The Zn-Al spinel oxide stands out as one of the most active catalysts for high-temperature methanol synthesis from CO_(2)hydrogenation.However,the structure–activity relationship of the reaction remains poorly unders...The Zn-Al spinel oxide stands out as one of the most active catalysts for high-temperature methanol synthesis from CO_(2)hydrogenation.However,the structure–activity relationship of the reaction remains poorly understood due to challenges in atomic-level structural characterizations and analysis of reaction intermediates.In this study,we prepared two Zn-Al spinel oxide catalysts via coprecipitation(ZnAl-C)and hydrothermal(ZnAl-H)methods,and conducted a comparative investigation in the CO_(2)hydrogenation reaction.Surprisingly,under similar conditions,ZnAl-C exhibited significantly higher selectivity towards methanol and DME compared to ZnAl-H.Comprehensive characterizations using X-ray diffraction(XRD),Raman spectroscopy and electron paramagnetic resonance(EPR)unveiled that ZnAl-C catalyst had abundant ZnO species on its surface,and the interaction between the ZnO species and its ZnAl spinel oxide matrix led to the formation of oxygen vacancies,which are crucial for CO_(2)adsorption and activation.Additionally,state-of-the-art solid-state nuclear magnetic resonance(NMR)techniques,including ex-situ and in-situ NMR analyses,confirmed that the surface ZnO facilitates the formation of unique highly reactive interfacial formate species,which was readily hydrogenated to methanol and DME.These insights elucidate the promotion effects of ZnO on the ZnAl spinel oxide in regulating active sites and reactive intermediates for CO_(2)-to-methanol hydrogenation reaction,which is further evidenced by the significant enhancement in methanol and DME selectivity observed upon loading ZnO onto the ZnAl-H catalyst.These molecular-level mechanism understandings reinforce the idea of optimizing the ZnO-ZnAl interface through tailored synthesis methods to achieve activity-selectivity balance.展开更多
Electrochemical conversion of lignin for the production of high-value heterocyclic aromatic compounds has great potential.We demonstrate the targeted synthesis and cation modulation of NiCo_(2)O_(4)spinel nanoboxes,sy...Electrochemical conversion of lignin for the production of high-value heterocyclic aromatic compounds has great potential.We demonstrate the targeted synthesis and cation modulation of NiCo_(2)O_(4)spinel nanoboxes,synthesized via cation exchange and calcination oxidation.These catalysts exhibit excellent efficacy in the electrocatalytic conversion of lignin model compounds,specifically 2-phenoxy-1-phenylethanol,into nitrogen-containing aromatics,achieving high conversion rates and selectivities.These catalysts were synthesized via a cation exchange and calcination oxidation process,using Prussian blue nanocubes as precursors.The porous architecture and polymetallic composition of the NiCo_(2)O_(4)spinel demonstrated superior performance in electrocatalytic oxidative coupling,achieving a 99.2 wt%conversion rate of the 2-phenoxy-1-phenylethanol with selectivities of 37.5 wt%for quinoline derivatives and 31.5 wt%for phenol.Key innovations include the development of a sustainable one-pot synthesis method for quinoline derivatives,the elucidation of a multistage reaction pathway involving CAO bond cleavage,hydroxyaldol condensation,and CAN bond formation,and a deeper mechanistic understanding derived from DFT simulations.This work establishes a new strategy for lignin valorization,offering a sustainable route to produce high-value nitrogen-containing aromatics from renewable biomass under mild conditions,without the need for additional reagents.展开更多
High-temperature industries,as the primary consumers of energy,are greatly concerned with energy savings.Designing refractory linings with low thermal conductivity to reduce heat dissipation through high-temperature f...High-temperature industries,as the primary consumers of energy,are greatly concerned with energy savings.Designing refractory linings with low thermal conductivity to reduce heat dissipation through high-temperature furnace linings is a critical concern.In this study,a series of novel entropy-stabilized spinel materials are reported,and their potential applications in high-temperature industries are investigated.XRD and TEM results indicate that all materials possess a cubic spinel crystal structure with the■space group.Furthermore,these materials exhibit good phase stability at high temperatures.All entropy-stabilized spinel aggregates demonstrated high refractoriness(>1800℃)and a high load softening temperature(>1700℃).The impact of configurational entropy on the properties of entropy-stabilized spinel materials was also studied.As configurational entropy increased,the thermal conductivity of the entropy-stabilized spinel decreased,while slag corrosion resistance deteriorated.For the entropy-stabilized spinel with a configurational entropy value of 1.126R,it showed good high-temperature stability,reliable resistance to slag attack,and a low thermal conductivity of 2.776 W·m^(-1)·K^(-1)at 1000℃.展开更多
Owing to the complexity of multicomponent gases,developing multifunctional catalysts for synergistic removal of benzene and toluene remains challenging.The spinel MMn_(2)O_(4)(M=Co,Ni,or Cu)catalysts were successfully...Owing to the complexity of multicomponent gases,developing multifunctional catalysts for synergistic removal of benzene and toluene remains challenging.The spinel MMn_(2)O_(4)(M=Co,Ni,or Cu)catalysts were successfully synthesized via the sol–gel method and tested for their catalytic performance for simultaneous degradation of benzene and toluene.The CuMn_(2)O_(4)sample exhibited the best catalytic performance,the conversion of benzene reached 100%at 350℃,and toluene conversion reached 100%at 250℃.XRD,N_(2)adsorption-desorption,HRTEM-EDS,ED-XRF,Raman spectroscopy,H_(2)-TPR,NH_(3)-TPD,O_(2)-TPD and XPS were used to characterize the physical and chemical properties of MMn_(2)O_(4)catalysts.The excellent redox properties,high concentration of surface Mn4+,and adsorption of oxygen species over the CuMn_(2)O_(4)sample facilitated the simultaneous and efficient removal of benzene and toluene.Additionally,in situ DRIFTS illustrated the intermediate species and reaction mechanism for the synergetic catalytic oxidation of benzene and toluene.Notably,as an effective catalytic material,spinel oxide exhibited excellent synergistic degradation performance for benzene and toluene,providing some insight for the development of efficient multicomponent VOC catalysts.展开更多
