Homogenous metallic deposition regulated by abundant lithiophilic sites in nickel/cobalt oxides nanoneedle arrays for lithium metal batteries

Although lithium(Li)metal delivers the highest theoretical capacity as a battery anode,its high reactivity can generate Li dendrites and"dead"Li during cycling,resulting in poor reversibility and low Li utilization.Inducing uniform Li plating/stripping is the core of solving these problems.Herein,we design a highly lithiophilic carbon film with an outer sheath of the nanoneedle arrays to induce homogeneous Li plating/stripping.The excellent conductivity and 3D framework of the carbon film not only offer fast charge transport across the entire electrode but also mitigate the volume change of Li metal during cycling.The abundant lithiophilic sites ensure stable Li plating/stripping,thereby inhibiting the Li dendritic growth and"dead"Li formation.The resulting composite anode allows for stable Li stripping/plating under 0.5 mA cm^(-2) with a capacity of 0.5 mA h cm^(-2) for 4000 h and 3 mA cm^(-2) with a capacity of3 mA h cm^(-2) for 1000 h.The Ex-SEM analysis reveals that lithiophilic property is different at the bottom,top,or channel in the structu re,which can regulate a bottom-up uniform Li deposition behavior.Full cells paired with LFP show a stable capacity of 155 mA h g^(-1) under a current density of 0.5C.The pouch cell can keep powering light-emitting diode even under 180°bending,suggesting its good flexibility and great practical applications.

Construction of a few-layer g-C_3N_4/α-MoO_3 nanoneedles all-solid-state Z-scheme photocatalytic system for photocatalytic degradation

The suppression of the recombination of electrons and holes(e–h) and the enhancement of the light absorption of semiconductors are two key points toward efficient photocatalytic degradation.Here,we report a few-layer g-C_3N_4/α-MoO_3 nanoneedles(flg-C_3N_4/α-MoO_3 NNs) all-solid-state Z-scheme mechanism photocatalyst synthesized via a typical hydrothermal method in a controlled manner.The recombination of the photo-induced e–h pairs could be effectively restrained by the Z-scheme passageway between the flg-C_3N_4 and α-MoO_3 NNs in the composite,which could also promise a high redox ability to degrade pollutants.And it became possible for the prepared photocatalyst to absorb light in a wide range of wavelengths.The detailed mechanism was studied by electron spin-resonance spectroscopy(ESR).The low-dimensional nanostructure of the two constituents(α-MoO_3 NNs with one-dimensional structure and flg-C_3N_4 with two-dimensional structure) endowed the composite with varieties of excellent physicochemical properties,which facilitated the transfer and diffusion of the photoelectrons and increased the specific surface area and the active sites.The 10 wt% flg-C_3N_4/α-MoO_3 NNs showed the best photocatalytic performance toward RhB degradation,the rate of which was 71.86%,～2.6 times higher than that ofα-MoO_3 NNs.

Bimetallic NiCo2S4 Nanoneedles Anchored on Mesocarbon Microbeads as Advanced Electrodes for Asymmetric Supercapacitors

Bimetallic Ni–Co sulfides are outstanding pseudocapacitive materials with high electrochemical activity and excellent energy storage performance as electrodes for high-performance supercapacitors.In this study,a novel urchin-like NiCo2S4@mesocarbon microbead(NCS@MCMB) composite with a core–shell structure was prepared by a facile two-step hydrothermal method.The highly conductive MCMBs offered abundant adsorption sites for the growth of NCS nanoneedles,which allowed each nanoneedle to fully unfold without aggregation,resulting in improved NCS utilization and efficient electron/ion transferin the electrolyte.When applied as an electrode material for supercapacitors,the composite exhibited a maximum specific capacitance of 936 Fg-1 at 1 Ag-1 and a capacitance retention of 94% after 3000 cycles at 5 Ag-1,because of the synergistic effect of MCMB and NCS.Moreover,we fabricated an asymmetric supercapacitor based on the NCS@MCMB composite,which exhibited enlarged voltage windows and could power a light-emitting diode device for several minutes,further demonstrating the exceptional electrochemical performance of the NCS@MCMB composite.

Room-temperature hydrogenation of halogenated nitrobenzenes over metal-organic-framework-derived ultra-dispersed Ni stabilized by N-doped carbon nanoneedles

Ultra-dispersed Ni nanoparticles(7.5 nm)on nitrogen-doped carbon nanoneedles(Ni@NCNs)were prepared by simple pyrolysis of Ni-based metal–organic-framework for selective hydrogenation of halogenated nitrobenzenes to corresponding anilines.Two different crystallization methods(stirring and static)were compared and the optimal pyrolysis temperature was explored.Ni@NCNs were systematically characterized by wide analytical techniques.In the hydrogenation of p-chloronitrobenzene,Ni@NCNs-600(pyrolyzed at 600°C)exhibited extraordinarily high performance with 77.9 h^(–1)catalytic productivity and>99%p-chloroaniline selectivity at full p-chloronitrobenzene conversion under mild conditions(90°C,1.5 MPa H2),showing obvious superiority compared with reported Ni-based catalysts.Notably,the reaction smoothly proceeded at room temperature with full conversion and>99%selectivity.Moreover,Ni@NCNs-600 afforded good tolerance to various nitroarenes substituted by sensitive groups(halogen,nitrile,keto,carboxylic,etc.),and could be easily recycled by magnetic separation and reused for 5 times without deactivation.The adsorption tests showed that the preferential adsorption of–NO2 on the catalyst can restrain the dehalogenation of p-chloronitrobenzene,thus achieving high p-chloroaniline selectivity.While the high activity can be attributed to high Ni dispersion,special morphology,and rich pore structure of the catalyst.

