Mechanically Robust Self-Organized Crack-Free Nanocellular Graphene with Outstanding Electrochemical Properties in Sodium Ion Battery.

Crack-free nanocellular graphenes are attractive materials with extraordinary mechanical and electrochemical properties, but their homogeneous synthesis on the centimeter scale is challenging. Here, a strong nanocellular graphene film achieved by the self-organization of carbon atoms using liquid metal dealloying and employing a defect-free amorphous precursor is reported. This study demonstrates that a Bi melt strongly catalyzes the self-structuring of graphene layers at low processing temperatures. The robust nanoarchitectured graphene displays a high-genus seamless framework and exhibits remarkable tensile strength (34.8 MPa) and high electrical conductivity (1.6 × 104 S m-1). This unique material has excellent potential for flexible and high-rate sodium-ion battery applications.

All-Solid-State Mg-Air Battery Enhanced with Free-Standing N-Doped 3D Nanoporous Graphene.

Nitrogen (N) doping of graphene with a three-dimensional (3D) porous structure, high flexibility, and low cost exhibits potential for developing metal-air batteries to power electric/electronic devices. The optimization of N-doping into graphene and the design of interconnected and monolithic graphene-based 3D porous structures are crucial for mass/ion diffusion and the final oxygen reduction reaction (ORR)/battery performance. Aqueous-type and all-solid-state primary Mg-air batteries using N-doped nanoporous graphene as air cathodes are assembled. N-doped nanoporous graphene with 50-150 nm pores and ≈99% porosity is found to exhibit a Pt-comparable ORR performance, along with satisfactory durability in both neutral and alkaline media. Remarkably, the all-solid-state battery exhibits a peak power density of 72.1 mW cm-2 ; this value is higher than that of a battery using Pt/carbon cathodes (54.3 mW cm-2 ) owing to the enhanced catalytic activity induced by N-doping and rapid air breathing in the 3D porous structure. Additionally, the all-solid-state battery demonstrates better performances than the aqueous-type battery owing to slow corrosion of the Mg anode by solid electrolytes. This study sheds light on the design of free-standing and catalytically active 3D nanoporous graphene that enhances the performance of both Mg-air batteries and various carbon-neutral-technologies using neutral electrolytes.

Stereolithography 3D Printed Carbon Microlattices with Hierarchical Porosity for Structural and Functional Applications.

Hierarchically porous carbon microlattices (HPCMLs) fabricated by using a composite photoresin and stereolithography (SLA) 3D printing is reported. Containing magnesium oxide nanoparticles (MgO NPs) as porogens and multilayer graphene nanosheets as UV-scattering inhibitors, the composite photoresin is formed to simple cubic microlattices with digitally designed porosity of 50%. After carbonization in vacuum at 1000 °C and chemical removal of MgO NPs, it is realized that carbon microlattices possessing hierarchical porosity are composed of the lattice architecture (≈100 µm), macropores (≈5 µm), mesopores (≈50 nm), and micropores (≈1 nm). The linear shrinkage after pyrolysis is as small as 33%. Compressive strength of 7.45 to 10.45 MPa and Young's modulus of 375 to 736 MPa are achieved, proving HPCMLs a robust mechanical component among reported carbon materials with a random pore structure. Having a few millimeters in thickness, the HPCMLs can serve as thick supercapacitor electrodes that demonstrate gravimetric capacitances 105 and 13.8 F g-1 in aqueous and organic electrolyte, reaching footprint areal capacitances beyond 10 and 1 F cm-2 , respectively. The results present that the composite photoresin for SLA can yield carbon microarchitectures that integrate structural and functional properties for structural energy storages .

Regulated Surface Electronic States of CuNi Nanoparticles through Metal-Support Interaction for Enhanced Electrocatalytic CO2 Reduction to Ethanol.

