Recent advances in cobalt phosphide-based materials for electrocatalytic water splitting:From catalytic mechanism and synthesis method to optimization design

Electrochemical water splitting has long been considered an effective energy conversion technology for trans-ferring intermittent renewable electricity into hydrogen fuel,and the exploration of cost-effective and high-performance electrocatalysts is crucial in making electrolyzed water technology commercially viable.Cobalt phosphide(Co-P)has emerged as a catalyst of high potential owing to its high catalytic activity and durability in water splitting.This paper systematically reviews the latest advances in the development of Co-P-based materials for use in water splitting.The essential effects of P in enhancing the catalytic performance of the hydrogen evolution reaction and oxygen evolution reaction are first outlined.Then,versatile synthesis techniques for Co-P electrocatalysts are summarized,followed by advanced strategies to enhance the electrocatalytic performance of Co-P materials,including heteroatom doping,composite construction,integration with well-conductive sub-strates,and structure control from the viewpoint of experiment.Along with these optimization strategies,the understanding of the inherent mechanism of enhanced catalytic performance is also discussed.Finally,some existing challenges in the development of highly active and stable Co-P-based materials are clarified,and pro-spective directions for prompting the wide commercialization of water electrolysis technology are proposed.

Recent advances in transition metal phosphide materials:Synthesis and applications in supercapacitors

Supercapacitors(SCs)are considered promising energy storge systems because of their outstanding power density,fast charge and discharge rate and long-term cycling stability.The exploitation of cheap and efficient electrode materials is the key to improve the performance of supercapacitors.As the battery-type materials,transition metal phosphides(TMPs)possess high theoretical specific capacity,good electrical conductivity and superior structural stability,which have been extensively studied to be electrode materials for supercapacitors.In this review,we summarize the up-to-date progress on TMPs materials from diversified synthetic methods,diverse nanostructures and several prominent TMPs and their composites in application of supercapacitors.In the end,we also propose the remaining challenges toward the rational discovery and synthesis of high-performance TMP electrodes materials for energy storage.

A dynamic database of solid-state electrolyte(DDSE)picturing all-solid-state batteries

All-solid-state batteries(ASSBs)are a class of safer and higher-energy-density materials compared to conventional devices,from which solid-state electrolytes(SSEs)are their essential components.To date,investigations to search for high ion-conducting solid-state electrolytes have attracted broad concern.However,obtaining SSEs with high ionic conductivity is challenging due to the complex structural information and the less-explored structure-performance relationship.To provide a solution to these challenges,developing a database containing typical SSEs from available experimental reports would be a new avenue to understand the structureperformance relationships and find out new design guidelines for reasonable SSEs.Herein,a dynamic experimental database containing>600 materials was developed in a wide range of temperatures(132.40–1261.60 K),including mono-and divalent cations(e.g.,Li^(+),Na^(+),K^(+),Ag^(+),Ca^(2+),Mg^(2+),and Zn^(2+))and various types of anions(e.g.,halide,hydride,sulfide,and oxide).Data-mining was conducted to explore the relationships among different variates(e.g.,transport ion,composition,activation energy,and conductivity).Overall,we expect that this database can provide essential guidelines for the design and development of high-performance SSEs in ASSB applications.This database is dynamically updated,which can be accessed via our open-source online system.

Phase composition,conductivity,and sensor properties of cerium-doped indium oxide

The hydrothermal synthesis of In_(2)O_(3)and CeO_(2)–In_(2)O_(3)is investigated as well as the properties of sensor layers based on these compounds.During the synthesis of In_(2)O_(3),intermediate products In(OH)_(3)and InOOH are formed,which are the precursors of stable cubic(c-In_(2)O_(3))and metastable rhombohedral(rh-In_(2)O_(3))phases,respectively.A transition from c-In_(2)O_(3)to rh-In_(2)O_(3)is observed with the addition of CeO_(2).The introduction of cerium into rh-In_(2)O_(3)results in a decrease in the sensor response to hydrogen,while it increases in composites based on c-In_(2)O_(3).The data on the sensor activity of the composites correlate with XPS results in which CeO_(2)causes a decrease in the concentrations of chemisorbed oxygen and oxygen vacancies in rh-In_(2)O_(3).The reverse situation is observed in composites based on c-In_(2)O_(3).Compared to In_(2)O_(3)and CeO_(2)–In_(2)O_(3)obtained by other methods,the synthesized composites demonstrate maximum response to H_(2)at low temperatures by 70–100℃,and have short response time(0.2–0.5 s),short recovery time(6–7 s),and long-term stability.A model is proposed for the dependence of sensitivity on the direction of electron transfer between In_(2)O_(3)and CeO_(2).