Plasma-induced Mo-doped Co_(3)O_(4)with enriched oxygen vacancies for electrocatalytic oxygen evolution in water splitting

Heteroatomic substitution and vacancy engineering of spinel oxides can theoretically optimize the oxygen evolution reaction(OER)through charge redistribution and d-band center modification but still remain a great challenge in both the preparation and catalytic mechanism.Herein,we proposed a novel and efficient Ar-plasma(P)-assisted strategy to construct heteroatom Mo-substituted and oxygen vacancies enriched hierarchical spinel Co_(3)O_(4)porous nanoneedle arrays in situ grown on carbon cloth(denoted P-Mo-Co_(3)O_(4)@CC)to improve the OER performance.Ar-plasma technology can efficiently generate vacancy sites at the surface of hydroxide,which induces the anchoring of Mo anion salts through electrostatic interaction,finally facilitating the substitution of Mo atoms and the formation of oxygen vacancies on the Co_(3)O_(4)surface.The P-Mo-Co_(3)O_(4)@CC affords a low overpotential of only 276 mV at 10 mA cm^(−2)for the OER,which is 58 mV superior to that of Mo-free Co_(3)O_(4)@CC and surpasses commercial RuO_(2)catalyst.The robust stability and satisfactory selectivity(nearly 100%Faradic efficiency)of P-Mo-Co_(3)O_(4)@CC for the OER are also demonstrated.Theoreti-cal studies demonstrate that Mo with variable valance states can efficiently regulates the atomic ratio of Co^(3+)/Co^(2+)and increases the number of oxygen vacancies,thereby inducing charge redistribution and tuning the d-band center of Co_(3)O_(4),which improve the adsorption energy of oxygen intermediates(e.g.,*OOH)on P-Mo-Co_(3)O_(4)@CC during OER.Furthermore,the two-electrode OER//HER electrolyzer equipped with P-Mo-Co_(3)O_(4)@CC as anode displays a low operation potential of 1.54 V to deliver a current density of 10 mA cm^(−2),and also exhibits good reversibility and anticurrent fluctuation ability under simulated real energy supply conditions,demonstrating the great potential of P-Mo-Co_(3)O_(4)@CC in water electrolysis.

A Review of Nano/Micro/Milli Needles Fabrications for Biomedical Engineering

Needles,as some of the most widely used medical devices,have been effectively applied in human disease prevention,diagnosis,treatment,and rehabilitation.Thin 1D needle can easily penetrate cells/organs by generating highly localized stress with their sharp tips to achieve bioliquid sampling,biosensing,drug delivery,surgery,and other such applications.In this review,we provide an overview of multiscale needle fabrication techniques and their biomedical applications.Needles are classified as nanoneedles,microneedles and millineedles based on the needle diameter,and their fabrication techniques are highlighted.Nanoneedles bridge the inside and outside of cells,achieving intracellular electrical recording,biochemical sensing,and drug delivery.Microneedles penetrate the stratum corneum layer to detect biomarkers/bioelectricity in interstitial fluid and deliver drugs through the skin into the human circulatory system.Millineedles,including puncture,syringe,acupuncture and suture needles,are presented.Finally,conclusions and future perspectives for next-generation nano/micro/milli needles are discussed.

Enhanced electrochemical oxidation of perfluorooctanoic acid on Ti/SnO_(2)-Sb electrode by surface morphology regulation

Electrochemical oxidation is an effective method to degrade persistent organic pollutants.However,due to the limited catalytic activity of traditional thin film electrodes,the anodic oxidation process is slow and usually requires high energy consumption.Herein,Ti/SnO_(2)-Sb electrode with regulated surface structure was reported to enhance the performance for electrochemical oxidation of persistent organic pollutants.The electrode deposited with SnO_(2)-Sb nanoneedles(Ti/N-SnO_(2)-Sb)showed higher oxidation activity.Its kinetic constant for perfluorooctanoic acid(PFOA)oxidation was 2.0 h^(-1)and the total organic carbon removal rate was 81.7%(4 h)at a relatively low current density of 6 mA/cm^2.Compared with Ti/SnO_(2)-Sb thin film and nanoparticles,Ti/N-SnO_(2)-Sb significantly improved the electrochemical active area and·OH yield,and simultaneously reduced the electron transfer resistance,which enabled it to oxidize PFOA more rapidly even at a lower potential.This work provides a new strategy for promoting the electrochemical oxidation performance.

Generation of multi-hollow crystalline Mo fibres

Flower-like micrometer-sized crystalline Mo fibres have been prepared by directly heating Mo powder on Mo foil, under Ar atmosphere. ED, EDX, SEM and HRTEM studies reveal that each fibre consists of a single Mo crystal containing multi-hollow cores. A one-dimensional growth mechanism, on the basis of the one-dimensional thermal flow during fibre formation, is discussed.