage anode materials with low potential windows remains a primary concern. Here, we report a two-dimensional polyarylimide covalent organic framework (PI-COF) anode with high-kinetics Zn2+-storage capability. The well-organized pore channels of PI-COF allow the high accessibility of the build-in redox-active carbonyl groups and efficient ion diffusion with a low energy barrier. The constructed PI-COF anode exhibits a specific capacity (332 C g-1 or 92 mAh g-1 at 0.7 A g-1), a high rate capability (79.8% at 7 A g-1), and a long cycle life (85% over 4000 cycles). In situ Raman investigation and first-principle calculations clarify the two-step Zn2+-storage mechanism, in which imide carbonyl groups reversibly form negatively charged enolates. Dendrite-free full Zn-ion devices are fabricated by coupling PI-COF anodes with MnO2 cathodes, delivering excellent energy densities (23.9 ∼ 66.5 Wh kg-1) and supercapacitor-level power densities (133 ∼ 4782 W kg-1). This study demonstrates the feasibility of covalent organic framework as Zn2+-storage anodes and shows a promising prospect for constructing reliable aqueous energy storage devices.

Interlayer gap widened α-phase molybdenum trioxide as high-rate anodes for dual-ion-intercalation energy storage devices.

Employing high-rate ion-intercalation electrodes represents a feasible way to mitigate the inherent trade-off between energy density and power density for electrochemical energy storage devices, but efficient approaches to boost the charge-storage kinetics of electrodes are still needed. Here, we demonstrate a water-incorporation strategy to expand the interlayer gap of α-MoO3, in which water molecules take the place of lattice oxygen of α-MoO3. Accordingly, the modified α-MoO3 electrode exhibits theoretical-value-close specific capacity (963 C g-1 at 0.1 mV s-1), greatly improved rate capability (from 4.4% to 40.2% at 100 mV s-1) and boosted cycling stability (from 21 to 71% over 600 cycles). A fast-kinetics dual-ion-intercalation energy storage device is further assembled by combining the modified α-MoO3 anode with an anion-intercalation graphite cathode, operating well over a wide discharge rate range. Our study sheds light on a promising design strategy of layered materials for high-kinetics charge storage.

Achieving Insertion-Like Capacity at Ultrahigh Rate via Tunable Surface Pseudocapacitance.

The insertion/deinsertion mechanism enables plenty of charge-storage sites in the bulk phase to be accessible to intercalated ions, giving rise to at least one more order of magnitude higher energy density than the adsorption/desorption mechanism. However, the sluggish ion diffusion in the bulk phase leads to several orders of magnitude slower charge-transport kinetics. An ideal energy-storage device should possess high power density and large energy density simultaneously. Herein, surface-modified Fe2 O3 quantum dots anchored on graphene nanosheets are developed and exhibit greatly enhanced pseudocapacitance via fast dual-ion-involved redox reactions with both large specific capacity and fast charge/discharge capability. By using an aqueous Na2 SO3 electrolyte, the oxygen-vacancy-tuned Fe2 O3 surface greatly enhances the absorption of SO32- anions that majorly increase the surface pseudocapacitance. Significantly, the Fe2 O3 -based electrode delivers a high specific capacity of 749 C g-1 at 5 mV s-1 and retains 290 C g-1 at an ultrahigh scan rate of 3.2 V s-1 . With a novel dual-electrolyte design, a 2 V Fe2 O3 /Na2 SO3 //MnO2 /Na2 SO4 asymmetric supercapacitor is constructed, delivering a high energy density of 75 W h kg-1 at a power density of 3125 W kg-1 .

Fabrication of Au25 (SG)18 -ZIF-8 Nanocomposites: A Facile Strategy to Position Au25 (SG)18 Nanoclusters Inside and Outside ZIF-8.

