Microwave-assisted exploration of the electron configuration-dependent electrocatalytic urea oxidation activity of 2D porous NiCo_(2)O_(4) spinel

Urea holds promise as an alternative water-oxidation substrate in electrolytic cells.High-valence nickelbased spinel,especially after heteroatom doping,excels in urea oxidation reactions(UOR).However,traditional spinel synthesis methods with prolonged high-temperature reactions lack kinetic precision,hindering the balance between controlled doping and highly active two-dimensional(2D)porous structures design.This significantly impedes the identification of electron configuration-dependent active sites in doped 2D nickel-based spinels.Herein,we present a microwave shock method for the preparation of 2D porous NiCo_(2)O_(4)spinel.Utilizing the transient on-off property of microwave pulses for precise heteroatom doping and 2D porous structural design,non-metal doping(boron,phosphorus,and sulfur)with distinct extranuclear electron disparities serves as straightforward examples for investigation.Precise tuning of lattice parameter reveals the impact of covalent bond strength on NiCo_(2)O_(4)structural stability.The introduced defect levels induce unpaired d-electrons in transition metals,enhancing the adsorption of electron-donating amino groups in urea molecules.Simultaneously,Bode plots confirm the impact mechanism of rapid electron migration caused by reduced band gaps on UOR activity.The prepared phosphorus-doped 2D porous NiCo_(2)O_(4),with optimal electron configuration control,outperforms most reported spinels.This controlled modification strategy advances understanding theoretical structure-activity mechanisms of high-performance 2D spinels in UOR.

Healing the structural defects of spinel MnFe_(2)O_(4) to enhance the electrocatalytic activity for oxygen reduction reaction

Spinel metal oxides containing Mn,Co,or Fe(AB_(2)O_(4),A/B=Mn/Fe/Co)are one of the most promising nonPt electrocatalysts for oxygen reduction reaction(ORR)in alkaline conditions.However,the low conductivity of metal oxides and the poor intrinsic activities of transition metal sites lead to unsatisfactory ORR performance.In this study,eutectic molten salt(EMS)treatment is employed to reconstruct the atomic arrangement of MnFe_(2)O_(4)electrocatalyst as a prototype for enhancing ORR performance.Comprehensive analyses by using XAFS,soft XAS,XPS,and electrochemical methods reveal that the EMS treatment reduces the oxygen vacancies and spinel inverse in MnFe_(2)O_(4)effectively,which improves the electric conductivity and increases the population of more catalytically active Mn^(2+)sites with tetrahedral coordination.Moreover,the enhanced Mn-O interaction after EMS treatment is conducive to the adsorption and activation of O_(2),which promotes the first electron transfer step(generally considered as the ratedetermining step)of the ORR process.As a result,the EMS treated MnFe_(2)O_(4)catalyst delivers a positive shift of 40 mV in the ORR half-wave potential and a two-fold enhanced mass/specific activity.This work provides a convenient approach to manipulate the atomic architecture and local electronic structure of spinel oxides as ORR electrocatalysts and a comprehensive understanding of the structureperformance relationship from the molecular/atomic scale.

Effects of iron oxide on crystallization behavior and spatial distribution of spinel in stainless steel slag

Chromium plays a vital role in stainless steel due to its ability to improve the corrosion resistance of the latter.However,the re-lease of chromium from stainless steel slag(SSS)during SSS stockpiling causes detrimental environmental issues.To prevent chromium pollution,the effects of iron oxide on crystallization behavior and spatial distribution of spinel were investigated in this work.The results revealed that FeO was more conducive to the growth of spinels compared with Fe2O3 and Fe3O4.Spinels were found to be mainly distrib-uted at the top and bottom of slag.The amount of spinel phase at the bottom decreased with the increasing FeO content,while that at the top increased.The average particle size of spinel in the slag with 18wt%FeO content was 12.8μm.Meanwhile,no notable structural changes were observed with a further increase in FeO content.In other words,the spatial distribution of spinel changed when the content of iron oxide varied in the range of 8wt%to 18wt%.Finally,less spinel was found at the bottom of slag with a FeO content of 23wt%.