Developing stable catalysts with higher selectivity and activity within a wide potential range is critical for efficiently converting CO2 to ethanol. Here, the carbon-encapsulated CuNi nanoparticles anchored on nitrogen-doped nanoporous graphene (CuNi@C/N-npG) composite are designedly prepared and display the excellent CO2 reduction performance with the higher ethanol Faradaic effiency (FEethanol  ≥ 60%) in a wide potential window (600 mV). The optimal cathodic energy efficiency (47.6%), Faradaic efficiency (84%), and selectivity (96.6%) are also obtained at -0.78 V versus reversible hydrogen electrode (RHE). Combining with the density functional theory (DFT) calculations, it is demonstrated that the stronger metal-support interaction (Ni-N-C) can regulate the surface electronic structure effectively, boosting the electron transfer and stabilizing the active sites (Cu0 -Cuδ+ ) on the surface of CuNi@C/N-npG, finally realizing the controllable transition of reaction intermediates. This work may guide the designs of electrocatalysts with highly catalytic performance for CO2 reduction to C2+ products.

Oriented attachment interfaces of zeolitic imidazolate framework nanocrystals.

Understanding the growth and coarsening mechanisms of metal-organic framework (MOF) nanoparticles is crucially important for the design and fabrication of MOF materials with diverse functionalities and controllable stability. Oriented attachment (OA) growth is a common manner of MOF nanocrystal coarsening and agglomeration, but the underlying molecular mechanisms have not been well understood to date. Here we report the molecular-scale characterization of the OA interfaces of zeolitic imidazolate framework (ZIF) crystals by state-of-the-art low-dose aberration-corrected transmission electron microscopy. A series of OA interfaces with different molecular structures are captured, implying that multiple kinetic steps are involved in the OA growth of ZIF crystals from non-directional physical attractions between primary nanocrystals, lattice-aligned attachment of the ligand-capped nanocrystals, to coherent interfaces with perfect lattice alignment or stacking faults. It was found that the surface-capping organic ligands not only play an essential role in crystal lattice alignment by near-field directional interactions, but also dominate the interfacial reaction kinetics by interfacial diffusion-controlled elimination of excess surface-capping ligands. These observations provide molecular-scale insights into the OA growth mechanisms of ZIF crystals, which is important for engineering MOF crystal growth pathways by designing surface-capping ligands.

Progress in screening strategies for neonatal developmental dysplasia of the hip.

Developmental dysplasia of the hip (DDH) is the most common congenital disease of the musculoskeletal system in newborns and encompasses a disease spectrum ranging from a stable hip with a mildly dysplastic acetabulum to complete hip dislocation. Systematic screening for infant DDH has been performed for several decades all over the world and has contributed greatly to the early detection, diagnosis and treatment of DDH. However, some cases of delayed diagnosis still occur among the screened population, or conversely, overdiagnosis or overtreatment occasionally occurs. Furthermore, screening strategies for DDH are still controversial. The aim of our study was to analyze the current literature on DDH screening, paying particular attention to DDH screening strategies and their effectiveness. We searched the DDH screening literature from 1958 to 2021 in MEDLINE and other databases using PubMed. In this study, we reviewed the history of DDH screening and the progress of screening strategies and discussed the controversies regarding clinical and ultrasound screening methods with particular emphasis on the current opinions. Given the existing scientific evidence and changes in newborn DDH screening practices, universal ultrasound screening seems to be the best option for preventing late-detected cases and can be recommended as a favorable prevention strategy.

Ultrafine nanoporous intermetallic catalysts by high-temperature liquid metal dealloying for electrochemical hydrogen production.

Intermetallic compounds formed from non-precious transition metals are promising cost-effective and robust catalysts for electrochemical hydrogen production. However, the development of monolithic nanoporous intermetallics, with ample active sites and sufficient electrocatalytic activity, remains a challenge. Here we report the fabrication of nanoporous Co7Mo6 and Fe7Mo6 intermetallic compounds via liquid metal dealloying. Along with the development of three-dimensional bicontinuous open porosity, high-temperature dealloying overcomes the kinetic energy barrier, enabling the direct formation of chemically ordered intermetallic phases. Unprecedented small characteristic lengths are observed for the nanoporous intermetallic compounds, resulting from an intermetallic effect whereby the chemical ordering during nanopore formation lowers surface diffusivity and significantly suppresses the thermal coarsening of dealloyed nanostructure. The resulting ultrafine nanoporous Co7Mo6 exhibits high catalytic activity and durability in electrochemical hydrogen evolution reactions. This study sheds light on the previously unexplored intermetallic effect in dealloying and facilitates the development of advanced intermetallic catalysts for energy applications.