Electroplating sludge(ES),a byproduct of the electroplating industry,is a significant environmental concern due to its high content of soluble heavy metals(HMs).The significance of spinel formation from ES lies in its...Electroplating sludge(ES),a byproduct of the electroplating industry,is a significant environmental concern due to its high content of soluble heavy metals(HMs).The significance of spinel formation from ES lies in its potential for HMs enrichment and environmental remediation,offering a sustainable solution for hazardous waste management.The article delves into themultifaceted recycling of HMs-rich spinel fromES,encompassing its synthesis,metal enrichment,and thermodynamic stability.The pyro-metallurgical and hydrometallurgical processes for spinel synthesis were discussed,with a focus on the critical role of thermodynamic data in predicting the stability and formation of spinel structures.The crystallographic and magnetic properties of spinels,with their applications in environmental remediation and energy storage are highlighted.The article provides a comprehensive reviewon the recycling of HMs-rich spinel fromES,offering a means to recycle HMs,mitigate ecological harm,and contribute to a circular economy through the recovery and application of valuable materials.The selective leaching of metals from ES also faces challenges,which was limited by the separation,purification steps and high energy consumption.This high energy consumption is a significant operational cost and also contributes to environmental concerns related to carbon emissions.It is essential to address the challenges through continued research and development,improved technologies,and supportive regulatory frameworks.展开更多
In this research work,sol-gel technique was employed to prepare the strontium based spinel ferrite nanoparticles(SrFe_(2)O_(4))with different ratios of terbium(Tb).Different characterization techniques were used to in...In this research work,sol-gel technique was employed to prepare the strontium based spinel ferrite nanoparticles(SrFe_(2)O_(4))with different ratios of terbium(Tb).Different characterization techniques were used to investigate the structural,morphological,dielectric and magnetic properties of the prepared samples.X-ray diffraction(XRD)result suggests that face-centered cube spinel nanocrystalline structure is formed.Crystallite size of the SrFe_(2)O_(4)decreases with rising of Tb ratio.The morphology,shape and size of the SrFe_(2)O_(4)were examined by scanning electron microscopy(SEM)analysis and results reveal inhomogeneous distributions of the nanostructures with high agglomeration.The electrical resistivity of the SrFe_(2)O_(4)increases with rising of Tb ratio,which is confirmed from the cyclic voltammetry.It is observed that dielectric constant of all the samples decreases with the increasing frequency range.It is determined that the dielectric constants of the spinel ferrites are frequency dependent and decrease with increasing the frequency of applied electric field.The magnetic behavior of SrFe_(2)O_(4)with different ratios of Tb was studied and it is found that the saturation magnetization values of samples decrease with increase in the substitution of Tb^(3+)at octahedral sites for Fe^(3+).This decrease in the values of M_(s) is also attributed to spin at surface of nanoparticles.展开更多
Spinel LiNi_(0.5)Mn_(1.5)O_(4)(LNMO)is a promising high-voltage cathode material for the next generation lithium metal batteries because of its high operating voltage plateau(4.7 V vs.Li+/Li),high theoretical specific...Spinel LiNi_(0.5)Mn_(1.5)O_(4)(LNMO)is a promising high-voltage cathode material for the next generation lithium metal batteries because of its high operating voltage plateau(4.7 V vs.Li+/Li),high theoretical specific capacity(147 mAh/g),relatively low cost and environmentally benign properties.Despite promising,the commercialization of LNMO cathodes is hindered by its electrochemical instability using conventional carbonate electrolytes,resulting in lower Coulombic efficiency and poor cycling stability.Herein,we adopt an all-fluorinated electrolyte(AFE)with a wide electrochemical stability window for Li//LNMO cells.Compared to conventional carbonate electrolytes,AFE significantly improves the discharge capacity and rate performance of Li//LNMO cells at various cut-off voltages and temperatures,attributed to the formation of a robust cathode-electrolyte interphase(CEI)layer.Specifically,the resultant Li//AFE//LNMO cells deliver a discharge capacity of 131.7 mAh/g with 84.1%capacity retention after 250 cycles at a charge cut-off voltage of 4.9 V,while it sustains only 114.8 mAh/g with 81.9%capacity retention for the cell using a conventional carbonate electrolyte.The influence of charge/discharge rate and temperature on the performance is also evaluated.Overall,this study presents a facile approach to promote the commercialization of high-voltage LNMO cathodes.展开更多
Antiphase boundaries(APBs)are intrinsic defects in Fe_(3)O_(4) films that significantly alter their magnetic and transport properties compared to the bulk material due to antiferromagnetic interactions across these bo...Antiphase boundaries(APBs)are intrinsic defects in Fe_(3)O_(4) films that significantly alter their magnetic and transport properties compared to the bulk material due to antiferromagnetic interactions across these boundaries.In the study,we realize ferromagnetically coupled APBs in spinel ferrite by cation disorder and oxygen vacancy defects.Ni and Zn are introduced into Fe_(3)O_(4) to form Ni and NiZn ferrites and cation disorder is found in the two ferrites with Ni and Zn occupied in both octahedral and tetrahedral sites.This disorder transforms the ferrites from semiconductors into half-metals,characterized by a nonzero majority spin density of states(DOS)and a zero minority spin DOS at Fermi level.The stacking fault of the cations(Fe,Ni,Zn)at the APB induces excess negative charges,leading to the formation of oxygen vacancies as charge compensators.These vacancies disrupt the antiferromagnetic superexchange interactions,preventing spin polarization reversal across the APB,thereby enabling ferromagnetic coupling.This work provides insights into tuning the magnetic properties of APBs in spinel ferrites through defect engineering and cation manipulation.展开更多