Striking Stabilization Effect of Spinel Cobalt Oxide Oxygen Evolution Electrocatalysts in Neutral pH by Dual-Sites Iron Incorporation

Developing stable and efficient nonprecious-metal-based oxygen evolution catalysts in the neutral electrolyte is a challenging but essential goal for various electrochemical systems.Particularly,cobalt-based spinels have drawn a considerable amount of attention but most of them operate in alkali solutions.However,the frequently studied Co-Fe spinel system never exhibits appreciable stability in nonbasic conditions,not to mention attract further investigation on its key structural motif and transition states for activity loss.Herein,we report exceptional stable Co-Fe spinel oxygen evolution catalysts(~30%Fe is optimal)in a neutral electrolyte,owing to its unique metal ion arrangements in the crystal lattice.The introduced iron content enters both the octahedral and tetrahedral sites of the spinel as Fe^(2+)and Fe^(3+)(with Co ions having mixed distribution as well).Combining density functional theory calculations,we find that the introduction of Fe to Co_(3)O_(4)lowers the covalency of metal-oxygen bonds and can help suppress the oxidation of Co^(2+/3+)and 0^(2-).It implies that the Co-Fe spinel will have minor surface reconstruction and less lattice oxygen loss during the oxygen evolution reaction process in comparison with Co_(3)O_(4)and hence show much better stability.These findings suggest that there is still much chance for the spinel structures,especially using reasonable sublattices engineering via multimetal doping to develop advanced oxygen evolution catalysts.

Unveiling the geometric site dependent activity of spinel Co_(3)O_(4)for electrocatalytic chlorine evolution reaction

Spinel cobalt oxide(Co_(3)O_(4)),consisting of tetrahedral Co^(2+)(CoTd)and octahedral Co^(3+)(CoOh),is considered as promising earth-abundant electrocatalyst for chlorine evolution reaction(CER).Identifying the catalytic contribution of geometric Co site in the electrocatalytic CER plays a pivotal role to precisely modulate electronic configuration of active Co sites to boost CER.Herein,combining density functional theory calculations and experiment results assisted with operando analysis,we found that the Co_(Oh) site acts as the main active site for CER in spinel Co_(3)O_(4),which shows better Cl^(-)adsorption and more moderate intermediate adsorption toward CER than CoTd site,and does not undergo redox transition under CER condition at applied potentials.Guided by above findings,the oxygen vacancies were further introduced into the Co_(3)O_(4) to precisely manipulate the electronic configuration of Co_(Oh) to boost Cl^(-)adsorption and optimize the reaction path of CER and thus to enhance the intrinsic CER activity significantly.Our work figures out the importance of geometric configuration dependent CER activity,shedding light on the rational design of advanced electrocatalysts from geometric configuration optimization at the atomic level.

The Spectral Characterization of Blue Spinel and Other Blue Gemstones with the Alexandrite Effect

In gemmology,the term“Alexandrite effect”is used to describe colour change phenomenon when a gemstone is observed under different light sources,usually between daylight and incandescent light.The definition of the Alexandrite effect is constantly being broadened with new discovery of gem resource.The traditional definition of the Alexandrite effect attributing the colour change phenomenon to the presence of two maximum transmission regions and a maximum absorption region in the absorption spectra.In this study,7 blue spinels and 5 blue gemstones(including tanzanite,kyanite,fluorite,and 2 sapphires)showing the Alexandrite effect were investigated.The goal is to explain the cause of blue-to-violet Alexandrite effect and the spectral features causing such colour change.In the UV-Vis spectra,all samples showed a maximum absorption peak in the range of 534-610 nm,within the green region to orange region.The traditional explanation of green to red Alexandrite effect required a transmission window in the red region;however,some of our samples did not show this transmission window and the blue-to-violet Alexandrite effect was still visible.Therefore,it is incomplete to explain the mechanism of the Alexandrite effect according to their characteristic absorption spectra,a systematic study based on modern colour science and colour perception in human vision is required to elucidate the blue-to-violet Alexandrite effect.

Effect of Yttrium on Microstructure and Hot Corrosion Preformance of Laser Clad Co-Based Alloy

The structure of the yttrium modified Co-base alloy layers formed by laser cladding on 2Cr13 and 1Cr18Ni9Ti steel surfaces and its hot corrosion performance have been investigated systematically.The re- sults show that the Y-containing cobalt base clad alloy has a finer microstructure and higher corrosion re- sistance to the salt mixture of 75% Na_2SO_4+25%NaCl at high temperature.The unique properties are ob- tained with addition of 0.875% Y for the formation of a continuous and compact oxide scale.The compact scale may act as a barrier for the inward diffusion of oxygen and sulphur and also for the outward diffusion of alloying elements.