A 3D-Printed, Freestanding Carbon Lattice for Sodium Ion Batteries.

Increasing mass loadings of battery electrodes critically enhances the energy density of an overall battery by eliminating much of the inactive components, while compacting the battery size and lowering the costs of the ingredients. A hard carbon microlattice, digitally designed and fabricated by stereolithography 3D-printing and pyrolysis, offers enormous potential for high-mass-loading electrodes. In this work, sodium-ion batteries using hard carbon microlattices produced by an inexpensive 3D printer are demonstrated. Controlled periodic carbon microlattices are created with enhanced ion transport through microchannels. Carbon microlattices with a beam width of 32.8 µm reach a record-high areal capacity of 21.3 mAh cm-2 at a loading of 98 mg cm-2 without degrading performance, which is much higher than the conventional monolithic electrodes (≈5.2 mAh cm-2 at 92 mg cm-2 ). Furthermore, binder-free, pure-carbon elements of microlattices enable the tracking of structural changes in hard carbon that support the hypothesized intercalation of ions at plateau regions by temporal ex situ X-ray diffraction measurements. These results will advance the development of high-performance and low-cost anodes for sodium-ion batteries as well as help with understanding the mechanisms of ion intercalations in hard carbon, expanding the utilities of 3D-printed carbon architectures in both applications and fundamental studies.

A General Strategy for Engineering Single-Metal Sites on 3D Porous N, P Co-Doped Ti3C2TX MXene.

Two-dimensional (2D) MXenes have been developed to stabilize single atoms via various methods, such as vacancy reduction and heteroatom-mediated interactions. However, anchoring single atoms on 3D porous MXenes to further increase catalytic active sites and thus construct electrocatalysts with high activity and stability remains unexplored. Here, we reported a general synthetic strategy for engineering single-metal sites on 3D porous N, P codoped Ti3C2TX nanosheets. Through a "gelation-and-pyrolysis" process, a series of atomically dispersed metal catalysts (Pt, Ir, Ru, Pd, and Au) supported by N, P codoped Ti3C2TX nanosheets with 3D porous structure can be obtained and serve as efficient catalysts for the electrochemical hydrogen evolution reaction (HER). As a result of the favorable electronic and geometric structure of N(O), P-coordinated metal atoms optimizing catalytic intermediates adsorption and 3D porous structure exposing the active surface sites and facilitating charge/mass transfer, the as-synthesized Pt SA-PNPM catalyst shows ∼20-fold higher activity than the commercial Pt/C catalyst for electrochemical HER over a wide pH range.

3D Continuously Porous Graphene for Energy Applications.

Constructing bulk graphene materials with well-reserved 2D properties is essential for device and engineering applications of atomically thick graphene. In this article, the recent progress in the fabrications and applications of sterically continuous porous graphene with designable microstructures, chemistries, and properties for energy storage and conversion are reviewed. Both template-based and template-free methods have been developed to synthesize the 3D continuously porous graphene, which typically has the microstructure reminiscent of pseudo-periodic minimal surfaces. The 3D graphene can well preserve the properties of 2D graphene of being highly conductive, surface abundant, and mechanically robust, together with unique 2D electronic behaviors. Additionally, the bicontinuous porosity and large curvature offer new functionalities, such as rapid mass transport, ample open space, mechanical flexibility, and tunable electric/thermal conductivity. Particularly, the 3D curvature provides a new degree of freedom for tailoring the catalysis and transport properties of graphene. The 3D graphene with those extraordinary properties has shown great promises for a wide range of applications, especially for energy conversion and storage. This article overviews the recent advances made in addressing the challenges of developing 3D continuously porous graphene, the benefits and opportunities of the new materials for energy-related applications, and the remaining challenges that warrant future study.