An experiment was conducted to assess the impact of fused calcia-stabilized zirconia micro-powder on the thermal shock behavior of magnesia–spinel refractories.The effects of calcia-stabilized zirconia on the microst...An experiment was conducted to assess the impact of fused calcia-stabilized zirconia micro-powder on the thermal shock behavior of magnesia–spinel refractories.The effects of calcia-stabilized zirconia on the microstructure evolution and properties of magnesia–spinel refractories were characterized by the high-temperature elastic modulus,thermal shock damage resistance parameters,retainment of elastic modulus after thermal shock,and scanning electron microscopy.The results indicated that the incorporation of calcia-stabilized zirconia improved the thermomechanical properties and thermal shock behavior of magnesia–spinel specimens.The hot modulus of rupture of magnesia–spinel specimens increased by 2.5-fold due to the incorporation of calcia-stabilized zirconia micro-powder.The presence of a martensitic phase transformation in partially unstable ZrO2 and thermal mismatches among various phases contributed to a controlled formation of microcracks.And the pinning effect caused by the calcia-stabilized zirconia particles surrounding the grain boundaries played a crucial role in preventing the propagation of microcracks.This phenomenon significantly bolstered the thermal shock stability of magnesia–spinel refractories,consequently prolonging their service life.展开更多
Spintronic technology and energy applications benefit greatly from the exceptional characteristics of rare-earth-based spinel chalcogenides.Examining the electrical,magnetic and thermoelectric properties of HgNd_(2)Z_...Spintronic technology and energy applications benefit greatly from the exceptional characteristics of rare-earth-based spinel chalcogenides.Examining the electrical,magnetic and thermoelectric properties of HgNd_(2)Z_(4)(Z=S,Se)in a systematic manner is essential for the strategic advancement of spin polarized current in a spintronic device.In this recent study,the WIEN2K code was employed to comprehensively analyze these properties.The calculated lattice constants,obtained using the generalized gradient approximation(GGAsol-PBE),closely match experimental findings of the similar family compounds.The examination of the stability of ferromagnetic states in the ground state involves comparing energies between anti-ferromagnetic and ferromagnetic states.Moreover,an assessment of the stability of the cubic phase in both spinels was conducted using analyses of the phonon dispersion curve,formation energy and Born stability criteria.The ductility characteristics were examined through the calculation of Poisson's and Pugh's ratios.Furthermore,details regarding the density of states,spin polarization,ex-change coupling and Curie temperature were provided to explore the characteristics associated with ferromagnetism.Potential optoelectronic applications were proposed,leveraging the direct band gaps of 1.4 and 1.0 eV for HgNd_(2)Z_(4)(Z=S,Se)respectively,within the visible spectrum.Particularly noteworthy is the effective light absorption of HgNd2Se4 in the visible range,characterized by prominent peaks that facilitate the transition of electrons from the valence band(VB)to the conduction band(CB).Additionally,the study extends to thermoelectric characteristics,determining various factors such as Seebeck coef-ficient(S),figure of merit(ZT),electrical and thermal conductivities of the evaluated spinels.展开更多
The Ni-ZnFe_(2)O_(4)(NixZn_(1-x)Fe_(2)O_(4),x=0.4-0.7)spinel was synthesized using Zn2+extracted from electric arc furnace dust(EAFD),nickel chloride hexahydrate,and Fe^(3+)extracted from iron scale as raw materials.T...The Ni-ZnFe_(2)O_(4)(NixZn_(1-x)Fe_(2)O_(4),x=0.4-0.7)spinel was synthesized using Zn2+extracted from electric arc furnace dust(EAFD),nickel chloride hexahydrate,and Fe^(3+)extracted from iron scale as raw materials.The zinc was selectively extracted from EAFD using CaO roasting followed by NH_(4)Cl solution leaching.The ferric ion was leached from iron scale using HCl solution as acid lixiviant.The experimental results demonstrate a high level of efficiency in the extraction of zinc,with a rate of 97.5%,and the leaching rate of ferric ion is 96.89%.The composition of the leaching solution is primary zinc and iron with low calcium,which is beneficial to the preparation of spinel ferrite.The influence of Ni content(x)and calcination temperature on the synthesis and magnetic properties of NixZn_(1-x)Fe_(2)O_(4)compounds was investigated by X-ray diffraction,scanning electron microscopy,and vibrating sample magnetometry.The results revealed that both Ni content and calcination temperature significantly affect the synthesis and magnetic properties of spinel NixZn_(1-x)Fe_(2)O_(4).Under the conditions of Ni content set at x=0.6,calcination temperature of 1100℃,and a duration of 2 h,a spinel NixZn_(1-x)Fe_(2)O_(4)with high saturation magnetization(Ms=65.7 A m2 kg-1)and low coercivity(Hc=0.056 A m^(-1))was obtained.展开更多
