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.

Formation and transformation of metastable LPSO building blocks clusters in Mg-Gd-Y-Zn-Zr alloys by spinodal decomposition and heterogeneous nucleation

To study the formation and transformation mechanism of long-period stacked ordered(LPSO)structures,a systematic atomic scale analysis was conducted for the structural evolution of long-period stacked ordered(LPSO)structures in the Mg-Gd-Y-Zn-Zr alloy annealed at 300℃~500℃.Various types of metastable LPSO building block clusters were found to exist in alloy structures at different temperatures,which precipitate during the solidification and homogenization process.The stability of Zn/Y clusters is explained by the first principles of density functional theory.The LPSO structure is distinguished by the arrangement of its different Zn/Y enriched LPSO structural units,which comprises local fcc stacking sequences upon a tightly packed plane.The presence of solute atoms causes local lattice distortion,thereby enabling the rearrangement of Mg atoms in the different configurations in the local lattice,and local HCP-FCC transitions occur between Mg and Zn atoms occupying the nearest neighbor positions.This finding indicates that LPSO structures can generate necessary Schockley partial dislocations on specific slip surfaces,providing direct evidence of the transition from 18R to 14H.Growth of the LPSO,devoid of any defects and non-coherent interfaces,was observed separately from other precipitated phases.As a result,the precipitation sequence of LPSO in the solidification stage was as follows:Zn/Ycluster+Mg layers→various metastable LPSO building block clusters→18R/24R LPSO;whereas the precipitation sequence of LPSO during homogenization treatment was observed to be as follows:18R LPSO→various metastable LPSO building block clusters→14H LPSO.Of these,14H LPSO was found to be the most thermodynamically stable structure.

Effect of FeSi additive in dual-chamber sample cup on thermal analysis characteristic values and vermiculating rate of compacted graphite iron

Thermal analysis plays a key role in the online inspection of molten iron quality.Different solidification process of molten iron can be reflected by thermal analysis curves,and silicon is one of important elements affecting the solidification of molten iron.In this study,FeSi75 was added in one chamber of the dual-chamber sample cup,and the influences of FeSi75 additive on the characteristic values of thermal analysis curves and vermiculating rate were investigated.The results show that with the increase of FeSi75,the start temperature of austenite formation TALfirstly decreases and then increases,but the start temperature of eutectic growth TSEF,the lowest eutectic temperature TEU,temperature at maximum eutectic reaction rate TEM,and highest eutectic temperature TERkeep always an increase.The temperature at final solidification point TEShas little change.The FeSi75 additive has different influences on the vermiculating rate of molten iron with different vermiculation,and the vermiculating rate increases for lower vermiculation molten iron while decreases for higher one.According to the thermal analysis curves obtained by a dual-chamber sample cup with 0.30wt.%FeSi75 additive in one chamber,the vermiculating rate of molten iron can be evaluated by comparing the characteristic values of these curves.The time differenceΔtERcorresponding to the highest eutectic temperature TERhas a closer relationship with the vermiculating rate,and a parabolic regression curve between the time differenceΔtERand vermiculating rateηhas been obtained within the range of 65%to 95%,which is suitable for the qualified melt.

Effect of In doping on the evolution of microstructure,magnetic properties and corrosion resistance of NdFeB magnets

The grain boundary phase affects the magnetic properties and corrosion resistance of sintered NdFeB magnets.In this work,a small amount of In was added to NdFeB magnets by induction melting to systematically investigate its effect on the evolution of the microstructure,magnetic properties and corrosion resistance of NdFeB magnets.Microstructural analysis illustrated that minor In addition generated more grain boundary phases and an abundant amorphous phase at the triple-junction grain boundary.While the addition of In failed to enhance the magnetic isolation effect between adjacent matrix grains,its incorporation fortuitously elevated the electrochemical potential of the In-containing magnets.Besides,during corrosion,an In-rich precipitate phase formed,hindering the ingress of the corrosive medium into the magnet.Consequently,this significantly bolstered the corrosion resistance of the sintered NdFeB magnets.The phase formation,magnetic properties and corrosion resistance of In-doped NdFeB magnets are detailed in this work,which provides new prospects for the preparation of high-performance sintered NdFeB magnets.