Microstructure and wear resistance of Fe-based and Co-based coating of AISI H13

Fe-based and Co-based cladding layers were prepared on the surface of AISI H13 hot die steel by laser cladding technology.The microstructure,hardness and abrasion resistance of the two cladding layers were studied by means of optical microscope,scanning electron microscope,rockwell hardness tester,and high temperature friction and wear tester.Also,the red hardness of the cladding layers was measured,after holding the layers at 600℃ for 1 hour by muffle furnace and repeated 4 times.The rockwell hardness values of the substrate,the Fe-based and the Co-based alloy coating measured were HRC 47,HRC 52 and HRC 48,respectively.The red hardness values of the substrate and the Fe-based cladding layer were decreased,while that of the Co-based cladding layer was increased.The Co-based cladding layer has the minimal wear loss weight and friction coefficient among them.The wear mechanisms of the substrate,the Fe-based layer and the Cobased layer attribute mainly to abrasive wear,adhesion wear,and both of them,respectively.

Thermal Fatigue Behaviour of Co-Based Alloy Coating Obtained by Laser Surface Melt-Casting on High Temperature Alloy

A thermal fatigue behaviour of Co-based alloy coating obtained by laser surface meltcasting on the high temperature alloy GH33 was studied.The results show that after each time of thermal cycling,the final residual stress was formed in the melt-casting layer which is attributed to the thermal stress and structural stress.Through the first 50 times of thermal cycling,the morphology of coating still inherits the laser casting one,but the dendrites get bigger;After the second 50 times of thermal cycling,corrosion pits emerge from coating,and mostly in the places where coating and substrate meet.The fatigue damage type of coating belongs to stress corrosion.

Microstructures and properties of Co-based alloy coatings prepared on surface of H13 steel

The Co-based alloy coatings had been prepared by laser cladding and vacuum fusion sintering. Microstructures of the coatings were investigated and the performance of thermal cycling was also tested using scanning electron microscopy （ SEM） and X-ray diffraction （ XRD ）. The results show that the coatings and substrates combine well. The main phase compositions of laser cladding coating are T-Co, Cr23 C6 and Ni2 9 Cro. 7 Feo. 36, while vacuum fusion sintering coating consists of Co, Cr7 C3, and Ni2.9 Cro. 7 Feo. 36. After thermal cycling, the minimum hot cracking width of laser cladding coating is 14 μm; moreover, laser cladding coating maintains high hardness and hot-cracking susceptibility. Those are beneficial to high temperature wear resistance of hot work dies.

Enabling structural and interfacial stability of 5 V spinel LiNi0.5Mn1.5O4 cathode by a coherent interface

Spinel LiNi_(0.5)Mn_(1.5)O_(4)(LNMO),a 5 V class high voltage cathode,has been regarded as an attractive candidate to further improve the energy density of lithium-ion battery.The issue simultaneously enabling side stability and maintaining high interfacial kinetics,however,has not yet been resolved.Herein,we design a coherent Li_(1.3)A_(l0.3)Ti_(1.7)(PO)_(4)(LATP)layer that is crystally connected to the spinel LNMO host lattices,which offers fast lithium ions transportation as well as enhances the mechanical stability that prevents the particle fracture.Furthermore,the inactive Li_(3)BO_(3)(LBO)coating layer inhibits the corrosion of transition metals and continuous side reactions.Consequently,the coherent-engineered LNMO-LATPLBO cathode material exhibits superior electrochemical cycling stability in a window of 3.0–5.0 V,for example a high-capacity retention that is 89.7%after 500 cycles at 200 m A g-1obtained and enhanced rate performance(85.1 m A h g^(-1)at 800 m A g^(-1))when tested with a LiPF6-based carbonate electrolyte.Our work presents a new approach of engineering 5 V class spinel oxide cathode that combines interfacial coherent crystal lattice design and surface coating.

Effects of ZnO,FeO and Fe_(2)O_(3)on the spinel formation,microstructure and physicochemical properties of augite-based glass ceramics

Augite-based glass ceramics were synthesised using ZnO,FeO,and Fe_(2)O_(3)as additives,and the spinel formation,matrix structure,crystallisation thermodynamics,and physicochemical properties were investigated.The results showed that oxides resulted in numerous preliminary spinels in the glass matrix.FeO,ZnO,and Fe_(2)O_(3)influenced the formation of spinel,while FeO simplified the glass network.FeO and ZnO promoted bulk crystallisation of the parent glass.After adding oxides,the grains of augite phase were refined,and the relative quantities of augite crystal planes were also influenced.All samples displayed good mechanical properties and chemical stability.The 2wt%ZnO-doping sample displayed the maximum flexural strength(170.3 MPa).Chromium leaching amount values of all the samples were less than the national standard(1.5 mg/L),confirming the safety of the materials.In conclusion,an appropriate amount of zinc-containing raw material is beneficial for the preparation of augite-based glass ceramics.