Ensuring high electrocatalytic performance simultaneously with low or even no precious-metal usage is still a big challenge for the development of electrocatalysts toward oxygen evolution reaction(OER)in anion exchang...Ensuring high electrocatalytic performance simultaneously with low or even no precious-metal usage is still a big challenge for the development of electrocatalysts toward oxygen evolution reaction(OER)in anion exchange membrane water electrolysis.Here,homogeneous high entropy oxide(HEO)film is in-situ fabricated on nickel foam(NF)substrate via magnetron sputtering technology without annealing process in air,which is composed of many spinel-structured(FeCoNiCrMo)_(3)O_(4) grains with an average particle size of 2.5 nm.The resulting HEO film(abbreviated as(FeCoNiCr-Mo)_(3)O_(4))exhibits a superior OER performance with a low OER overpotential of 216 mV at 10 mA cm^(–2) and steadily operates at 100 mA cm^(–2) for 200 h with a decay of only 272μV h^(–1),which is far better than that of commercial IrO_(2) catalyst(290 mV,1090μV h^(–1)).Tetramethylammonium cation(TMA^(+))probe experiment,activation energy analysis and theoretical calculations unveil that the OER on(FeCoNiCrMo)_(3)O_(4) follows an adsorbate evolution mechanism pathway,where the energy barrier of rate-determining step for OER on(FeCoNiCrMo)_(3)O_(4) is substantially lowered.Also,methanol molecular probe experiment suggests that a weakened ^(*)OH bonding on the(FeCoNiCrMo)_(3)O_(4) surface and a rapid deprotonation of ^(*)OH,further enhancing its OER performance.This work provides a feasible solution for designing efficient high entropy oxides electrocatalysts for OER,accelerating the practical process of water electrolysis for H2 production.展开更多
In order to prepare high density magnesium aluminate spinel materials,the light-burned magnesia and alumina powder were used as the main raw materials.Active magnesium aluminate spinel powders were synthesized at diff...In order to prepare high density magnesium aluminate spinel materials,the light-burned magnesia and alumina powder were used as the main raw materials.Active magnesium aluminate spinel powders were synthesized at different temperatures,and the sintering properties of the synthesized materials were characterized.The results show that the optimal light-burned temperature for synthesizing active magnesium aluminate spinel raw materials with small grain sizes and high sintering activity is 1400℃.The active spinel raw materials were sintered at 1750℃ for 3 h to form a dense spinel material,in which the spinel grains were well developed,exhibited a dense interlocking structure,and were uniformly distributed,with an average grain size of about 7.26μm.The bulk density and apparent porosity of the dense spinel material were 3.29 g·cm^(-3) and 3.5%,respectively.展开更多
Spinel LiNi_(0.5)Mn_(1.5)O_(4)(LNMO)cathode draws significant attention in the field of energy storage due to its unique voltage plateau.To further enhance the long-term electrochemical stability of LNMO,the LNMO cath...Spinel LiNi_(0.5)Mn_(1.5)O_(4)(LNMO)cathode draws significant attention in the field of energy storage due to its unique voltage plateau.To further enhance the long-term electrochemical stability of LNMO,the LNMO cathode covered with an ultrathin ZrO_(2)layer was prepared through atomic layer deposition(ALD).It is found that the LNMO cathode deposited with 20 layers of ZrO_(2)(LNMOZ20)exhibits the best electrochemical performance,achieving a high discharge capacity of 117.1 mA·h/g,with a capacity retention of 87.4%after 600 cycles at a current density of 1C.Furthermore,even at higher current densities of 5C and 10C,the LNMOZ20 electrode still demonstrates excellent stability with discharge capacities reaching 111.7 and 103.6 mA·h/g,and capacity retentions maintaining at 81.0%and 101.4%after 2000 cycles,respectively.This study highlights that the incorporation of an ultrathin ZrO_(2)layer by ALD is an effective strategy for enhancing the long-term cycling stability of LNMO cathodes.展开更多
The densification and microstructure of different spinelized magnesium aluminate spinels（MAS） were studied adding Sc_2O_3 as additive. Sintered products were then characterized in terms of densification, phase analy...The densification and microstructure of different spinelized magnesium aluminate spinels（MAS） were studied adding Sc_2O_3 as additive. Sintered products were then characterized in terms of densification, phase analysis, quantitative elemental analysis and microstructure. The results show that Sc_2O_3 is found to be beneficial for the densification of MAS. Sc_2O_3 has a more significant effect on the densification of partially spinelized MAS batch than that of fully spinelized MAS batch. At the sintering temperature of 1650 °C, the bulk density of sintered products of partially spinelized powders increases by 0.243 g/cm3 as the Sc_2O_3 content increases from 0 to 4%（mass fraction） and that of fully spinelized powder increases by 0.14 g/cm3. Compared with the sintered samples prepared from the fully spinelized powder, the sintered samples using the partially spinelized powders as raw materials have more compact microstructures.展开更多
The effects of Sm_(2) O_(3) as an additive on the densification of a pre-synthesized magnesia-rich spinel were investigated.The sintering behavior of the material was characterized by analyzing its dilatometric charac...The effects of Sm_(2) O_(3) as an additive on the densification of a pre-synthesized magnesia-rich spinel were investigated.The sintering behavior of the material was characterized by analyzing its dilatometric characteristics,linear shrinkage,bulk density,apparent porosity,phase structure,and micro structure.Moreover,the cold modulus of rupture(CMOR) and microhardness of the spinel were measured.The results show that samarium oxide reacts with the spinel to form SmAlO_(3)(a rare-earth aluminate) to improve the sintering performance and mechanical properties of the spinel. The formation of magnesite phases decreases the rupture strength of the spinel.However,this MgO phase is inlaid in spinel grains boundary,has a pinning effect which can improve the sinterability of the spinel.展开更多
Nanocrystalline Ni-Fe FCC alloy coatings with Fe content of 1.3%-39%（mass fraction） were fabricated on the nickel substrates using a DC electrodeposition technique. The crystal structure, lattice strain, grain size ...Nanocrystalline Ni-Fe FCC alloy coatings with Fe content of 1.3%-39%（mass fraction） were fabricated on the nickel substrates using a DC electrodeposition technique. The crystal structure, lattice strain, grain size and lattice constant of the Ni-Fe alloy coatings were studied by X-ray diffraction technique. The chemical composition and surface morphology of the FCC Ni-Fe alloy coatings were investigated with the energy dispersive X-ray spectroscopy（EDS） and atomic force microscopy（AFM）. The results show that the Fe content of the Ni-Fe alloy coatings has a great influence on the preferred orientation, grain size, lattice constant and lattice strain. FCC Ni-Fe alloy coatings exhibit preferred orientations of（200） or（200）（111）. With an increase of Fe content, the preferred growth orientation of（200） plane is weakened gradually, while the preferred growth orientation of（111） increases. An increase of the Fe content in the range of 1.3%-25%（mass fraction） results in a significant grain refinement of the coatings. Increasing the Fe content beyond 25% does not decrease the grain size of FCC Ni-Fe alloys further. The lattice strain increases with increasing the Fe content in the FCC Ni-Fe alloys. Since the alloys with Fe content not less than 25% has similar grain size（~11 nm）, the increase in the lattice strain with the increase of Fe content cannot be attributed to the change in the grain size.展开更多