Instant formation of excellent oxygen evolution catalyst film via controlled spray pyrolysis for electrocatalytic and photoelectrochemical water splitting

The retarded kinetics of oxygen evolution on electrodes is a bottleneck for electrochemical energy conversion and storage systems.NiFe-based electrocatalysts provide a cost-effective choice to confront this challenge.However,there is a lack of facile techniques for depositing compact catalytic films of high coverage and possessing a state-of-the-art performance,which is especially desired in photoelectrochemical(PEC)systems.Herein,we demonstrate a spray pyrolysis(SP)route to address this issue,featuring the kinetic selective preparation towards the desired catalytic-active material.Differing from reported SP protocols which only produce inactive oxides,this approach directly generates a unique composite film consisting of NiFe layered oxyhydroxides and amorphous oxides,exhibiting an overpotential as small as 255 mV(10 mA cm^(−2))and a turnover frequency of∼0.4 s^(−1)per metal atom.By using such a facile protocol,the surface rate-limiting issue of BiVO_(4)photoanodes can be effectively resolved,resulting in a charge injection efficiency of over 90%.Considering this deposition directly start from simple nitrates but only takes several seconds to complete,we believe it can be developed as a widely applicable and welcomed functionalization technique for diverse electrochemical devices.

Science Letters; In-situ synthesis and luminescence properties of titanium oxide gels containing 1,10-phenanthroline europium(Ⅲ) complex

It is difficult to directly dope europium complexes in gel because the excessive water or high acidic condition may lead to their decomposition. We prepared a novel homogeneous TiO2 gel containing Eu-phen complexes by using an in-situ synthesis method. The formation of Eu-phen complexes in sol-gel derived TiO2 was confirmed by luminescence excitation spectra. The effects of temperature and aging time on in-situ synthesis are discussed. The luminescence spectra of gel containing europium complexes were also compared with the pure Eu-phen complexes.

Effect of CeO_(2)doping on the coercivity of 2:17 type SmCo magnets

The effects of CeO_(2)doping on the magnetic properties and microstructure of 2:17 type SmCo magnets are studied.With the increase of CeO_(2)from 0 wt.%to 3 wt.%,the coercivity of the magnets increases from 22.22 kOe to over 29.37 kOe,which is an increase of more than 30%.When the doping content is lower than 1 wt.%,the remanence and magnetic energy product of the magnets remain almost constant.Both decrease sharply as the doping concentration further increases.After CeO_(2)doping,the oxide content in the magnet increases significantly and the Ce element is uniformly distributed in the magnet.Observing the magnetic domains reveals that doping with CeO_(2)can refine the magnetic domains and make the magnetic domain wall more stable,resulting in a significant increase in the coercivity of the magnets.

Effect of compound treatment of rotating magnetic field and Al-5Ti-1B refiner on microstructure and properties of Al-5Cu alloy

The Al-5Cu alloys were prepared by different treatment methods,including adding a refiner Al-5Ti-1B,exerting a rotating magnetic field(RMF),and compound treatment of both refiner and RMF.The effects of treatment methods on the microstructure,properties,and solid solubility of the Al-5Cu alloy were investigated.The optimal magnetic field parameters and addition amount of refiner were confirmed by experiment.Results show that either RMF or adding refiner Al-5Ti-1B alone can refine the grain size,and the refining effect can be further improved by a compound refining treatment with optimized magnetic field parameters(120 A current and 8 Hz frequency) and 1.0wt.% Al-5Ti-1B refiner(RMF*+Al-5Ti-1B*).The average grain size is decreased to 68.1 μm,which is 60.8%,21.1%,and 83.5% lower than that of the alloy treated by the optimized rotating magnetic field,the Al-5Ti-1B refiner,and the alloy without any treatment,respectively.The tensile strength and elongation of the alloy reach 232.5 MPa and 18.6%,respectively,which are obviously higher than those of the alloys treated by rotating magnetic field,Al-5Ti-1B refiner,and the alloy without any treatment,respectively.Additionally,the solid solubility of the alloy is also obviously improved compared to the alloys treated by other methods.