Influence of welding on low cycle fatigue properties of Co-based superalloy FSX-414

Co-based superalloys such as FSX-414 have been recently used in gas turbine first stage nozzles. During service, nozzles are exposed to low cycle fatigue, which can lead to cracking of these components. The cracks on these nozzles are usually welded with ttmgsten arc welding （TIG） using Co-based filler metals. In this paper, the effect of TIG on the tensile and low cycle fatigue properties of Co-based superalloy FSX-414 was studied at 950℃. The experimental results show that the yield and ultimate tensile stresses of welded and unwelded specimens are comparable to each other. But toughness of welded specimens is lower than that of unwelded ones. The low cycle fatigue properties of FSX-414 were studied at a strain rate of 3.3×10^-4 s^-1, strain ratio R=-1 （R=emin/emax） and Aet （total strain change） from 0.8% to 2%. In welded specimens, at high strain cycling, the nucleation and growth of cracks occur in the welded zone. But at Aet=0.8%, fracture occurs in the same zones of unwelded specimens. The results show that the total fatigue lives of the welded specimens are shorter than those of unwelded ones. In all of the low cycle fatigue tests, softening phenomena are observed.

High-Temperature Electric Properties and X-ray Photoemission Spectra of Layered Co-Based Oxides Bi_(2-x)La_xSr_2Co_2O_(8-δ)

Layered Co-based ceramics with a nominal composition Bi2-xLaxSr2Co2O8-δ (x=0.0, 0.4, 0.8, short by BLC-222) were prepared using conventional solid state reaction method. X-ray photoemission spectroscopy (XPS) was used to investigate their electronic structures. The cobalt ions are highly mixed valences of Co3+ and Co4+. The fraction of Co4+ almost keeps unchanged with the increase of x. The O-1s photoemission spectra show that there are lattice oxygen and chemical absorbed oxygen in all the samples. The substitution of Bi3+ by La3+ results in a change from metallic-like behavior to semiconductor behavior. This abnormal phenomenon means that La3+ plays a key role in effecting the electrical transport property of BLC-222. The O-Co covalence bond is strengthened by the increase of La3+, which results in the decrease of conductivity.

Preparation, Structures and Magnetic Properties of Two Co-based Clusters with Triangular Core and Cuboidal Core Geometries

Two novel Co-based clusters with the 2-(hydroxylmethyl)pyridine(hmpH)ligand,formulated as[Co3(hmp)6(hmpH)]×2NO3×3H2O(ZTU-3)and[Co4(hmp)4(CH3CO2)2(H2O)4]×2NO3(ZTU-4),have been successfully synthesized and structurally characterized.ZTU-3 features a triangular core geometry,while ZTU-4 exhibits a cuboidal core geometry.In addition,the magnetic properties of ZTU-3 and ZTU-4 are also all investigated.

Effects of Al and Co doping on the structural stability and high temperature cycling performance of LiNi_(0.5)Mn_(1.5)O_(4) spinel cathode materials

The poor structural stability and capacity retention of the high-voltage spinel-type LiNi_(0.5)Mn_(1.5)O_(4)(LNMO)limits their further application.Herein,Al and Co were doped in LNMO materials for a more stable structure and capacity.The LNMO,LiNi_(0.45)Al_(0.05)Mn_(1.5)O_(4)(LNAMO)and LiNi_(0.45)Co_(0.05)Mn_(1.5)O_(4)(LNCMO)were synthesized by calcination at 900℃ for 8 h,which was called as solid-phase method and applied universally in industry.XRD,FT-IR and CV test results showed the synthesized samples have cation disordering Fd-3m space group structures.Moreover,the incorporation of Al and Co increased the cation disordering of LNMO,thereby increasing the transfer rate of Li+.The SEM results showed that the doped samples performed more regular and ortho-octahedral.The EDS elemental analysis confirmed the uniform distribution of each metal element in the samples.Moreover,the doped samples showed better electrochemical properties than undoped LNMO.The LNAMO and LNCMO samples were discharged with specific capacities of 116.3 mA·h·g^(-1)and 122.8 mA·h·g^(-1)at 1 C charge/discharge rate with good capacity retention of 95.8% and 94.8% after 200 cycles at room temperature,respectively.The capacity fading phenomenon of the doped samples at 50℃ and 1 C rate was significantly improved.Further,cations doping also enhanced the rate performance,especially for the LNCMO,the discharge specific capacity of 117.9 mA·h·g^(-1)can be obtained at a rate of 5 C.