Tuning the reactivity of TiO_(2)layer with uniform distribution of Sub-5 nm Fe_(2)O_(3)particles via in situ voltage-assisted oxidation for robust catalytic reduction

The trade-off between efficiency and stability has limited the application of TiO_(2)as a catalyst due to its poor surface reactivity.Here,we present a modification of a TiO_(2)layer with highly stable Sub-5 nm Fe_(2)O_(3)nanoparticles(NP)by modulating its structure-surface reactivity relationship to attain efficiency-stability balance via a voltage-assisted oxidation approach.In situ simultaneous oxidation of the Ti substrate and Fe precursor using high-energy plasma driven by high voltage resulted in uniform distribution of Fe_(2)O_(3)NP embedded within porous TiO_(2)layer.Comprehensive surface characterizations with density functional theory demonstrated an improved electronic transition in TiO_(2)due to the presence of surface defects from reactive oxygen species and possible charge transfer from Ti to Fe;it also unexpectedly increased the active site in the TiO_(2)layer due to uncoordinated electrons in Sub-5 nm Fe_(2)O_(3)NP/TiO_(2)catalyst,thereby enhancing the adsorption of chemical functional groups on the catalyst.This unique embedded structure exhibited remarkable improvement in reducing 4-nitrophenol to 4-aminophenol,achieving approximately 99%efficiency in 20 min without stability decay after 20 consecutive cycles,outperforming previously reported TiO_(2)-based catalysts.This finding proposes a modified-electrochemical strategy enabling facile construction of TiO_(2)with nanoscale oxides extandable to other metal oxide systems.

Experimental and computational study of annealed nickel sulfide quantum dots for catalytic and antibacterial activity

This research investigates the hydrothermal synthesis and annealing duration effects on nickel sulfide(NiS_(2) quantum dots(QDs)for catalytic decolorization of methylene blue(MB)dye and antimicrobial efficacy.QD size increased with longer annealing,reducing catalytic activity.UV–vis,XRD,TEM,and FTIR analyses probed optical structural,morphological,and vibrational features.XRD confirmed NiS2's anorthic structure,with crystallite size growing from 6.53 to 7.81 nm during extended annealing.UV–Vis exhibited a bathochromic shift,reflecting reduced band gap energy(Eg)in NiS_(2).TEM revealed NiS_(2)QD formation,with agglomerated QD average size increasing from 7.13 to 9.65 nm with prolonged annealing.Pure NiS_(2) showed significant MB decolorization(89.85%)in acidic conditions.Annealed NiS_(2) QDs demonstrated notable antibacterial activity,yielding a 6.15mm inhibition zone against Escherichia coli(E.coli)compared to Ciprofloxacin.First-principles computation supported a robust interaction between MB and NiS_(2),evidenced by obtained adsorption energies.This study highlights the nuanced relationship between annealing duration,structural changes,and functional properties in NiS_(2)QDs,emphasizing their potential applications in catalysis and antibacterial interventions.

Electronic properties of 2D materials and their junctions

With an extensive range of distinctive features at nano meter-scale thicknesses,two-dimensional(2D)materials drawn the attention of the scientific community.Despite tremendous advancements in exploratory research on 2D materials,knowledge of 2D electrical transport and carrier dynamics still in its infancy.Thus,here we highlighted the electrical characteristics of 2D materials with electronic band structure,electronic transport,dielectric constant,carriers mobility.The atomic thinness of 2D materials makes substantially scaled field-effect transistors(FETs)with reduced short-channel effects conceivable,even though strong carrier mobility required for high performance,low-voltage device operations.We also discussed here about factors affecting 2D materials which easily enhanced the activity of those materials for various applications.Presently,Those 2D materials used in state-of-the-art electrical and optoelectronic devices because of the extensive nature of their electronic band structure.2D materials offer unprecedented freedom for the design of novel p-n junction device topologies in contrast to conventional bulk semiconductors.We also,describe the numerous 2D p-n junctions,such as homo junction and hetero junction including mixed dimensional junctions.Finally,we talked about the problems and potential for the future.