Visualizing the {110} surface structure of equilibrium-form ZIF-8 crystals by low-dose Cs-corrected TEM.

The properties of zeolitic imidazolate framework (ZIF) crystals highly depend on the structures of the low-energy surfaces, such as {110} of ZIF-8. However, the atomic/molecular configurations of the ZIF-8 {110} surfaces remain debated. In this study, the near-atomic-scale characterization of {110} surfaces of ZIF-8 is conducted by low-dose aberration-corrected transmission electron microscopy (TEM). The real-space images with mitigated surface delocalization by minimized spherical aberration of TEM, together with the solvent corrected surface energy calculations, demonstrate that the {110} surfaces of ZIF-8 crystals with an equilibrium-form rhombic morphology have a zigzag-type termination. This study provides experimental evidence to clarify the debated structure of {110} ZIF-8 surfaces and has important implications in understanding the crystal growth and surface related properties of ZIF-8.

Nanoporous B13 C2 towards Highly Efficient Electrochemical Nitrogen Fixation.

The electrochemical nitrogen fixation under mild conditions is a promising alternative to the current nitrogen industry with high energy consumption and greenhouse gas emission. Here, a nanoporous boron carbide (np-B13 C2 ) catalyst is reported for electrochemical nitrogen fixation, which is fabricated by the combination of metallurgical alloy design and chemical etching. The resulting np-B13 C2 exhibits versatile catalytic activities towards N2 reduction reactions (NRR) and N2 oxidation reaction (NOR). A high NH3 yield of 91.28 µg h-1 mgcat.-1 and Faradaic efficiency (FE) of 35.53% at -0.05 V versus the reversible hydrogen electrode are obtained for NRR, as well as long-term stability of up to 70 h, making them among the most active NRR electrocatalysts. This catalyst can also achieve a NO3- yield of 165.8 µg h-1  mgcat.-1 and a FE of 8.4% for NOR. In situ Raman spectroscopy and density functional theory calculations reveal that strong coupling between the BC sites modulates the electronic structures of adjacent B atoms of B13 C2 , which enables the B sites to effectively adsorb and activate chemical inert N2 molecules, resulting in lowered energy required by the potential-determining step. Besides, the introduction of carbon can increase the inherent conductivity and reduce the binding energy of the reactants, thus improving N2 fixation performance.

Atomic Ni and Cu co-anchored 3D nanoporous graphene as an efficient oxygen reduction electrocatalyst for zinc-air batteries.

Highly active, cost-effective and durable electrocatalysts for the oxygen reduction reaction (ORR) are critically important for renewable energy conversion and storage. Here we report a 3D bicontinuous nitrogen doped nanoporous graphene electrocatalyst co-anchoring with atomically dispersed nickel and copper atoms ((Ni,Cu)-NG) as a highly active single-atom ORR catalyst, fabricated by the combination of chemical vapor deposition and high temperature gas transportation. The resultant (Ni,Cu)-NG exhibits an exceptional ORR activity in alkaline electrolytes, comparable to the Pt-based benchmarks, from the synergistic effect of the CuNx and NiNx complexes. Endowed with high catalytic activity and outstanding durability under harsh electrochemical environments, rechargeable zinc-air batteries using (Ni,Cu)-NG as the cathodes show excellent energy efficiency (voltage gap of 0.74 V), large power density (150.6 mW cm-2 at 250 mA cm-2) and high cycling stability (>500 discharge-charge cycles at 10 mA cm-2). This study may pave an efficient avenue for designing highly durable single-atom ORR catalysts for metal-air batteries.

Effect of Local Atomic Structure on Sodium Ion Storage in Hard Amorphous Carbon.