Effect of Laser Annealing on Permeability Spectra in Co-based Amorphous Ribbon

We investigated the variation of permeability spectra and relaxation frequency in Co-based amorphous ribbon annealed by pulsed Nd:YAG laser at various annealing energy Ea. The complex permeability spectra varies sensitively with the annealing energy, where the spectra could be decomposed into two contributions from domain wall motion,μdw(f) and rotational magnetization μrot(f) by analyzing the measured spectra as a function of driving ac field amplitude. The magnitude of μdw(f) and μrot(f) in dc limit shows maximum at Ea = 176 mJ. The maximum relaxation frequency for rotational magnetization, determined by μ'(f) curve, is about 700 kHz at Ea=62 mJ but that for wall motion is about 26 kHz at 230 mJ. These variations reflect the increase of magnetic softness and microstructural change by the annealing.

Development of bimetallic spinel catalysts for low-temperature decomposition of ammonium dinitramide monopropellants

Ammonium dinitramide(ADN)based liquid monopropellants have been identified as environmentally benign substitutes for hydrazine monopropellant.However,new catalysts are to be developed for making ADN monopropellants cold-start capable.In the present study,performance of Co and Ba doped CuCr_2O_4 nanocatalysts prepared by hydrothermal method was evaluated on the decomposition of aqueous ADN solution and ADN liquid monopropellant(LMP103X).The catalysts were characterized by PXRD(Powder X-ray Diffraction),FTIR(Fourier Transform Infrared spectroscopy),SEM(Scanning Electron Microscopy),TEM(Transmission Electron Microscopy),EDS(Energy Dispersive X-ray Spectroscopy),and XPS(X-ray Photoelectron Spectroscopy).The nanosize was confirmed by SEM and TEM,while the nanoflake morphology was confirmed by the SEM analysis.Further,we obtained the elemental composition from the EDS analysis.We investigated the catalytic activity of the catalysts by thermogravimetric(TG)analysis and the developed catalysts lowered the decomposition temperature of ADN monopropellant by about 55℃.The XPS analysis confirmed the presence of metal ions with different chemical states.Apparently,increase in the surface area of the catalysts and the mixed active sites as well as the development of oxygen vacancy on the catalyst surface introduced by metal doping are influencing the decomposition temperature of ADN samples.

Effect of Al Powder and Si Powder Additions on Structure and Properties of Unburned Magnesium Aluminate Spinel Refractories

Unburned magnesium aluminate spinel refractories were prepared using sintered magnesium aluminate spinel as the main raw material,phenolic resin as the binder,aluminum powder(2%,4%,and 6%by mass)and silicon powder(when Al powder addition is 4%,Si powder addition varies:1%and 2%,by mass)as additives.The effects of the Al powder and Si powder additions on the properties and microstructure of the refractories heat treated at different temperatures(1000,1400,and 1600℃for 3 h)were studied.The results show that the Al powder addition can greatly enhance the cold modulus of rupture of the samples fired at 1000 or 1400℃,and meanwhile AlN reinforcement phase forms in the matrix,which greatly improves the hot modulus of rupture of the samples at 1400℃;however,the heat treatment at 1600℃has little influence on the strength;the addition of Al powder and Si powder results in the formation of low melting point phases,greatly reducing the hot modulus of rupture.However,the low melting point phases promote sintering,which enhances the density and the cold modulus of rupture,and decreases the volume change during heating.The samples added with Al and Si all have higher cold modulus of rupture than those added with Al powder only.

Gemological-Mineralogical Characteristic of Spinels from Sri Lanka

Detailed mineralogical and gemological records were conducted on 340 unheated spinels from the Horana, Eheliyagoda, Ratnapura, and Okkampatiya mining areas in Sri Lanka. The color of Sri Lankan spinel varies greatly: in addition to the mainstream pink to purple pink, green and blue can also be seen. Compared with spinel from other regions such as Myanmar, Vietnam, and Tanzania, Sri Lanka's spinel has more abundant inclusions: several mining areas generally have inclusions such as dolomite, apatite, zircon, and chondrodite. Minerals such as graphite and forsterite are also found in spinel produced in the Horana region;graphite and rutile have been found in spinel produced in the Okkamptiya region. Partially healed fissures are most common in spinel in the Okkampatiya mining area;Unlike Vietnamese spinel, dislocations and growth structures are almost absent in Sri Lankan spinel. The LA-ICP-MS analysis results showed that there were no significant differences among the mining areas. LA-ICP-MS analysis of 5 Sri Lankan cobalt blue spinels showed a variation of 11 to 120 ppm in this chromogenic element. The UV visible absorption spectrum results show that Sri Lankan spinel has a combination spectra with variable ratios of the spectral components Cr 3+ , V 3+ and Fe 2+ from pink to red, orange, purple to purple, and blue-green. The results of infrared spectroscopy and laser Raman spectroscopy analysis showed that all samples showed no indications for heat treatment.