Multifunctional composite materials are currently highly desired for sustainable energy applications. A general strategy to integrate atomically precise Au25 (SG)18 with ZIF-8 (Zn(MeIm)2 , MeIm = 2-methylimidazole), is developed via the typical Zn-carboxylate type of linkage. Au25 (SG)18 are uniformly encapsulated into a ZIF-8 framework (Au25 (SG)18 @ZIF-8) by coordination-assisted self-assembly. In contrast, Au25 (SG)18 integrated by simple impregnation is oriented along the outer surface of ZIF-8 (Au25 (SG)18 /ZIF-8). The porous structure and thermal stability of these nanocomposites are characterized by N2 adsorption-desorption isothermal analysis and thermal gravimetric analysis. The distribution of Au25 (SG)18 in the two nanocomposites is confirmed by electron microscopy, and the accessibility of Au25 (SG)18 is evaluated by the 4-nitrophenol reduction reaction. The as-prepared nanocomposites retain the high porosity and thermal stability of the ZIF-8 matrix, while also exhibiting the desired catalytic and optical properties derived from the integrated Au25 (SG)18 nanoclusters (NCs). Au25 (SG)18 @ZIF-8 with isolated Au25 sites is a promising heterogenous catalyst with size selectivity imparted by the ZIF-8 matrix. The structural distinction between Au25 (SG)18 @ZIF-8 and Au25 (SG)18 /ZIF-8 determines their different emission features, and provides a new strategy to adjust the optical behavior of Au25 (SG)18 for applications in bioimaging and biotherapy.

In Situ Derived NixFe1-xOOH/NiFe/NixFe1-xOOH Nanotube Arrays from NiFe Alloys as Efficient Electrocatalysts for Oxygen Evolution.

Herein, NixFe1-xOOH/NiFe/NixFe1-xOOH sandwich-structured nanotube arrays (SNTAs) supported on carbon fiber cloth (CFC) (NixFe1-xOOH/NiFe/NixFe1-xOOH SNTAs-CFC) have been developed as flexible high-performance oxygen evolution reaction (OER) catalysts by a facile in situ electrochemical oxidation of NiFe metallic alloy nanotube arrays during oxygen evolution process. Benefiting from the advantages of high conductivity, hollow nanotube array, and porous structure, NixFe1-xOOH/NiFe/NixFe1-xOOH SNTAs-CFC exhibited a low overpotential of ∼220 mV at the current density of 10 mA cm-2 and a small Tafel slope of 57 mV dec-1 in alkaline solution, both of which are smaller than those of most OER electrocatalysts. Furthermore, NixFe1-xOOH/NiFe/NixFe1-xOOH SNTAs-CFC exhibits excellent stability at 100 mA cm-2 for more than 30 h. It is believed that the present work can provide a valuable route for the design and synthesis of inexpensive and efficient OER electrocatalysts.

Nitrogen-Doped Co3 O4 Mesoporous Nanowire Arrays as an Additive-Free Air-Cathode for Flexible Solid-State Zinc-Air Batteries.

The kinetically sluggish rate of oxygen reduction reaction (ORR) on the cathode side is one of the main bottlenecks of zinc-air batteries (ZABs), and thus the search for an efficient and cost-effective catalyst for ORR is highly pursued. Co3 O4 has received ever-growing interest as a promising ORR catalyst due to the unique advantages of low-cost, earth abundance and decent catalytic activity. However, owing to the poor conductivity as a result of its semiconducting nature, the ORR activity of the Co3 O4 catalyst is still far below the expectation. Herein, we report a controllable N-doping strategy to significantly improve the catalytic activity of Co3 O4 for ORR and demonstrate these N doped Co3 O4 nanowires as an additive-free air-cathode for flexible solid-state zinc-air batteries. The results of experiments and DFT calculations reveal that the catalytic activity is promoted by the N dopant through a combined set of factors, including enhanced electronic conductivity, increased O2 adsorption strength and improved reaction kinetics. Finally, the assembly of all-solid-state ZABs based on the optimized cathode exhibit a high volumetric capacity of 98.1 mAh cm-3 and outstanding flexibility. The demonstration of such flexible ZABs provides valuable insights that point the way to the redesign of emerging portable electronics.

Plasmon-enhanced nanoporous BiVO4 photoanodes for efficient photoelectrochemical water oxidation.

Conversion of solar irradiation into chemical fuels such as hydrogen with the use of a photoelectrochemical (PEC) cell is an attractive strategy for green energy. The promising technique of incorporating metal nanoparticles (NPs) in the photoelectrodes is being explored to enhance the performance of the photoelectrodes. In this work, we developed Au-NPs-functionalized nanoporous BiVO4 photoanodes, and utilized the plasmonic effects of Au NPs to enhance the photoresponse. The plasmonic enhancement leads to an AM 1.5 photocurrent of 5.1 ± 0.1 mA cm(-2) at 1.23 V versus a reverse hydrogen electrode. We observed an enhancement of five times with respect to pristine BiVO4 in the photocurrent with long-term stability and high energy-conversion efficiency. The overall performance enhancement is attributed to the synergy between the nanoporous architecture of BiVO4 and the plasmonic effects of Au NPs. Our further study reveals that the commendable photoactivity arises from the different plasmonic effects and co-catalyst effects of Au NPs.