The fundamental understanding of sodium storage mechanisms in amorphous carbon is essential to develop high-performance anode materials for sodium-ion batteries. However, the intrinsic relation between the structure of amorphous carbon and Na+ storage remains to be debated due to the difficulty in controlling and characterizing the local atomic configurations of amorphous carbon. Here we report quantitative measurements of Na+ storage in a low-temperature dealloyed hard carbon with a tunable local structure from completely disordered micropores to gradually increased graphitic order domains. The structure-capacity-potential correlation not only verifies the disputing "adsorption-intercalation" mechanisms, i.e., Na+ intercalation into local graphitic domains for the low-voltage plateaus and adsorption in fully disordered carbon for the sloping voltage profiles, but also unveils a new mechanism of Na+ adsorption on defective sites of graphitic carbon in the medium-potential sloping region. The quantitative investigations provide essential insights into the reaction mechanisms of Na+ with amorphous carbon for designing advanced sodium-ion battery anodes.

Graphene-coated nanoporous nickel towards a metal-catalyzed oxygen evolution reaction.

Developing highly active electrocatalysts with low costs and long durability for oxygen evolution reactions (OERs) is crucial towards the practical implementations of electrocatalytic water-splitting and rechargeable metal-air batteries. Anodized nanostructured 3d transition metals and alloys with the formation of OER-active oxides/hydroxides are known to have high catalytic activity towards OERs but suffer from poor electrical conductivity and electrochemical stability in harsh oxidation environments. Here we report that high OER activity can be achieved from the metallic state of Ni which is passivated by atomically thick graphene in a three-dimensional nanoporous architecture. As a free-standing catalytic anode, the non-oxide transition metal catalyst shows a low OER overpotential, high OER current density and long cycling lifetime in alkaline solutions, benefiting from the high electrical conductivity and low impedance resistance for charge transfer and transport. This study may pave a new way to develop high efficiency transition metal OER catalysts for a wide range of applications in renewable energy.

Comparative efficacy and safety profile for the treatment of humeral bone cysts in children: curettage and mixed bone grafting either with or without elastic intramedullary nailing.

PURPOSE: The primary aim of our study was to evaluate the comparative efficacy and safety profile of curettage and mixed bone grafting without instrument or with elastic intramedullary nailing in the treatment of humeral bone cyst in children. METHODS: Our retrospective study included a total of 48 children harboring humeral bone cyst in our hospital from August 2012 to February 2019. The patients enrolled were divided into elastic nailing group with the application of elastic intramedullary nailing (n = 25) and control group without using instrument (n = 23) during the management of curettage and mixed bone grafting. The following medical outcomes of the two groups were monitored and recorded: the amount of intraoperative blood loss, operation time and postoperative full weight-bearing time, in addition to postoperative clinical effects after 1 year, the function and pain level of shoulder joint before and 1, 3, 6, 9, 12, and 16 months after operation. Follow-up radiographic outcomes were reviewed to observe bone healing, local recurrence and internal fixation loosening, and other postoperative complications. RESULTS: The clinical curative effect of the elastic nailing group was higher than that of the control group 16 months after operation (96.00% > 73.91%, P < 0.05). The intraoperative blood loss and postoperative full weight-bearing time in the elastic nailing group were less than those in the control group (P < 0.05), but the operation time was statistically insignificant between the two groups (P > 0.05). Before operation, the shoulder joint function of the two groups was comparable (P > 0.05), while the function showed remarkably better outcome in the elastic nailing group than control group 1 to 16 months after operation (P < 0.05). Before operation, the pain level of the two groups was comparable (P > 0.05), while 1 to 16 months after operation, the pain level of the elastic nailing group was significantly lower than that of the control group (P < 0.05). Patients in both groups were followed up for 16 months. Mixed bone grafting fusion was indicated by imaging CT and X-ray during the follow-up period, with an average fusion time of 11.3 ± 1.2 months (range, 8-16 months). Three months after operation, there was 1 case of incomplete pathological fracture in the control group, while no related complications occurred in the elastic nailing group. Moreover, no tumor recurrence was observed in the two groups. The two groups were comparable in terms of the incidence of complications (P > 0.05). CONCLUSION: Children with humeral cyst treated with curettage and mixed bone grafting with the additional use of elastic intramedullary nailing exerted superior results to those without using instrument as there are beneficial outcomes and safety profile and no complications.

