Understanding the catalysis of chromium trioxide added magnesium hydride for hydrogen storage and Li ion battery applications

This study explores how the chemical interaction between magnesium hydride(MgH_(2))and the additive CrO_(3) influences the hydrogen/lithium storage characteristics of MgH_(2).We have observed that a 5 wt.%CrO_(3) additive reduces the dehydrogenation activation energy of MgH_(2) by 68 kJ/mol and lowers the required dehydrogenation temperature by 80℃.CrO_(3) added MgH_(2) was also tested as an anode in an Li ion battery,and it is possible to deliver over 90%of the total theoretical capacity(2038 mAh/g).Evidence for improved reversibility in the battery reaction is found only after the incorporation of additives with MgH_(2).In depth characterization study by X-ray diffraction(XRD)technique provides convincing evidence that the CrO_(3) additive interacts with MgH_(2) and produces Cr/MgO byproducts.Gibbs free energy analyses confirm the thermodynamic feasibility of conversion from MgH_(2)/CrO_(3) to MgO/Cr,which is well supported by the identification of Cr(0)in the powder by X ray photoelectron spectroscopy(XPS)technique.Through high resolution transmission electron microscopy(HRTEM)and energy dispersive spectroscopy(EDS)we found evidence for the presence of 5 nm size Cr nanocrystals on the surface of MgO rock salt nanoparticles.There is also convincing ground to consider that MgO rock salt accommodates Cr in the lattice.These observations support the argument that creation of active metal–metal dissolved rock salt oxide interface may be vital for improving the reactivity of MgH_(2),both for the improved storage of hydrogen and lithium.

Memristive feature and mechanism induced by laser-doping in defect-free 2D semiconductor materials

Memristors as non-volatile memory devices have gained numerous attentions owing to their advantages in storage,in-memory computing, synaptic applications, etc. In recent years, two-dimensional(2D) materials with moderate defects have been discovered to exist memristive feature. However, it is very difficult to obtain moderate defect degree in 2D materials, and studied on modulation means and mechanism becomes urgent and essential. In this work, we realized memristive feature with a bipolar switching and a configurable on/off ratio in a two-terminal MoS_(2) device(on/off ratio ~100), for the first time, from absent to present using laser-modulation to few-layer defect-free MoS_(2)(about 10 layers), and its retention time in both high resistance state and low resistance state can reach 2×10^(4) s. The mechanism of the laser-induced memristive feature has been cleared by dynamic Monte Carlo simulations and first-principles calculations. Furthermore, we verified the universality of the laser-modulation by investigating other 2D materials of TMDs. Our work will open a route to modulate and optimize the performance of 2D semiconductor memristive devices.

Mechanical stimulation devices formechanobiology studies:a market,literature,and patents review

Significant advancements in various research and technological fields have contributed to remarkable findings on the physiological dynamics of the human body.Tomore closely mimic the complex physiological environment,research has moved from two-dimensional(2D)culture systems to more sophisticated three-dimensional(3D)dynamic cultures.Unlike bioreactors or microfluidic-based culture models,cells are typically seeded on polymeric substrates or incorporated into 3D constructs which are mechanically stimulated to investigate cell response to mechanical stresses,such as tensile or compressive.This review focuses on the working principles of mechanical stimulation devices currently available on the market or custom-built by research groups or protected by patents and highlights the main features still open to improvement.These are the features which could be focused on to perform,in the future,more reliable and accurate mechanobiology studies.

Fabrication of ultra-high strength magnesium alloys over 540 MPa with low alloying concentration by double continuously extrusion

We prepare a new type of patented biodegradable biomedical Mg-Nd-Zn-Zr(JDBM)alloy system and impose double continuously extrusion(DCE)processing.The lowest processing temperature is 250℃for JDBM-2.1Nd and 310℃for JDBM-2.8Nd,which increases with the Nd concentration.The highest yield strength of 541 MPa is achieved in JDBM-2.1 Nd samples when extruded at 250℃and the elongation is about 3.7%.Moreover,the alloy with a lower alloying element content can reach a higher yield strength while that with a higher alloying element content can reach a larger elongation after DCE processing.However,when extruded under the same conditions,the alloy with a higher alloying contents exhibits better tensile properties.