基金financially National Key R&D Program of China(No.2022YFA1504800)National Natural Science Foundation of China(Grant No.22325405,22372160,22321002)+1 种基金Liaoning Revitalization Talents Program(XLYC1807207)DICP I202104。
文摘The Zn-Al spinel oxide stands out as one of the most active catalysts for high-temperature methanol synthesis from CO_(2)hydrogenation.However,the structure–activity relationship of the reaction remains poorly understood due to challenges in atomic-level structural characterizations and analysis of reaction intermediates.In this study,we prepared two Zn-Al spinel oxide catalysts via coprecipitation(ZnAl-C)and hydrothermal(ZnAl-H)methods,and conducted a comparative investigation in the CO_(2)hydrogenation reaction.Surprisingly,under similar conditions,ZnAl-C exhibited significantly higher selectivity towards methanol and DME compared to ZnAl-H.Comprehensive characterizations using X-ray diffraction(XRD),Raman spectroscopy and electron paramagnetic resonance(EPR)unveiled that ZnAl-C catalyst had abundant ZnO species on its surface,and the interaction between the ZnO species and its ZnAl spinel oxide matrix led to the formation of oxygen vacancies,which are crucial for CO_(2)adsorption and activation.Additionally,state-of-the-art solid-state nuclear magnetic resonance(NMR)techniques,including ex-situ and in-situ NMR analyses,confirmed that the surface ZnO facilitates the formation of unique highly reactive interfacial formate species,which was readily hydrogenated to methanol and DME.These insights elucidate the promotion effects of ZnO on the ZnAl spinel oxide in regulating active sites and reactive intermediates for CO_(2)-to-methanol hydrogenation reaction,which is further evidenced by the significant enhancement in methanol and DME selectivity observed upon loading ZnO onto the ZnAl-H catalyst.These molecular-level mechanism understandings reinforce the idea of optimizing the ZnO-ZnAl interface through tailored synthesis methods to achieve activity-selectivity balance.
基金National Natural Science Foundation of China (U23A6005 and 22078069)Project funded by China Postdoctoral Science Foundation (GZB20230172 and 2023M740748)。
文摘Electrochemical conversion of lignin for the production of high-value heterocyclic aromatic compounds has great potential.We demonstrate the targeted synthesis and cation modulation of NiCo_(2)O_(4)spinel nanoboxes,synthesized via cation exchange and calcination oxidation.These catalysts exhibit excellent efficacy in the electrocatalytic conversion of lignin model compounds,specifically 2-phenoxy-1-phenylethanol,into nitrogen-containing aromatics,achieving high conversion rates and selectivities.These catalysts were synthesized via a cation exchange and calcination oxidation process,using Prussian blue nanocubes as precursors.The porous architecture and polymetallic composition of the NiCo_(2)O_(4)spinel demonstrated superior performance in electrocatalytic oxidative coupling,achieving a 99.2 wt%conversion rate of the 2-phenoxy-1-phenylethanol with selectivities of 37.5 wt%for quinoline derivatives and 31.5 wt%for phenol.Key innovations include the development of a sustainable one-pot synthesis method for quinoline derivatives,the elucidation of a multistage reaction pathway involving CAO bond cleavage,hydroxyaldol condensation,and CAN bond formation,and a deeper mechanistic understanding derived from DFT simulations.This work establishes a new strategy for lignin valorization,offering a sustainable route to produce high-value nitrogen-containing aromatics from renewable biomass under mild conditions,without the need for additional reagents.
基金financially supported by the National Natural Science Foundation of China(Nos.52472032 and 52172023)the Key Program of Natural Science Foundation of Hubei Province(No.2024AFA083)
文摘High-temperature industries,as the primary consumers of energy,are greatly concerned with energy savings.Designing refractory linings with low thermal conductivity to reduce heat dissipation through high-temperature furnace linings is a critical concern.In this study,a series of novel entropy-stabilized spinel materials are reported,and their potential applications in high-temperature industries are investigated.XRD and TEM results indicate that all materials possess a cubic spinel crystal structure with the■space group.Furthermore,these materials exhibit good phase stability at high temperatures.All entropy-stabilized spinel aggregates demonstrated high refractoriness(>1800℃)and a high load softening temperature(>1700℃).The impact of configurational entropy on the properties of entropy-stabilized spinel materials was also studied.As configurational entropy increased,the thermal conductivity of the entropy-stabilized spinel decreased,while slag corrosion resistance deteriorated.For the entropy-stabilized spinel with a configurational entropy value of 1.126R,it showed good high-temperature stability,reliable resistance to slag attack,and a low thermal conductivity of 2.776 W·m^(-1)·K^(-1)at 1000℃.
基金supported by the National Natural Science Foundation of China(Nos.22206146,22006079,and U21A20524)the Fundamental Research Funds for the Central Universities,the Youth Innovation Promotion Association of Chinese Academy of Sciences,the Fundamental Research Program of Shanxi Province(No.202103021223280)+1 种基金the Special Fund for Science and Technology Innovation Teams of Shanxi Province(No.202204051002026)the Natural Science Foundation of Shandong Province(No.ZR2021QB133).