Dislocation-mediated shear amorphization in boron carbide.

The failure of superhard materials is often associated with stress-induced amorphization. However, the underlying mechanisms of the structural evolution remain largely unknown. Here, we report the experimental measurements of the onset of shear amorphization in single-crystal boron carbide by nanoindentation and transmission electron microscopy. We verified that rate-dependent loading discontinuity, i.e., pop-in, in nanoindentation load-displacement curves results from the formation of nanosized amorphous bands via shear amorphization. Stochastic analysis of the pop-in events reveals an exceptionally small activation volume, slow nucleation rate, and lower activation energy of the shear amorphization, suggesting that the high-pressure structural transition is activated and initiated by dislocation nucleation. This dislocation-mediated amorphization has important implications in understanding the failure mechanisms of superhard materials at stresses far below their theoretical strengths.

Ultrastable Silicon Anode by Three-Dimensional Nanoarchitecture Design.

State-of-the-art carbonaceous anodes are approaching their achievable performance limit in Li-ion batteries (LIBs). Silicon has been recognized as one of the most promising anodes for next-generation LIBs because of its advantageous specific capacity and secure working potential. However, the practical implementation of silicon anodes needs to overcome the challenges of substantial volume changes, intrinsic low conductivity, and unstable solid electrolyte interphase (SEI) films. Here, we report an inventive design of a sandwich N-doped graphene@Si@hybrid silicate anode with bicontinuous porous nanoarchitecture, which is expected to simultaneously conquer all these critical issues. In the ingeniously designed hybrid Si anode, the nanoporous N-doped graphene acts as a flexible and conductive support and the amorphous hybrid silicate coating enhances the robustness and suppleness of the electrode and facilitates the formation of stable SEI films. This binder-free and stackable hybrid electrode achieves excellent rate capability and cycling performance (817 mAh/g at 5 C for 10 000 cycles). Paired with LiFePO4 cathodes, more than 100 stable cycles can be readily realized in full batteries.

Dealloying Kinetics of AgAu Nanoparticles by In Situ Liquid-Cell Scanning Transmission Electron Microscopy.

Understanding the formation and evolution of bicontinuous nanoporous structure during dealloying has been one of the most challenging subjects of dealloying research. However, previous in situ investigations either suffer from insufficient spatial resolution (e.g., X-ray tomography) or lack morphology visualization and mass information (e.g., scanning tunneling microscopy). In this work, we report the kinetics of the whole course of dealloying by utilizing liquid-cell aberration-corrected scanning transmission electron microscopy. With Z-contrast imaging analysis, the in situ sub-nanoscale characterization reveals two new phenomena, an initial period of dealloying indicative of an initial length scale for bulk dealloying and a large volume shrinkage in a nanoscale alloy precursor. We explain the particle-size-dependent volume shrinkage with the formation of a dense shell and quantify the dependence with a simple geometric model. These insights into the mechanisms of dealloying will enable deliberate designs of nanoporous structures.

Synergetic Effect of Liquid and Solid Catalysts on the Energy Efficiency of Li-O2 Batteries: Cell Performances and Operando STEM Observations.

The sluggish cathodic kinetics and lower energy efficiency, associated with solid and insulating discharge products of Li2O2, are the key factors that prevent the practical implementation of Li-O2 batteries (LOBs). Here we demonstrate that the combination of the solid catalyst (RuO2) and soluble redox mediator tetrathiafulvalene (TTF) exhibits a synergetic effect in improving the cathodic kinetics and energy efficiency of LOBs by reducing both charge and discharge overpotentials. Operando electron microscopy observations and electrochemical measurements reveal that RuO2 not only exhibits bifunctional catalysis for Li-O2 reactions but also benefits the catalytic efficiency of TTF. Meanwhile, TTF plays an important role in activating the Li2O2 passivated RuO2 catalysts and in helping RuO2 effectively oxidize the discharge products during charging. The synergetic effect of solid and liquid catalysts, beyond traditional bifunctional catalysis, obviously increases the cathodic kinetics and round-trip energy efficiency of LOBs.