High-performance junction field-effect transistor based on black phosphorus/β-Ga2O3 heterostructure

Black phosphorous(BP),an excellent two-dimensional(2D)monoelemental layered p-type semiconductor material with high carrier mobility and thickness-dependent tunable direct bandgap structure,has been widely applied in various devices.As the essential building blocks for modern electronic and optoelectronic devices,high quality PN junctions based on semiconductors have attracted widespread attention.Herein,we report a junction field-effect transistor(JFET)by integrating narrow-gap p-type BP and ultra-wide gap n-typeβ-Ga2O3 nanoflakes for the first time.BP andβ-Ga2O3 form a vertical van der Waals(vdW)heterostructure by mechanically exfoliated method.The BP/β-Ga2O3 vdW heterostructure exhibits remarkable PN diode rectifying characteristics with a high rectifying ratio about 107 and a low reverse current around pA.More interestingly,by using the BP as the gate andβ-Ga2O3 as the channel,the BP/β-Ga2O3 JFET devices demonstrate excellent n-channel JFET characteristics with the on/off ratio as high as 107,gate leakage current around as low as pA,maximum transconductance(gm)up to 25.3μS and saturation drain current(IDSS)of 16.5μA/μm.Moreover,it has a pinch-off voltage of–20 V and a minimum subthreshold swing of 260 mV/dec.These excellent n-channel JFET characteristics will expand the application of BP in future nanoelectronic devices.

Stable overall water splitting in an asymmetric acid/ alkaline electrolyzer comprising a bipolar membrane sandwiched by bifunctional cobalt-nickel phosphide nanowire electrodes

Water splitting has been proposed to be a promising approach to producing clean hydrogen fuel.The two half-reactions of water splitting,that is,the hydrogen evolution reaction(HER)and oxygen evolution reaction(OER),take place kinetically fast in solutions with completely different pH values.Enabling HER and OER to simultaneously occur under kinetically favorable conditions while using exclusively low-cost,earth-abundant electrocatalysts is highly desirable but remains a challenge.Herein,we demonstrate that using a bipolar membrane(BPM)we can accomplish HER in a strongly acidic solution and OER in a strongly basic solution,with bifunctional self-supported cobaltnickel phosphide nanowire electrodes to catalyze both reactions.Such asymmetric acid/alkaline water electrolysis can be achieved at 1.567 V to deliver a current density of 10 mA/cm2 with ca.100%Faradaic efficiency.Moreover,using an“irregular”BPM with unintentional crossover the voltage needed to afford 10 mA/cm2 can be reduced to 0.847 V,due to the assistance of electrochemical neutralization between acid and alkaline.Furthermore,we show that BPM-based asymmetric water electrolysis can be accomplished in a circulated single-cell electrolyzer delivering 10 mA/cm2 at 1.550 V and splitting water very stably for at least 25 hours,and that water electrolysis is enabled by a solar panel operating at 0.908 V(@13 mA/cm2),using an“irregular”BPM.BPMbased asymmetric water electrolysis is a promising alternative to conventional proton and anion exchange membrane water electrolysis.

Easy preparation of multifunctional ternary PdNiP/C catalysts toward enhanced small organic molecule electro-oxidation and hydrogen evolution reactions

The small organic molecule electro-oxidation(OMEO) and the hydrogen evolution(HER) are two important half-reactions in direct liquid fuel cells(DLFCs) and water electrolyzers,respectively,whose performance is largely hindered by the low activity and poor stability of electrocatalysts.Herein,we demonstrate that a simple phosphorization treatment of commercially available palladium-nickel(PdNi) catalysts results in multifunctional ternary palladium nickel phosphide(PdNiP) catalysts,which exhibit substantially enhanced electrocatalytic activity and stability for HER and OMEO of a number of molecules including formic acid,methanol,ethanol,and ethylene glycol,in acidic and/or alkaline media.The improved performance results from the modification of electronic structure of palladium and nickel by the introduced phosphorus and the enhanced corrosion resistance of PdNiP.The simple phosphorization approach reported here allows for mass production of highly-active OMEO and HER electrocatalysts,holding substantial promise for their large-scale application in direct liquid fuel cells and water electrolyzers.

Realization of flexible in-memory computing in a van der Waals ferroelectric heterostructure tri-gate transistor

Combining logical function and memory characteristics of transistors is an ideal strategy for enhancing computational efficiency of transistor devices.Here,we rationally design a tri-gate two-dimensional(2D)ferroelectric van der Waals heterostructures device based on copper indium thiophosphate(CuInP_(2)S_(6))and few layers tungsten disulfide(WS_(2)),and demonstrate its multi-functional applications in multi-valued state of data,non-volatile storage,and logic operation.By co-regulating the input signals across the tri-gate,we show that the device can switch functions flexibly at a low supply voltage of 6 V,giving rise to an ultra-high current switching ratio of 107 and a low subthreshold swing of 53.9 mV/dec.These findings offer perspectives in designing smart 2D devices with excellent functions based on ferroelectric van der Waals heterostructures.