文摘Owing to the complexity of multicomponent gases,developing multifunctional catalysts for synergistic removal of benzene and toluene remains challenging.The spinel MMn_(2)O_(4)(M=Co,Ni,or Cu)catalysts were successfully synthesized via the sol–gel method and tested for their catalytic performance for simultaneous degradation of benzene and toluene.The CuMn_(2)O_(4)sample exhibited the best catalytic performance,the conversion of benzene reached 100%at 350℃,and toluene conversion reached 100%at 250℃.XRD,N_(2)adsorption-desorption,HRTEM-EDS,ED-XRF,Raman spectroscopy,H_(2)-TPR,NH_(3)-TPD,O_(2)-TPD and XPS were used to characterize the physical and chemical properties of MMn_(2)O_(4)catalysts.The excellent redox properties,high concentration of surface Mn4+,and adsorption of oxygen species over the CuMn_(2)O_(4)sample facilitated the simultaneous and efficient removal of benzene and toluene.Additionally,in situ DRIFTS illustrated the intermediate species and reaction mechanism for the synergetic catalytic oxidation of benzene and toluene.Notably,as an effective catalytic material,spinel oxide exhibited excellent synergistic degradation performance for benzene and toluene,providing some insight for the development of efficient multicomponent VOC catalysts.
基金supported by the National Natural Science Foundation of China(Nos.52370158 and 22006053)Guangzhou Science and Technology Plan Project(No.2024A04J0821)Guangdong Provincial Education Science Planning Project(Higher Education Special Project)(No.2023GXJK108).
文摘Electroplating sludge(ES),a byproduct of the electroplating industry,is a significant environmental concern due to its high content of soluble heavy metals(HMs).The significance of spinel formation from ES lies in its potential for HMs enrichment and environmental remediation,offering a sustainable solution for hazardous waste management.The article delves into themultifaceted recycling of HMs-rich spinel fromES,encompassing its synthesis,metal enrichment,and thermodynamic stability.The pyro-metallurgical and hydrometallurgical processes for spinel synthesis were discussed,with a focus on the critical role of thermodynamic data in predicting the stability and formation of spinel structures.The crystallographic and magnetic properties of spinels,with their applications in environmental remediation and energy storage are highlighted.The article provides a comprehensive reviewon the recycling of HMs-rich spinel fromES,offering a means to recycle HMs,mitigate ecological harm,and contribute to a circular economy through the recovery and application of valuable materials.The selective leaching of metals from ES also faces challenges,which was limited by the separation,purification steps and high energy consumption.This high energy consumption is a significant operational cost and also contributes to environmental concerns related to carbon emissions.It is essential to address the challenges through continued research and development,improved technologies,and supportive regulatory frameworks.
基金the Deanship of Scientific Research at King Khalid University for funding this work through Large Groups Project under(RGP.2/111/44)。
文摘In this research work,sol-gel technique was employed to prepare the strontium based spinel ferrite nanoparticles(SrFe_(2)O_(4))with different ratios of terbium(Tb).Different characterization techniques were used to investigate the structural,morphological,dielectric and magnetic properties of the prepared samples.X-ray diffraction(XRD)result suggests that face-centered cube spinel nanocrystalline structure is formed.Crystallite size of the SrFe_(2)O_(4)decreases with rising of Tb ratio.The morphology,shape and size of the SrFe_(2)O_(4)were examined by scanning electron microscopy(SEM)analysis and results reveal inhomogeneous distributions of the nanostructures with high agglomeration.The electrical resistivity of the SrFe_(2)O_(4)increases with rising of Tb ratio,which is confirmed from the cyclic voltammetry.It is observed that dielectric constant of all the samples decreases with the increasing frequency range.It is determined that the dielectric constants of the spinel ferrites are frequency dependent and decrease with increasing the frequency of applied electric field.The magnetic behavior of SrFe_(2)O_(4)with different ratios of Tb was studied and it is found that the saturation magnetization values of samples decrease with increase in the substitution of Tb^(3+)at octahedral sites for Fe^(3+).This decrease in the values of M_(s) is also attributed to spin at surface of nanoparticles.
基金supported by the startup funding of HLX provided by UC Irvine.
文摘Spinel LiNi_(0.5)Mn_(1.5)O_(4)(LNMO)is a promising high-voltage cathode material for the next generation lithium metal batteries because of its high operating voltage plateau(4.7 V vs.Li+/Li),high theoretical specific capacity(147 mAh/g),relatively low cost and environmentally benign properties.Despite promising,the commercialization of LNMO cathodes is hindered by its electrochemical instability using conventional carbonate electrolytes,resulting in lower Coulombic efficiency and poor cycling stability.Herein,we adopt an all-fluorinated electrolyte(AFE)with a wide electrochemical stability window for Li//LNMO cells.Compared to conventional carbonate electrolytes,AFE significantly improves the discharge capacity and rate performance of Li//LNMO cells at various cut-off voltages and temperatures,attributed to the formation of a robust cathode-electrolyte interphase(CEI)layer.Specifically,the resultant Li//AFE//LNMO cells deliver a discharge capacity of 131.7 mAh/g with 84.1%capacity retention after 250 cycles at a charge cut-off voltage of 4.9 V,while it sustains only 114.8 mAh/g with 81.9%capacity retention for the cell using a conventional carbonate electrolyte.The influence of charge/discharge rate and temperature on the performance is also evaluated.Overall,this study presents a facile approach to promote the commercialization of high-voltage LNMO cathodes.
基金financially supported by the National Science Fund for Distinguished Young Scholars(No.52225312)the Na-tional Natural Science Foundation of China(Nos.11904068 and 52272292)the Zhejiang Provincial Natural Science Foundation(No.LY23A040009).
文摘Antiphase boundaries(APBs)are intrinsic defects in Fe_(3)O_(4) films that significantly alter their magnetic and transport properties compared to the bulk material due to antiferromagnetic interactions across these boundaries.In the study,we realize ferromagnetically coupled APBs in spinel ferrite by cation disorder and oxygen vacancy defects.Ni and Zn are introduced into Fe_(3)O_(4) to form Ni and NiZn ferrites and cation disorder is found in the two ferrites with Ni and Zn occupied in both octahedral and tetrahedral sites.This disorder transforms the ferrites from semiconductors into half-metals,characterized by a nonzero majority spin density of states(DOS)and a zero minority spin DOS at Fermi level.The stacking fault of the cations(Fe,Ni,Zn)at the APB induces excess negative charges,leading to the formation of oxygen vacancies as charge compensators.These vacancies disrupt the antiferromagnetic superexchange interactions,preventing spin polarization reversal across the APB,thereby enabling ferromagnetic coupling.This work provides insights into tuning the magnetic properties of APBs in spinel ferrites through defect engineering and cation manipulation.