Coercivity enhancement of sintered Nd–Fe–B magnets by grain boundary diffusion with Pr_(80-x)Al_(x)Cu_(20)alloys

A grain boundary diffusion(GBD)process with Pr_(80-x)Al_(x)Cu_(20)(x=0,10,15,20)low melting point alloys was applied to commercial 42M sintered Nd–Fe–B magnets.The best coercivity enhancement of a diffused magnet was for the Pr_(65)Al_(15)Cu_(20)GBD magnet,from 16.38 kOe to 22.38 kOe.Microstructural investigations indicated that increase in the Al content in the diffusion source can form a continuous grain boundary(GB)phase,optimizing the microstructure to enhance the coercivity.The coercivity enhancement is mainly due to the formation of a continuous GB phase to separate the main phase grains.Exchange decoupling between the adjacent main phase grains is enhanced after the GBD process.Meanwhile,the introduction of Al can effectively promote the infiltration of Pr into the magnet,which increases the diffusion rate of rare-earth elements within a certain range.This work provides a feasible method to enhance coercivity and reduce the use of rare-earth resources by partial replacement of rare-earth elements with non-rare-earth elements in the diffusion source.

Bimetallic AgNi nanoparticles anchored onto MOF-derived nitrogen-doped carbon nanostrips for efficient hydrogen evolution

Hydrogen energy has long been recognized as a clean alternative to conventional fossil fuels,which can be applied in a wide range of transportation and power generation applications.The rational design and engineering of high-performance and robust catalysts for hydrogen evolution reaction(HER)shows not a great significance but a challenge for efficient electrochemical water splitting.Herein,a new type of Nibased Ni-ABDC precursor has been obtained,which leads to the formation of N-doped porous carbon nanomaterials uniformly coated with wellproportioned bimetallic AgNi alloys via a stepwise strategy.To their credit,all samples of AgNi/NC-X are structurally calcined from the pristine AgNi-ABDC-X by tuning the different concentration of AgNO3,which means all of them maintain the vermicelli-like morphology compared with Ni-ABDC.The series of AgNi/NC-X materials can be regarded as effective electrocatalysts for HER both in acidic and alkaline media,but an acid-leaching phenomenon is observed.Among them,the as-prepared AgNi/NC-2 exhibits a low overpotential of 103 mV at the current density of 10 mA cm^(-2)and decent durability with a high retention rate of 90.9%after 10 h in 1.0 mol L^(-1)KOH electrolyte.The compelling HER properties of AgNi/NC-2 can be attributed to the synergistic effect between the hierarchical carbon materials,partial N-doping and abundant AgNi alloys.Meanwhile,this study provides a practicable method for the development of efficient HER electrocatalysts for energy applications,which can be conveniently prepared through the reasonable introduction of active components in the crystalline inorganic-organic precursors.©2021 Institute of Process Engineering,Chinese Academy of Sciences.Publishing services by Elsevier B.V.on behalf of KeAi Communications Co.,Ltd.This is an open access article under the CC BY-NC-ND license(http://creativecommons.org/licenses/by-nc-nd/4.0/).

Transformation of Hexagonal Lu to Cubic LuH_(2+x)Single-Crystalline Films

With the recent report of near ambient superconductivity at room temperature in the N-doped lutetium hydride(Lu-H-N)system,the understanding of cubic Lu-H compounds has attracted worldwide attention.Generally,compared to polycrystals with non-negligible impurities,the single-crystalline form of materials with high purity can provide an opportunity to show their hidden properties.However,the experimental synthesis of single-crystalline cubic Lu-H compounds has not been reported so far.Here,we develop an easy way to synthesize highly pure LuH_(2+x)single-crystalline films by the post-annealing of Lu single-crystalline films(purity of 99.99%)in H_(2)atmosphere.The crystal and electronic structures of films were characterized by x-ray diffraction,Raman spectroscopy,and electrical transport.Interestingly,Lu films are silver-white and metallic,whereas their transformed LuH_(2+x)films become purple-red and insulating,indicating the possible formation of an unreported electronic state of Lu-H compounds.Our work provides a novel route to synthesize and explore more singlecrystalline Lu-H compounds.