Interface engineering of Co_(9)S_(8)/SnS heterostructure as a high-performance anode for lithium/sodium-ion batteries

Transition metal sulfide(TMS)anodes exhibit the characteristics of phase stability and high capacity for lithium/sodium-ion batteries(LIBs/SIBs).However,the TMS anodes often suffer from poor electronic conductivity,low ionic diffusion and large volume expansion during Li/Na-ion intercalation significantly impairing the Li/Na-storage performance.Herein,a long chain heterostructure composed of the Co_(9)S_(8) and SnS are first reported,which can generate rich phase interfaces,and small crystal domains.The unique structure can facilitate the properties of reactivity,conductivity and ionic diffusion.In addition,the heterostructure surface is modified by the N-doped carbon(N-DC@(CoSn)S),successfully improving the structural stability.The synergistic effects of Co_(9)S_(8)/SnS heterostructure and coated carbon layer effectively increase the capacity and cycling stability.The N-DC@(CoSn)S anode delivers enhanced high specific capacities of 820.6 mAh·g^(−1) at 1.0 A·g^(–1) after 500 cycles for LIBs and 339.2 mAh·g^(–1)at 0.5 A·g^(–1) after 1000 cycles for SIBs,respectively.This work is expected to provide a material design idea for preparing LIBs/SIBs with high capacity and long cycling life.

An integrated portable bio-monitoring system based on tough hydrogels for comprehensive detection of physiological activities

Advanced soft ion-conducting hydrogels have been developed rapidly in the integrated portable health monitoring equipment due to their higher sensitivity,sensory traits,tunable conductivity,and stretchability for physiological activities and personal healthcare detection.However,traditional hydrogel conductors are normally susceptible to large deformation and strong mechanical stress,which leads to inferior electro-mechanical stability for real application scenarios.Herein,a strong ionically conductive hydrogel(poly(vinyl alcohol)-boric acid-glycerol/sodium alginate-calcium chloride/electrolyte ions(PBG/SC/EI))was designed by engineering the covalently and ionically crosslinked networks followed by the salting-out effect to further enhance the mechanical strength and ionic conductivity of the hydrogel.Owing to the collective effects of the energy-dissipation mechanism and salting-out effect,the designed PBG/SC/EI with excellent structural integrity and robustness exhibits exceptional mechanical properties(elongation at break for 559.1%and tensile strength of 869.4 kPa)and high ionic conductivity(1.618 S·m^(-1)).As such,the PBG/SC/EI strain sensor features high sensitivity(gauge factor=2.29),which can effectively monitor various kinds of human motions(joint motions,facial micro-expression,faint respiration,and voice recognition).Meanwhile,the hydrogel-based Zn||MnO_(2)battery delivers a high capacity of 267.2 mAh·g^(-1)and a maximal energy density of 356.8 Wh·kg^(-1)associated with good cycle performance of 71.8%capacity retention after 8000 cycles.Additionally,an integrated bio-monitoring system with the sensor and Zn||MnO_(2)battery can accurately identify diverse physiological activities in a real-time and non-invasive way.This work presents a feasible strategy for designing high-performance conductive hydrogels for highly-reliable integrated bio-monitoring systems with excellent practicability.

Spray pyrolysis-derived W-doped MoSe_(2)/rGO paper-like microspheres:optimization of microstructure and mesostructure for enhanced lithium storage

Two-dimensional MoSe_(2) is a promising candidate for lithium-ion battery anodes.However,its conductivity and lithium storage volumetric effect still need to be optimized.In this work,W-doped MoSe_(2)/rGO paper-like microspheres are successfully prepared through ultrasonic spray pyrolysis,achieving optimization at both the microstructure and mesostructure to enhance the lithium storage performance of the material.Firstly,by utilizing the similar two-dimensional structure between MoSe_(2) and rGO,self-assembly is achieved through spray pyrolysis,resulting in a well-defined van der Waals heterostructure at the interface on the microscale,enhancing the electron and ion transfer capability of the composite.Secondly,the mesoscale paper-like microsphere morphology provides additional volume expansion buffering space.Moreover,W-doping not only increases the interlayer spacing of MoSe_(2)(0.73 nm),thereby reducing the diffusion resistance of Li+,but also allow for the modulation of the energy band structure of the material.Density functional theory(DFT)calculations confirm that W-doped MoSe_(2)/rGO exhibits the narrowest bandgap(0.892 eV).Therefore,the composite demonstrates excellent lithium storage performance,maintaining a specific capacity of 732.9 mAh·g^(-1)after 300 cycles at a current density of 1 A·g^(-1).