基金supported by the Key Project of the National Natural Science Foundation of China(Grant No.U21A2058)the Hebei Guoliang New Materials Co.,Ltd.(Grant No.22150239J).
文摘An experiment was conducted to assess the impact of fused calcia-stabilized zirconia micro-powder on the thermal shock behavior of magnesia–spinel refractories.The effects of calcia-stabilized zirconia on the microstructure evolution and properties of magnesia–spinel refractories were characterized by the high-temperature elastic modulus,thermal shock damage resistance parameters,retainment of elastic modulus after thermal shock,and scanning electron microscopy.The results indicated that the incorporation of calcia-stabilized zirconia improved the thermomechanical properties and thermal shock behavior of magnesia–spinel specimens.The hot modulus of rupture of magnesia–spinel specimens increased by 2.5-fold due to the incorporation of calcia-stabilized zirconia micro-powder.The presence of a martensitic phase transformation in partially unstable ZrO2 and thermal mismatches among various phases contributed to a controlled formation of microcracks.And the pinning effect caused by the calcia-stabilized zirconia particles surrounding the grain boundaries played a crucial role in preventing the propagation of microcracks.This phenomenon significantly bolstered the thermal shock stability of magnesia–spinel refractories,consequently prolonging their service life.
基金the Deanship of Scientific Research at King Khalid University for funding this work through large group Research Project under grant number RGP2/450/44。
文摘Spintronic technology and energy applications benefit greatly from the exceptional characteristics of rare-earth-based spinel chalcogenides.Examining the electrical,magnetic and thermoelectric properties of HgNd_(2)Z_(4)(Z=S,Se)in a systematic manner is essential for the strategic advancement of spin polarized current in a spintronic device.In this recent study,the WIEN2K code was employed to comprehensively analyze these properties.The calculated lattice constants,obtained using the generalized gradient approximation(GGAsol-PBE),closely match experimental findings of the similar family compounds.The examination of the stability of ferromagnetic states in the ground state involves comparing energies between anti-ferromagnetic and ferromagnetic states.Moreover,an assessment of the stability of the cubic phase in both spinels was conducted using analyses of the phonon dispersion curve,formation energy and Born stability criteria.The ductility characteristics were examined through the calculation of Poisson's and Pugh's ratios.Furthermore,details regarding the density of states,spin polarization,ex-change coupling and Curie temperature were provided to explore the characteristics associated with ferromagnetism.Potential optoelectronic applications were proposed,leveraging the direct band gaps of 1.4 and 1.0 eV for HgNd_(2)Z_(4)(Z=S,Se)respectively,within the visible spectrum.Particularly noteworthy is the effective light absorption of HgNd2Se4 in the visible range,characterized by prominent peaks that facilitate the transition of electrons from the valence band(VB)to the conduction band(CB).Additionally,the study extends to thermoelectric characteristics,determining various factors such as Seebeck coef-ficient(S),figure of merit(ZT),electrical and thermal conductivities of the evaluated spinels.
基金supported by the National Natural Science Foundation of China(No.52374344).
文摘The Ni-ZnFe_(2)O_(4)(NixZn_(1-x)Fe_(2)O_(4),x=0.4-0.7)spinel was synthesized using Zn2+extracted from electric arc furnace dust(EAFD),nickel chloride hexahydrate,and Fe^(3+)extracted from iron scale as raw materials.The zinc was selectively extracted from EAFD using CaO roasting followed by NH_(4)Cl solution leaching.The ferric ion was leached from iron scale using HCl solution as acid lixiviant.The experimental results demonstrate a high level of efficiency in the extraction of zinc,with a rate of 97.5%,and the leaching rate of ferric ion is 96.89%.The composition of the leaching solution is primary zinc and iron with low calcium,which is beneficial to the preparation of spinel ferrite.The influence of Ni content(x)and calcination temperature on the synthesis and magnetic properties of NixZn_(1-x)Fe_(2)O_(4)compounds was investigated by X-ray diffraction,scanning electron microscopy,and vibrating sample magnetometry.The results revealed that both Ni content and calcination temperature significantly affect the synthesis and magnetic properties of spinel NixZn_(1-x)Fe_(2)O_(4).Under the conditions of Ni content set at x=0.6,calcination temperature of 1100℃,and a duration of 2 h,a spinel NixZn_(1-x)Fe_(2)O_(4)with high saturation magnetization(Ms=65.7 A m2 kg-1)and low coercivity(Hc=0.056 A m^(-1))was obtained.
文摘Ensuring high electrocatalytic performance simultaneously with low or even no precious-metal usage is still a big challenge for the development of electrocatalysts toward oxygen evolution reaction(OER)in anion exchange membrane water electrolysis.Here,homogeneous high entropy oxide(HEO)film is in-situ fabricated on nickel foam(NF)substrate via magnetron sputtering technology without annealing process in air,which is composed of many spinel-structured(FeCoNiCrMo)_(3)O_(4) grains with an average particle size of 2.5 nm.The resulting HEO film(abbreviated as(FeCoNiCr-Mo)_(3)O_(4))exhibits a superior OER performance with a low OER overpotential of 216 mV at 10 mA cm^(–2) and steadily operates at 100 mA cm^(–2) for 200 h with a decay of only 272μV h^(–1),which is far better than that of commercial IrO_(2) catalyst(290 mV,1090μV h^(–1)).Tetramethylammonium cation(TMA^(+))probe experiment,activation energy analysis and theoretical calculations unveil that the OER on(FeCoNiCrMo)_(3)O_(4) follows an adsorbate evolution mechanism pathway,where the energy barrier of rate-determining step for OER on(FeCoNiCrMo)_(3)O_(4) is substantially lowered.Also,methanol molecular probe experiment suggests that a weakened ^(*)OH bonding on the(FeCoNiCrMo)_(3)O_(4) surface and a rapid deprotonation of ^(*)OH,further enhancing its OER performance.This work provides a feasible solution for designing efficient high entropy oxides electrocatalysts for OER,accelerating the practical process of water electrolysis for H2 production.