Application of artificial synapse based on all-inorganic perovskite memristor in neuromorphic computing

Artificial synapse inspired by the biological brain has great potential in the field of neuromorphic computing and artificial intelligence.The memristor is an ideal artificial synaptic device with fast operation and good tolerance.Here,we have prepared a memristor device with Au/CsPbBr_(3)/ITO structure.The memristor device exhibits resistance switching behavior,the high and low resistance states no obvious decline after 400 switching times.The memristor device is stimulated by voltage pulses to simulate biological synaptic plasticity,such as long-term potentiation,long-term depression,pair-pulse facilitation,short-term depression,and short-term potentiation.The transformation from short-term memory to long-term memory is achieved by changing the stimulation frequency.In addition,a convolutional neural network was constructed to train/recognize MNIST handwritten data sets;a distinguished recognition accuracy of~96.7%on the digital image was obtained in 100 epochs,which is more accurate than other memristor-based neural networks.These results show that the memristor device based on CsPbBr3 has immense potential in the neuromorphic computing system.

Low-temperature replacement construction of three-dimensional corrosion-resistant interface for deeply rechargeable Zn metal batteries

Aqueous Zn batteries are promising candidates for grid-scale renewable energy storage.Foil electrodes have been widely investigated and applied as anode materials for aqueous Zn batteries,however,they suffer from limited surface area and severe interfacial issues including metallic dendrites and corrosion side reactions,limiting the depth of discharge(DOD)of the foil electrode materials.Herein,a low-temperature replacement reaction is utilized to in-situ construct a three-dimensional(3D)corrosion-resistant interface for deeply rechargeable Zn foil electrodes.Specifically,the deliberate low-temperature environment controlled the replacement rate between polycrystalline Zn metal and oxalic acid,producing a Zn foil electrode with distinct 3D corrosion-resistant interface(3DCI-Zn),which differed from conventional two-dimensional(2D)protective structure and showed an order of magnitude higher surface area.Consequently,the 3DCI-Zn electrode exhibited dendrite-free and anticorrosion properties,and achieved stable plating/stripping performance for 1000 h at 10 mA cm^(-2)and 10 mAh cm^(-2)with a remarkable DOD of 79%.After pairing with a MnO2cathode with a high areal capacity of 4.2 mAh cm^(-2),the pouch cells delivered 168 Wh L^(-1)and a capacity retention of 89.7%after 100 cycles with a low negative/positive(N/P)ratio of 3:1.

Mechanical behavior of nanorubber reinforced epoxy over a wide strain rate loading

Nanorubber/epoxy composites containing 0,2,6 and 10 wt%nanorubber are subjected to uniaxial compression over a wide range of strain rate from 8×10^(-4) s^(-1) to~2×10^(4) s^(-1).Unexpectedly,their strain rate sensitivity and strain hardening index increase with increasing nanorubber content.Potential mechanisms are proposed based on numerical simulations using a unit cell model.An increase in the strain rate sensitivity with increasing nanorubber content results from the fact that the nanorubber becomes less incompressible at high strain,generating a higher hydro-static pressure.Adiabatic shear localization starts to occur in the epoxy under a strain rate of 22,000 s^(-1) when the strain exceeds 0.35.The presence of nanorubber in the epoxy reduces adiabatic shear localization by preventing it from propagating.

Extrusion 3D printing of carbon nanotube-assembled carbon aerogel nanocomposites with high electrical conductivity