Sm含量对挤压态Mg-6Al-2Sr合金组织及性能的影响

本文研究了不同Sm含量对挤压态Mg-6Al-2Sr合金的强化机理,采用金相实验、X射线衍射、扫描电镜和透射电镜对显微组织进行观察,并通过EBSD分析了Sm含量对合金显微组织的影响。本文主要是对不同Sm含量的Mg-6Al-2Sr铸态合金进行挤压实验。结果表明:随着Sm含量的增加,生成的Al_(2)Sm相在挤压的作用下破碎,并且沿挤压方向在晶界处均匀弥散,阻碍晶粒长大;继续不断增加Sm,使得在晶界处Al_(2)Sm相增多聚集,反而对合金力学性能产生不利影响;当Sm含量为1.5 wt%时,合金的平均晶粒尺寸最细小,其抗拉强度、屈服强度和伸长率达到297.9 MPa、257.8 MPa和21.3%,硬度达到HV78.9,较Sm含量为0 wt%的合金,抗拉强度提升了15.6%,屈服强度提升了34.6%,伸长率提升了34.8%。

衬板叠轧Mg/Al复合板基体组织演变优化强塑性机制

Mg/Al复合板兼并了镁合金的轻质性及铝合金的可塑性、耐腐蚀等性能,显著增强了其综合性能,但制造周期长、工艺要求高等不足制约了异质复合板成形技术的快速发展。为此,本文提出一种衬板辅助叠轧成形新方法。研究结果表明:3ARB时Mg/Al复合板抗拉强度可达235 MPa,伸长率为14.7%,镁板中出现明显的韧窝,呈韧性断裂特征,综合性能为最佳。由于此时Mg板基面滑移与非基面滑移同时开动,促进了动态再结晶的生成,此时Mg板再结晶比例为77.21%。随着累积叠轧的进行,大角度晶界增加和晶粒细化明显,原始晶粒已经基本破碎细化成等轴晶,Mg、Al基体硬度波动逐渐减小,复合板内部结构逐渐趋于稳定。本研究可为高性能异质复合板成形制造提供了一种新思路。

Structurally Flexible 2D Spacer for Suppressing the Electron-Phonon Coupling Induced Non-Radiative Decay in Perovskite Solar Cells

This study presents experimental evidence of the dependence of non-radiative recombination processes on the electron-phonon coupling of perovskite in perovskite solar cells(PSCs).Via A-site cation engineering,a weaker electron-phonon coupling in perovskite has been achieved by introducing the structurally soft cyclohexane methylamine(CMA^(+))cation,which could serve as a damper to alleviate the mechanical stress caused by lattice oscillations,compared to the rigid phenethyl methylamine(PEA^(+))analog.It demonstrates a significantly lower non-radiative recombination rate,even though the two types of bulky cations have similar chemical passivation effects on perovskite,which might be explained by the suppressed carrier capture process and improved lattice geometry relaxation.The resulting PSCs achieve an exceptional power conversion efficiency(PCE)of 25.5%with a record-high opencircuit voltage(V_(OC))of 1.20 V for narrow bandgap perovskite(FAPbI_(3)).The established correlations between electron-phonon coupling and non-radiative decay provide design and screening criteria for more effective passivators for highly efficient PSCs approaching the Shockley-Queisser limit.

Biodegradation of crude oil by Pseudomonas aeruginosa in the presence of rhamnolipids

The potential biodegradation of crude oil was assessed based on the development of a fermentative process with a strain of Pseudomonas aeruginosa which produced 15.4 g/L rhamnolipids when cultured in a basal mineral medium using glycerol as a sole carbon source. However, neither cell growth nor rhamnolipid production was observed in the comparative culture system using crude oil as the sole carbon source instead. As rhamnolipid, an effective biosurfactant, has been reported to stimulate the biodegradation of hydrocarbons, 1 g/L glycerol or 0.22 g/L rhamnolipid was initially added into the medium to facilitate the biodegradation of crude oil. In both situations, more than 58% of crude oil was degraded and further converted into accumulated cell biomass and rhamnolipids. These results suggest that Pseudomonas aeruginosa could degrade most of crude oil with direct or indirect addition of rhamnolipid. And this conclusion was further supported by another adsorption experiment, where the ad-sorption capacity of crude oil by killed cell biomass was negligible in comparison with the biologic activities of live cell biomass.