文摘In order to prepare high density magnesium aluminate spinel materials,the light-burned magnesia and alumina powder were used as the main raw materials.Active magnesium aluminate spinel powders were synthesized at different temperatures,and the sintering properties of the synthesized materials were characterized.The results show that the optimal light-burned temperature for synthesizing active magnesium aluminate spinel raw materials with small grain sizes and high sintering activity is 1400℃.The active spinel raw materials were sintered at 1750℃ for 3 h to form a dense spinel material,in which the spinel grains were well developed,exhibited a dense interlocking structure,and were uniformly distributed,with an average grain size of about 7.26μm.The bulk density and apparent porosity of the dense spinel material were 3.29 g·cm^(-3) and 3.5%,respectively.
基金supported by the National Natural Science Foundation of China(Nos.51931006,U22A20118).
文摘Spinel LiNi_(0.5)Mn_(1.5)O_(4)(LNMO)cathode draws significant attention in the field of energy storage due to its unique voltage plateau.To further enhance the long-term electrochemical stability of LNMO,the LNMO cathode covered with an ultrathin ZrO_(2)layer was prepared through atomic layer deposition(ALD).It is found that the LNMO cathode deposited with 20 layers of ZrO_(2)(LNMOZ20)exhibits the best electrochemical performance,achieving a high discharge capacity of 117.1 mA·h/g,with a capacity retention of 87.4%after 600 cycles at a current density of 1C.Furthermore,even at higher current densities of 5C and 10C,the LNMOZ20 electrode still demonstrates excellent stability with discharge capacities reaching 111.7 and 103.6 mA·h/g,and capacity retentions maintaining at 81.0%and 101.4%after 2000 cycles,respectively.This study highlights that the incorporation of an ultrathin ZrO_(2)layer by ALD is an effective strategy for enhancing the long-term cycling stability of LNMO cathodes.
基金Project(51374240) supported by the National Natural Science Foundation of ChinaProject(2012BAE08B02) supported by the National Science and Technology Pillar Program of China
文摘The densification and microstructure of different spinelized magnesium aluminate spinels（MAS） were studied adding Sc_2O_3 as additive. Sintered products were then characterized in terms of densification, phase analysis, quantitative elemental analysis and microstructure. The results show that Sc_2O_3 is found to be beneficial for the densification of MAS. Sc_2O_3 has a more significant effect on the densification of partially spinelized MAS batch than that of fully spinelized MAS batch. At the sintering temperature of 1650 °C, the bulk density of sintered products of partially spinelized powders increases by 0.243 g/cm3 as the Sc_2O_3 content increases from 0 to 4%（mass fraction） and that of fully spinelized powder increases by 0.14 g/cm3. Compared with the sintered samples prepared from the fully spinelized powder, the sintered samples using the partially spinelized powders as raw materials have more compact microstructures.
基金Project supported by the National Natural Science Foundation of China (U20A20239,51672195,51474166)。
文摘The effects of Sm_(2) O_(3) as an additive on the densification of a pre-synthesized magnesia-rich spinel were investigated.The sintering behavior of the material was characterized by analyzing its dilatometric characteristics,linear shrinkage,bulk density,apparent porosity,phase structure,and micro structure.Moreover,the cold modulus of rupture(CMOR) and microhardness of the spinel were measured.The results show that samarium oxide reacts with the spinel to form SmAlO_(3)(a rare-earth aluminate) to improve the sintering performance and mechanical properties of the spinel. The formation of magnesite phases decreases the rupture strength of the spinel.However,this MgO phase is inlaid in spinel grains boundary,has a pinning effect which can improve the sinterability of the spinel.
基金Project(51021063)supported by the National Natural Science Fund for Innovation Group of ChinaProject(2012M521540)supported by China Post Doctoral Science Foundation+1 种基金Project(2013RS4027)supported by the Post Doctoral Scientific Foundation of Hunan Province,ChinaProject(CSUZC2013023)supported by the Precious Apparatus Open Share Foundation of Central South University,China
文摘Nanocrystalline Ni-Fe FCC alloy coatings with Fe content of 1.3%-39%（mass fraction） were fabricated on the nickel substrates using a DC electrodeposition technique. The crystal structure, lattice strain, grain size and lattice constant of the Ni-Fe alloy coatings were studied by X-ray diffraction technique. The chemical composition and surface morphology of the FCC Ni-Fe alloy coatings were investigated with the energy dispersive X-ray spectroscopy（EDS） and atomic force microscopy（AFM）. The results show that the Fe content of the Ni-Fe alloy coatings has a great influence on the preferred orientation, grain size, lattice constant and lattice strain. FCC Ni-Fe alloy coatings exhibit preferred orientations of（200） or（200）（111）. With an increase of Fe content, the preferred growth orientation of（200） plane is weakened gradually, while the preferred growth orientation of（111） increases. An increase of the Fe content in the range of 1.3%-25%（mass fraction） results in a significant grain refinement of the coatings. Increasing the Fe content beyond 25% does not decrease the grain size of FCC Ni-Fe alloys further. The lattice strain increases with increasing the Fe content in the FCC Ni-Fe alloys. Since the alloys with Fe content not less than 25% has similar grain size（~11 nm）, the increase in the lattice strain with the increase of Fe content cannot be attributed to the change in the grain size.