Carbon nanotubes(CNTs)with high aspect ratio and excellent electrical conduction offer huge functional improvements for current carbon aerogels.However,there remains a major challenge for achieving the on-demand shaping of carbon aerogels with tailored micro-nano structural textures and geometric features.Herein,a facile extrusion 3D printing strategy has been proposed for fabricating CNT-assembled carbon(CNT/C)aerogel nanocomposites through the extrusion printing of pseudoplastic carbomer-based inks,in which the stable dispersion of CNT nanofibers has been achieved relying on the high viscosity of carbomer microgels.After extrusion printing,the chemical solidification through polymerizing RF sols enables 3D-printed aerogel nanocomposites to display high shape fidelity in macroscopic geometries.Benefiting from the micro-nano scale assembly of CNT nanofiber networks and carbon nanoparticle networks in composite phases,3D-printed CNT/C aerogels exhibit enhanced mechanical strength(fracture strength,0.79 MPa)and typical porous structure characteristics,including low density(0.220 g cm^(-3)),high surface area(298.4 m^(2)g^(-1)),and concentrated pore diameter distribution(~32.8nm).More importantly,CNT nanofibers provide an efficient electron transport pathway,imparting 3D-printed CNT/C aerogel composites with a high electrical conductivity of 1.49 S cm^(-1).Our work would offer feasible guidelines for the design and fabrication of shape-dominated functional materials by additive manufacturing.

Facile electrochemical surface-alloying and etching of Au wires to enable high-performance substrates for surface enhanced Raman scattering

Surface-enhanced Raman Spectroscopy(SERS)is a nondestructive technique for rapid detection of analytes even at the single-molecule level.However,highly sensitive and reliable SERS substrates are mostly fabricated with complex nanofabrication techniques,greatly restricting their practical applications.A convenient electrochemical method for transforming the surface of commercial gold wires/foils into silver-alloyed nanostructures is demonstrated in this report.Au substrates are treated with repetitive anodic and cathodic bias in an electrolyte of thiourea,in a one-pot one-step manner.X-rays absorption fine structure(XAFS)spectroscopy confirms that the AuAg alloy is induced at the surface.The unique AuAg alloyed surface nanostructures are particularly advantageous when served as SERS substrates,enabling a remarkably sensitive detection of Rhodamine B(a detection limit of 10^(-14)M,and uniform strong response throughout the substrates at 10^(-12)M).

Effects of surface chlorine atoms on charge distribution and reaction barriers for photocatalytic CO_(2)reduction

Photocatalytic CO_(2)reduction to produce high value-added carbon-based fuel has been proposed as a promising approach to mitigate global warming issues.However,the conversion efficiency and product selectivity are still low due to the sluggish dynamics of transfer processes involved in proton-assisted multi-electron reactions.Lowering the formation energy barriers of intermediate products is an effective method to enhance the selectivity and productivity of final products.In this study,we aim to regulate the surface electronic structure of Bi_(2)WO_(6)by doping surface chlorine atoms to achieve effective photocatalytic CO_(2)reduction.Surface Cl atoms can enhance the absorption ability of light,affect its energy band structure and promote charge separation.Combined with DFT calculations,it is revealed that surface Cl atoms can not only change the surface charge distribution which affects the competitive adsorption of H_(2)O and CO_(2),but also lower the formation energy barrier of intermediate products to generate more intermediate*COOH,thus facilitating CO production.Overall,this study demonstrates a promising surface halogenation strategy to enhance the photocatalytic CO_(2)reduction activity of a layered structure Bi-based catalyst.

Controllable large-scale processing of temperature regulating sheath-core fibers with high-enthalpy for thermal management

Temperature regulating fibers(TRF_(s)) with high enthalpy and high form stability are the key factors for thermal management. However, the enthalpies of most TRFsare not high, and the preparation methods are still at the laboratory scale. It remains a great challenge to use industrial spinning equipment to achieve continuous processing of TRF_(s) with excellent thermal and mechanical properties. Here, polyamide 6(PA6) based TRF_(s) with a sheath-core structure were prepared by bicomponent melt-spinning. The sheath-core TRF(TRF_(sc)) are composed of PA6 as sheath and functional PA6 as core, which are filled with the shape stable phase change materials(ssPCM),dendritic silica@polyethylene glycol(SiO_(2)@PEG). With the aid of the sheath structure, the filling content of SiO_(2)@PEG can reach 30 %, so that the enthalpy of the TRF_(s) can be as high as 21.3 J/g. The ultra-high enthalpy guarantees the temperature regulation ability during the alternating process of cooling and heating. In hot environment, the temperature regulation time is 6.59 min, and the temperature difference is 12.93℃. In addition, the mechanical strength of the prepared TRF_(sc) reaches 2.26 cN/dtex, which can fully meet its application in the field of thermal management textiles and devices to manage the temperature regulation of the human body or precision equipment, etc.