Carbon Quantum Dot Surface-Engineered VO2 Interwoven Nanowires: A Flexible Cathode Material for Lithium and Sodium Ion Batteries.

The use of electrode materials in their powdery form requires binders and conductive additives for the fabrication of the cells, which leads to unsatisfactory energy storage performance. Recently, a new strategy to design flexible, binder-, and additive-free three-dimensional electrodes with nanoscale surface engineering has been exploited in boosting the storage performance of electrode materials. In this paper, we design a new type of free-standing carbon quantum dot coated VO2 interwoven nanowires through a simple fabrication process and demonstrate its potential to be used as cathode material for lithium and sodium ion batteries. The versatile carbon quantum dots that are vastly flexible for surface engineering serve the function of protecting the nanowire surface and play an important role in the diffusion of electrons. Also, the three-dimensional carbon cloth coated with VO2 interwoven nanowires assisted in the diffusion of ions through the inner and the outer surface. With this unique architecture, the carbon quantum dot nanosurface engineered VO2 electrode exhibited capacities of 420 and 328 mAh g(-1) at current density rate of 0.3 C for lithium and sodium storage, respectively. This work serves as a milestone for the potential replacement of lithium ion batteries and next generation postbatteries.

Chemically Lithiated TiO2 Heterostructured Nanosheet Anode with Excellent Rate Capability and Long Cycle Life for High-Performance Lithium-Ion Batteries.

A new form of dual-phase heterostructured nanosheet comprised of oxygen-deficient TiO2/Li4Ti5O12 has been successfully synthesized and used as anode material for lithium ion batteries. With the three-dimensional (3D) Ti mesh as both the conducting substrate and the Ti(3+)/Ti(4+) source, blue anatase Ti(3+)/TiO2nanosheets were grown by a hydrothermal reaction. By controlling the chemical lithiation period of TiO2 nanosheets, a phase boundary was created between the TiO2 and the newly formed Li4Ti5O12, which contribute additional capacity benefiting from favorable charge separation between the two phase interfaces. Through further hydrogenation of the 3D TiO2/Li4Ti5O12 heterostructured nanosheets (denoted as H-TiO2/LTO HNS), an extraordinary rate performance with capacity of 174 mAh g(-1) at 200 C and outstanding long-term cycling stability with only an ∼6% decrease of its initial specific capacity after 6000 cycles were delivered. The heterostructured nanosheet morphology provides a short length of lithium diffusion and high electrode/electrolyte contact area, which could also explain the remarkable lithium storage performance. In addition, the full battery assembled based on the H-TiO2/LTO anode achieves high energy and power densities.

Vanadium Nitride Nanowire Supported SnS2 Nanosheets with High Reversible Capacity as Anode Material for Lithium Ion Batteries.

The vulnerable restacking problem of tin disulfide (SnS2) usually leads to poor initial reversible capacity and poor cyclic stability, which hinders its practical application as lithium ion battery anode (LIB). In this work, we demonstrated an effective strategy to improve the first reversible capacity and lithium storage properties of SnS2 by growing SnS2 nanosheets on porous flexible vanadium nitride (VN) substrates. When evaluating lithium-storage properties, the three-dimensional (3D) porous VN coated SnS2 nanosheets (denoted as CC-VN@SnS2) yield a high reversible capacity of 75% with high specific capacity of about 819 mAh g(-1) at a current density of 0.65 A g(-1). Remarkable cyclic stability capacity of 791 mAh g(-1) after 100 cycles with excellent capacity retention of 97% was also achieved. Furthermore, discharge capacity as high as 349 mAh g(-1) is still retained after 70 cycles even at a elevated current density of 13 A g(-1). The excellent performance was due to the conductive flexible VN substrate support, which provides short Li-ion and electron pathways, accommodates large volume variation, contributes to the capacity, and provides mechanical stability, which allows the electrode to maintain its structural stability.

Nanometer-scale separation of d(10) Zn(2+)-layers and twin-shift competition in Ba8ZnNb6O24-based 8-layered hexagonal perovskites.