Diamond: asymmetry leads to continuous hardening

Naturally occurring and synthetic materials are often polycrystalline comprising various species of grain boundaries(GBs),many of which are randomly oriented.It is known that GBs play a pivotal role in affecting a broad range of material properties,and the nature of GBs is dedicated by grain orientation,growth history and processing conditions.

High entropy materials as emerging electrocatalysts for hydrogen production through low-temperature water electrolysis

The production of hydrogen through water electrolysis(WE)from renewable electricity is set to revolutionise the energy sector that is at present heavily dependent on fossil fuels.However,there is still a pressing need to develop advanced electrocatalysts able to show high activity and withstand industrially-relevant operating conditions for a prolonged period of time.In this regard,high entropy materials(HEMs),including high entropy alloys and high entropy oxides,comprising five or more homogeneously distributed metal components,have emerged as a new class of electrocatalysts owing to their unique properties such as low atomic diffusion,structural stability,a wide variety of adsorption energies and multi-component synergy,making them promising catalysts for challenging electrochemical reactions,including those involved in WE.This review begins with a brief overview about WE technologies and a short introduction to HEMs including their synthesis and general physicochemical properties,followed by a nearly exhaustive summary of HEMs catalysts reported so far for the hydrogen evolution reaction,the oxygen evolution reaction and the overall water splitting in both alkaline and acidic conditions.The review concludes with a brief summary and an outlook about the future development of HEM-based catalysts and further research to be done to understand the catalytic mechanism and eventually deploy HEMs in practical water electrolysers.

Anomalous refinement and uniformization of grains in metallic thin films

When a laser beam writes on a metallic film,it usually coarsens and deuniformizes grains because of Ostwald ripening,similar to the case of annealing.Here we show an anomalous refinement effect of metal grains:A metallic silver film with large grains melts and breaks into uniform,close-packed,and ultrafine(~10 nm)grains by laser direct writing with a nanoscale laser spot size and nanosecond pulse that causes localized heating and adaptive shock-cooling.This method exhibits high controllability in both grain size and uniformity,which lies in a linear relationship between the film thickness(h)and grain size(D),D∝h.The linear relationship is significantly different from the classical spinodal dewetting theory obeying a nonlinear relationship(D∝h5/3)in common laser heating.We also demonstrate the application of such a silver film with a grain size of~10.9 nm as a surface-enhanced Raman scattering chip,exhibiting superhigh spatial-uniformity and low detection limit down to 10-15 M.This anomalous refinement effect is general and can be extended to many other metallic films.

In situ observation of the pseudoelasticity of twin boundary

Twin boundary(TB)is a special and fundamental internal interface that plays a key role in altering the mechanical and physical properties of materials.However,the atomistic deformation mechanism of TB re-mains under debate,of which the most concerned aspect is how TB would affect the mechanical strength and plasticity of a material.Herein,we introduce our new discovery that the pseudoelastic strain of a TB can recover with decomposition and escape of pile-up dislocations,demonstrated by imposing a sponta-neous pseudoelastic deformation with recoverable plastic bending strain up to 5.1%on a TB.We found that the steps on the curved TB gradually annihilated during the migration of the TB,which was in-duced by the slip of decomposition dislocations on the TB.The TB not only provides local strain harden-ing through interaction with dislocations during the loading stage but also acts as a channel for the fast movement of decomposition dislocations during the recovery stage.Beside,the TB can maintain excellent pseudoelasticity under a multicycle bending test,which may play an important role in improving the fa-tigue resistance of materials.These findings could open up a new avenue for optimizing the mechanical properties of materials by manipulating their twin boundaries at the nanoscale.

Recent advances of SiO_(x)-based anodes for sustainable lithium-ion batteries

The world is facing an ever-growing global energy crisis with unprecedented depth and complexity.The sustainable development of high energy density lithium-ion batteries for electric vehicles and portable electric devices has become a feasible way to deal with this problem.Silicon suboxides(SiO_(x))have been deemed as one of the most promising anode materials because of their ultrahigh theoretical lithium storage capacity,proper working potential,natural abundance,and environmental friendliness.However,the mass utilization of SiO_(x)-based anodes is severely obstructed by their low electrical conductivity and inevitable volume expansion.While lithium silicate and lithium oxide formed in the first lithiation process act as buffer layers to some extent,it is urgent to address the accompanying low initial Coulombic efficiency and unsatisfactory cycling stability.In this review,we summarized recent advances in the synthesis methods of SiO_(x)-based materials.Besides,the benefits and shortcomings of the various methods are briefly concluded.Then,we discussed the effective combination of SiO_(x) with carbon materials and designs of porous structure,which could considerably enhance the electrochemical performance in detail.Furthermore,progresses on the modified strategies,advanced characteristics and industrial applications for SiO_(x)-based anodes are also mentioned.Finally,the remaining challenges encountered and future perspectives on SiO_(x)-based anodes are highlighted.