A simple atomization approach enables monolayer dispersion of nano graphenes in cementitious composites with excellent strength gains

Carbon nano additives(CNAs)are critical to achieving the unique properties of functionalized composites,however,controlling the dispersion of CNAs in material matrix is always a challenging task.In this study,a simple atomization approach was successfully developed to promote the dispersion efficiency of graphene nanoplatelets(GNPs)in cement composites.This atomization approach can be integrated with the direct,indirect and combined ultrasonic stirrings in a homemade automatic stirring-atomization device.Mechanical and microstructure tests were performed on hardened cement pastes blended with GNPs in different stirring and mixing approaches.Results show that the direct ultrasonic stirrings enabled more homogeneous dispersions of GNP particles with a smaller size for a longer duration.The atomized droplets with the mean size of~100μm largely mitigated GNPs’agglomerations.Monolayer GNPs were observed in the cement matrix with the strength gain by up to 54%,and the total porosity decrease by 21%in 0.3 wt%GNPs dosage.The greatly enhanced dispersion efficiency of GNPs in cement also raised the cement hydration.This work provides an effective and manpower saving technique toward dispersing CNAs in engineering materials with great industrialization prospects.

Double enzyme mimetic activities of multifunctional Ag nanoparticle-decorated Co_(3)V_(2)O_(8)hollow hexagonal prismatic pencils for application in colorimetric sensors and disinfection

Since the catalytic activity of most nanozymes is still far lower than the corresponding natural enzymes,there is urgent need to discover novel highly efficient enzyme-like materials.In this work,Co_(3)V_(2)O_(8)with hollow hexagonal prismatic pencil structures were prepared as novel artificial enzyme mimics.They were then decorated by photo-depositing Ag nanoparticles(Ag NPs)on the surface to further improve its catalytic activities.The Ag NPs decorated Co_(3)V_(2)O_(8)(ACVPs)showed both excellent oxidase-and peroxidase-like catalytic activities.They can oxidize the colorless 3,3’,5,5’-tetramethylbenzidine rapidly to induce a blue change.The enhanced enzyme mimetic activities can be attributed to the surface plasma resonance(SPR)effect of Ag NPs as well as the synergistic catalytic effect between Ag NPs and Co_(3)V_(2)O_(8),accelerating electron transfer and promoting the catalytic process.ACVPs were applied in constructing a colorimetric sensor,validating the occurrence of the Fenton reaction,and disinfection,presenting favorable catalytic performance.The enzyme-like catalytic mechanism was studied,indicating the chief role of⋅O_(2)-radicals in the catalytic process.This work not only discovers a novel functional material with double enzyme mimetic activity but also provides a new insight into exploiting artificial enzyme mimics with highly efficient catalytic ability.

CuO–TiO_(2) based self-powered broad band photodetector

An efficient room-temperature self-powered,broadband(300 nm–1100 nm)photodetector based on a CuO–TiO_(2)/TiO_(2)/p-Si(100)heterostructure is demonstrated.The CuO–TiO_(2)nanocomposites were grown in a two-zone horizontal tube furnace on a 40 nm TiO_(2)thin film deposited on a p-type Si(100)substrate.The CuO–TiO_(2)/TiO_(2)/p-Si(100)devices exhibited excellent rectification characteristics under dark and individual photoillumination conditions.The devices showed remarkable photo-response under broadband(300–1100 nm)light illumination at zero bias voltage,indicating the achievement of highly sensitive self-powered photodetectors at visible and near-infrared light illuminations.The maximum response of the devices is observed at 300 nm for an illumination power of 10 W.The response and recovery times were calculated as 86 ms and 78 ms,respectively.Moreover,under a small bias,the devices showed a prompt binary response by altering the current from positive to negative under illumination conditions.The main reason behind this binary response is the low turn-on voltage and photovoltaic characteristics of the devices.Under illumination conditions,the generation of photocurrent is due to the separation of photogenerated electron-hole pairs within the built-in electric field at the CuO–TiO_(2)/TiO_(2)interface.These characteristics make the CuO–TiO_(2)/TiO_(2)broadband photodetectors suitable for applications that require high response speeds and self-sufficient functionality.