The 8-layered shifted hexagonal perovskite compound Ba8ZnNb6O24 was isolated via controlling the ZnO volatilization, which features long-range B-cation ordering with nanometer-scale separation by ∼1.9 nm of octahedral d(10) cationic (Zn(2+)) layers within the purely corner-sharing octahedral d(0) cationic (Nb(5+)) host. The long-range ordering of the B-site vacancy and out-of-center distortion of the highly-charged d(0) Nb(5+) that is assisted by the second-order Jahn-Teller effect contribute to this unusual B-cation ordering in Ba8ZnNb6O24. A small amount (∼15%) of d(10) Sb(5+) substitution for Nb(5+) in Ba8ZnNb6-xSbxO24 dramatically transformed the shifted structure to a twinned structure, in contrast with the Ba8ZnNb6-xTaxO24 case requiring 50% d(0) Ta(5+) substitution for Nb(5+) for such a shift-to-twin transformation. Multiple factors including B-cationic sizes, electrostatic repulsion forces, long-range ordering of B-site vacancies, and bonding preferences arising from a covalent contribution to the B-O bonding that includes out-of-center octahedral distortion and the B-O-B bonding angle could subtly contribute to the twin-shift phase competition of B-site deficient 8-layered hexagonal perovskites Ba8B7O24. The ceramics of new shifted Ba8ZnNb6O24 and twinned Ba8ZnNb5.1Sb0.9O24 compounds exhibited good microwave dielectric properties (εr ∼ 35, Qf ∼ 36 200-43 400 GHz and τf ∼ 38-44 ppm/°C).

Field-Induced Crystalline-to-Amorphous Phase Transformation on the Si Nano-Apex and the Achieving of Highly Reliable Si Nano-Cathodes.

Nano-scale vacuum channel transistors possess merits of higher cutoff frequency and greater gain power as compared with the conventional solid-state transistors. The improvement in cathode reliability is one of the major challenges to obtain high performance vacuum channel transistors. We report the experimental findings and the physical insight into the field induced crystalline-to-amorphous phase transformation on the surface of the Si nano-cathode. The crystalline Si tip apex deformed to amorphous structure at a low macroscopic field (0.6~1.65 V/nm) with an ultra-low emission current (1~10 pA). First-principle calculation suggests that the strong electrostatic force exerting on the electrons in the surface lattices would take the account for the field-induced atomic migration that result in an amorphization. The arsenic-dopant in the Si surface lattice would increase the inner stress as well as the electron density, leading to a lower amorphization field. Highly reliable Si nano-cathodes were obtained by employing diamond like carbon coating to enhance the electron emission and thus decrease the surface charge accumulation. The findings are crucial for developing highly reliable Si-based nano-scale vacuum channel transistors and have the significance for future Si nano-electronic devices with narrow separation.

Localization of oxygen interstitials in CeSrGa3O(7+δ) melilite.

The solubility of Ce in the La(1-x)Ce(x)SrGa3O(7+δ) and La(1.54-x)Ce(x)Sr0.46Ga3O(7.27+δ) melilites was investigated, along with the thermal redox stability in air of these melilites and the conductivity variation associated with oxidization of Ce(3+) into Ce(4+). Under CO reducing atmosphere, the La in LaSrGa3O7 may be completely substituted by Ce to form the La(1-x)Ce(x)SrGa3O(7+δ) solid solution, which is stable in air to ∼600 °C when x ≥ 0.6. On the other side, the La(1.54-x)Ce(x)Sr0.46Ga3O(7.27+δ) compositions displayed much lower Ce solubility (x ≤ 0.1), irrespective of the synthesis atmosphere. In the as-made La(1-x)CexSrGa3O(7+δ), the conductivity increased with the cerium content, due to the enhanced electronic conduction arising from the 4f electrons in Ce(3+) cations. At 600 °C, CeSrGa3O(7+δ) showed a conductivity of ∼10(-4) S/cm in air, nearly 4 orders of magnitude higher than that of LaSrGa3O7. The oxidation of Ce(3+) into Ce(4+) in CeSrGa3O(7+δ) slightly reduced the conductivity, and the oxygen excess did not result in apparent increase of oxide ion conduction in CeSrGa3O(7+δ). The Ce doping in air also reduced the interstitial oxide ion conductivity of La1.54Sr0.46Ga3O7.27. Neutron powder diffraction study on CeSrGa3O7.39 composition revealed that the extra oxygen is incorporated in the four-linked GaO4 polyhedral environment, leading to distorted GaO5 trigonal bipyramid. The stabilization and low mobility of interstitial oxygen atoms in CeSrGa3O(7+δ), in contrast with those in La(1+x)Sr(1-x)Ga3O(7+0.5x), may be correlated with the cationic size contraction from the oxidation of Ce(3+) to Ce(4+). These results provide a new comprehensive understanding of the accommodation and conduction mechanism of the oxygen interstitials in the melilite structure.