Microstructure and Mechanical Properties of AZ31 Mg Alloy Fabricated by Pre-compression and Frustum Shearing Extrusion

The AZ31 Mg alloys were processed by 6% pre-compression and frustum shearing extrusion at various temperatures, and the microstructure, texture and mechanical properties of the resulting alloys are systematically investigated. The results show that the grain size monotonically increases from 6.4 to 12.6 lm and the texture intensity increases from 6.7 to 9.6with the increase in the extrusion temperature. The combining effect of the pre-twinning and the frustum shearing deformation is found to contribute to the development of the weak basal texture in Mg alloys. The Mg alloy sheet produced at the extrusion temperature of 563 K exhibits excellent mechanical properties. The yield strength, ultimate tensile strength and elongation for the extruded alloys are 189.6 MPa, 288.4 MPa and 24.9%, respectively. Such improved mechanical properties are comparable or even superior to those of the alloys subjected to other deformation techniques, rendering the pre-compression and frustum shearing extrusion a promising way for further tailoring properties of Mg alloys.

Novel intelligent devices: Two-dimensional materials based memristors

Two-dimensional(2D)materials with atomic thickness,non-volatile resistive switching feature and compatibility with the semiconducting technology are naturally a good media of memristors.2D materials-based memristors with excellent performance,low-power consumption and high integration density can be integrated with other circuit components to implement the complicate logic computing,which will become a key driving force for the development of artificial intelligence.

Three-dimensional graphene and its composite for gas sensors

As a two-dimensional(2D)material,graphene shows excellent advantages in the field of gas sensors due to its inherent large specific surface area and unique electrical properties.However,in the practical application of gas detection,graphene sheet is easy to form irreversible agglomeration and has some limitations such as low sensitivity,long response time and slow recovery speed,which greatly reduce its gas sensing performance.As a gas sensing material,three-dimensional(3D)porous graphene has been extensively studied in recent years owing to its larger specific surface area and stable structure.In order to synthesize graphene with different three-dimensional structures,many methods have been developed.Herein,the synthesis and assembly of three-dimensional graphene and its composites were reviewed,with emphasis on the application of three-dimensional graphene and its composites in the field of gas sensors.The challenges and development prospects of three-dimensional graphene materials in the application of gas sensors were briefly described.

Conformal and continuous deposition of bifunctional cobalt phosphide layers on p-silicon nanowire arrays for improved solar hydrogen evolution

Vertically aligned p-silicon nanowire （SiNW） arrays have been extensively investigated in recent years as promising photocathodes for solar-driven hydrogen evolution. However, the fabrication of SiNW photocathodes with both high photoelectrocatalytic activity and long-term operational stability using a simple and affordable approach is a challenging task. Herein, we report conformal and continuous deposition of a di-cobalt phosphide （C02P） layer on lithography- patterned highly ordered SiNW arrays via a cost-effective drop-casting method followed by a low-temperature phosphorization treatment. The as-deposited C02P layer consists of crystalline nanoparticles and has an intimate contact with SiNWs, forming a well-defined SiNW@Co2P core/shell nanostructure. The conformal and continuous Co2P layer functions as a highly efficient catalyst capable of substantially improving the photoelectrocatalytic activity for the hydrogen evolution reaction （HER） and effectively passivates the SiNWs to protect them from photo-oxidation, thus prolonging the lifetime of the electrode. As a consequence, the SiNW@Co2P photocathode with an optimized C02P layer thickness exhibits a high photocurrent density of -21.9 mA·cm^-2 at 0 V versus reversible hydrogen electrode and excellent operational stability up to 20 h for solar-driven hydrogen evolution, outperforming many nanostructured silicon photocathodes reported in the literature. The combination of passivation and catalytic functions in a single continuous layer represents a promising strategy for designing high-performance semiconductor photoelectrodes for use in solar-driven water splitting, which may simplify fabrication procedures and potentially reduce production costs.