A novel“Snowflake”--rGO-CuO for ultrasonic degradation of rhodamine and methyl orange

Graphene-doped CuO(rGO-CuO)nanocomposites with flower shapes were prepared by an improved solvothermal method.The samples were characterized by X-ray diffraction,X-ray photoelectron spectroscopy and UV–visible spectroscopy.The active species in the degradation reaction of rGO-CuO composites under ultrasonic irradiation were detected by electron paramagnetic resonance.On the basis of comparative experiments,the photodegradation mechanisms of two typical dyes,Rhodamine B(Rh B)and methyl orange(MO),were proposed.The results demonstrated that the doped CuO could improve the degradation efficiency.The catalytic degradation efficiency of rGO-CuO(2:1)to rhodamine B(RhB)and methyl orange(MO)reached 90%and 87%respectively,which were 2.1 times and 4.4 times of the reduced graphene oxide.Through the first-principles and other theories,we give the reasons for the enhanced catalytic performance of rGO-CuO:combined with internal and external factors,rGO-CuO under ultrasound could produce more hole and active sites that could interact with the OH·in pollutant molecules to achieve degradation.The rGO-CuO nanocomposite has a simple preparation process and low price,and has a high efficiency of degrading water pollution products and no secondary pollution products.It has a low-cost and high-efficiency application prospect in water pollution industrial production and life.

Novel sandwich structured glass fiber Cloth/Poly(ethylene oxide)-MXene composite electrolyte

Recently,poly(ethylene oxide)(PEO)-based solid polymer electrolytes have been attracting great attention,and efforts are currently underway to develop PEO-based composite electrolytes for next generation high performance all-solid-state lithium metal batteries.In this article,a novel sandwich structured solid-state PEO composite electrolyte is developed for high performance all-solid-state lithium metal batteries.The PEO-based composite electrolyte is fabricated by hot-pressing PEO,LiTFSI and Ti_(3)C_(2)T_(x) MXene nanosheets into glass fiber cloth(GFC).The as-prepared GFC@PEO-MXene electrolyte shows high mechanical properties,good electrochemical stability,and high lithium-ion migration number,which indicates an obvious synergistic effect from the microscale GFC and the nanoscale MXene.Such as,the GFC@PEO-1 wt%MXene electrolyte shows a high tensile strength of 43.43 MPa and an impressive Young's modulus of 496 MPa,which are increased by 1205%and 6048%over those of PEO.Meanwhile,the ionic conductivity of GFC@PEO-1 wt%MXene at 60℃ reaches 5.01×10^(-2) S m^(-1),which is increased by around 200%compared with that of GFC@PEO electrolyte.In addition,the Li/Li symmetric battery based on GFC@PEO-1 wt%MXene electrolyte shows an excellent cycling stability over 800 h(0.3 mA cm^(-2),0.3 mAh cm^(-2)),which is obviously longer than that based on PEO and GFC@PEO electrolytes due to the better compatibility of GFC@PEO-1 wt%MXene electrolyte with Li anode.Furthermore,the solid-state Li/LiFePO_(4) battery with GFC@PEO-1 wt%MXene as electrolyte demonstrates a high capacity of 110.2–166.1 mAh g^(-1) in a wide temperature range of 25–60C,and an excellent capacity retention rate.The developed sandwich structured GFC@PEO-1 wt%MXene electrolyte with the excellent overall performance is promising for next generation high performance all-solid-state lithium metal batteries.

Recent advances in graphene-based phase change composites for thermal energy storage and management

Energy storage and conservation are receiving increased attention due to rising global energy demands.Therefore,the development of energy storage materials is crucial.Thermal energy storage(TES)systems based on phase change materials(PCMs)have increased in prominence over the past two decades,not only because of their outstanding heat storage capacities but also their superior thermal energy regulation capability.However,issues such as leakage and low thermal conductivity limit their applicability in a variety of settings.Carbon-based materials such as graphene and its derivatives can be utilized to surmount these obstacles.This study examines the recent advancements in graphene-based phase change composites(PCCs),where graphene-based nanostructures such as graphene,graphene oxide(GO),functionalized graphene/GO,and graphene aerogel(GA)are incorporated into PCMs to substantially enhance their shape stability and thermal conductivity that could be translated to better storage capacity,durability,and temperature response,thus boosting their attractiveness for TES systems.In addition,the applications of these graphene-based PCCs in various TES disciplines,such as energy conservation in buildings,solar utilization,and battery thermal management,are discussed and summarized.