Characterization and Properties of Duplex a-C:H/MAO Coatings on Magnesium Alloy using Combined Microarc Oxidation and Hybrid Magnetron Sputtering

The combined microarc oxidation （MAO） and magnetron sputtering deposition process was used to deposit duplex a-C：H/MAO and Ti-a-C：H/MAO coatings on AM80 magnesium alloy. The microstructure, mechanical properties and tribological behavior of the two duplex coatings were investigated. The experimental results showed that the a-C：H and Ti-a-C：H top films on Si substrates were dense and had a low G peak position and ID/IG ratio, compared with the hydrogen-free amorphous carbon films. Numerous micropores were found on the duplex a-C：H/MAO and Ti-a-C：H/MAO coatings together with low values of hardness （H） and elastic modulus （E）, which also showed good binding strength with the Mg alloy substrates. Compared to MAO treated substrate used for the protection of the Mg alloy, the duplex a-C：H/MAO and Ti-a- C：H/MAO coatings still had stable and low value of friction coefficient, even though the surface of the duplex coatings was rough and porous. Furthermore, the mechanism of friction reduction of the two duplex coatings on the Mg alloy substrates was discussed.

Microstructure and Properties of Graphene Oxide-doped TiO_2 Coating on Titanium by Micro Arc Oxidation

Micro arc oxidation(MAO) coatings doped with graphene oxide(GO) were prepared on pure titanium by adding GO and sodium dodecyl benzene sulfonate(SDBS) into a sodium silicate solution. The as-deposited coatings were comparatively analyzed by scanning electron microscopy(SEM), energydispersive X-ray spectroscopy(EDS) and X-ray diffraction(XRD). The binding forces of the MAO, MAO+GO and MAO+GO+SDBS three coatings were measured by a scratch tester. The mechanical property of the three coatings was analyzed using the nano-indentation technique. The corrosion resistance of the coatings was tested by the electrochemical system in 3.5% NaCl solution. The photocatalytic activity of the prepared samples was evaluated by determining the degradation of methylene blue(MB) solution. The results showed that compared to the MAO coating, the morphologies and phase compositions of MAO+GO and MAO+GO+SDBS composite coatings were significantly different. These two composite coatings all had superior photocatalytic activity. Especially, the MAO+GO composite coating still had enhanced binding force and excellent corrosion resistance. Furthermore, the relationship between the microstructure and the properties of these three MAO coatings was analyzed.

Microstructure and Corrosion Resistance of Modified AZ31 Magnesium Alloy Using Microarc Oxidation Combined with Electrophoresis Process

A top electrophoresis coating was deposited on the surface microarc oxidation （MAO） modified ceramic coating on AZ31 magnesium alloy. Microstructure and corrosion resistance of this composite coating were studied by SEM, electrochemical potentiodynamic polarization, and acid corrosion test. The results showed that the composite coating with a top electrophoresis coating on the surface of ceramic coating exhibited a better corrosion resistance compared with the coating formed by chemical conversion film combined with electrophoresis process. Corrosive ions could permeate into the substrate with corrosion time, and the composite coating was firstly destroyed around the scratch. The formation of composite coating with a higher adhesive force due to the porosity of the ceramic coating contributed to the improved corrosion resistance property.

Optimization of investment casting process for K477 superalloy aero-engine turbine nozzle by simulation and experiment

In order to reduce the shrinkage porosity of nickel-based superalloy castings in the investment casting process,the effects of different gating systems on mold filling,solidification process,and prediction of shrinkage porosity of aero-engine turbine nozzle castings were investigated by simulation and experimental methods.Results show that the design of the vertical runner would cause greater turbulence of the melt in the riser during the mold filling process,and the outer runner is not necessary.With the decrease in number of runners,the hot spot moves down towards the casting,and the shrinkage and porosity defects are formed in the casting below the riser.In the original designs,a certain tendency of shrinkage and porosity defect is found in the vanes,inner rings,and outer rings of the castings by both simulation prediction and experiment.Finally,based on the processing optimization,the aero-engine turbine nozzle casting with no shrinkage and porosity defects is obtained.

Isothermal Crystallization Kinetics of Microencapsulated Polyethylene Glycol Particles

The microencapsulated polyethylene glycol (PEG) with different molecular weight by a fluidized coating method has been prepared and the crystallization behaviors of PEG particles in three-dimensional confined volume were investigated by using differential scanning calorimetry (DSC) measurement. The results showed that the width of the crystallization peak of PEG increases and its height gradually diminishes in case that the PEG particles are microencapsulated. Compared with the non-microencapsulated PEG particles, the proportion of the first crystallization peak of microencapsulated PEG particle increases, and that of the second one decreases. The reason for the difference maybe is that the crystallization process of microencapsulated PEG particles is uniform and the crystallization ends when the spherulites touch the wall, thus the opportunity of producing the second crystallization peak was relatively reduced.