Balancing electron transfer and intermediate adsorption ability of metallic Ni-Fe-RE-P bifunctional catalysts via 4f-2p-3d electron interaction for enhanced water splitting

Balancing electron transfer and intermediate adsorption ability of bifunctional catalysts via tailoring electronic structures is crucial for green hydrogen production,while it still remains challenging due to lacking efficient strategies.Herein,one efficient and universal strategy is developed to greatly regulate electronic structures of the metallic Ni-Fe-P catalysts via in-situ introducing the rare earth(RE)atoms(Ni-Fe-RE-P,RE=La,Ce,Pr,and Nd).Accordingly,the as-prepared optimal Ni-Fe-Ce-P/CC self-supported bifunctional electrodes exhibited superior electrocatalytic activity and excellent stability with the low overpotentials of 247 and 331 mV at 100 mA cm^(-2) for HER and OER,respectively.In the assembled electrolyzer,the Ni-Fe-Ce-P/CC as bifunctional electrodes displayed low operation potential of 1.49 V to achieve a current density of 10 mA cm^(-2),and the catalytic performance can be maintained for 100 h.Experimental results combined with density functional theory(DFT)calculation reveal that Ce doping leads to electron decentralization and crystal structure distortion,which can tailor the band structures and d-band center of Ni-Fe-P,further increasing conductivity and optimizing intermediate adsorption energy.Our work not only proposes a valuable strategy to regulate the electron transfer and intermediate adsorption of electrocatalysts via RE atoms doping,but also provides a deep under-standing of regulation mechanism of metallic electrocatalysts for enhanced water splitting.

Magnetic and magnetocaloric effect of Er_(20)Ho_(20)Dy_(20)Cu_(20)Ni_(20)high-entropy metallic glass

Er_(20)Ho_(20)Dy_(20)Cu_(20)Ni_(20)high-entropy metallic glass exhibited excellent magnetic refrigeration material with a wide temperature range and high refrigeration capacity(RC)was reported.Er_(20)Ho_(20)Dy_(20)Cu_(20)Ni_(20)high-entropy metallic glass was observed with typical spin glass behavior around 15.5 K.In addition,we find that the magnetic entropy change(-△S_(M))originates from the sample undergoing a ferromagnetic(FM)to paramagnetic(PM)transition around 20 K.Under a field change from 0 T to 7 T,the value of maximum magnetic entropy change(-△S_(M)^(max))reaches 12.5 J/kg·K,and the corresponding value of RC reaches 487.7 J/kg in the temperature range from 6 K to 60 K.The large RC and wide temperature range make the Er_(20)Ho_(20)Dy_(20)Cu_(20)Ni_(20)high-entropy metallic glass be a promising material for application in magnetic refrigerators.

Influences of divalent ion substitution on the magnetic and dielectric properties of W-type barium ferrite

Saturation magnetization,magneto-crystalline anisotropy field,and dielectric properties are closely related to microwave devices applied at different frequencies.For regulating the magnetic and dielectric properties of W-type barium ferrites,single-phase BaMe_(2)Fe_(16)O_(27)(Me=Fe,Mn,Zn,Ni,Co) with different Me ions were synthesized by the high-temperature solid-state method.The saturation magnetization(Ms) range from 47.77 emu/g to 95.34 emu/g and the magnetic anisotropy field(H_a) range from 10700.60 Oe(1 Oe=79.5775 A·m^(-1)) to 13739.57 Oe,depending on the type of cation substitution in the hexagonal lattice.The dielectric permittivity and dielectric loss decrease with increasing frequency of the AC electric field in the low-frequency region,while they almost remain constant in the high-frequency region.The charac teristics of easy regulation and preparation make it a potential candidate for use in microwave device applications.

Laser additive manufacturing of zinc:formation quality,texture,and cell behavior

Laser powder bed fusion(LPBF)makes it possible for biodegradable zinc(Zn)to be used to produce customized orthopedic implants.In this research,we investigate the impact of laser power and scanning speed on the development of surface quality,relative densification,and texture during LPBF of Zn implants.Increasing laser power was able to decrease melt viscosity and surface tension,which improved the metallurgical bonding between adjacent tracks.Uneven and twisted tracks also became continuous and straight.Scanning speed could controlmolten-pool temperature to restrain grain natural orientation,achieving various crystal orientations and a weakened texture.Importantly,it further avoided the thermal expansion and contraction caused by excessive energy storage and accumulation in the matrix,thus reducing the generation of high-dislocation density.As a result,by selecting a reasonable laser power and scanning speed,the LPBF parts exhibited a flat surface morphology and a high density over 99.5%.Their average hardness,mechanical strength,and elongation reached 50.2 HV,127.8 MPa,and 7.6%,respectively.Additionally,the parts displayed a moderate degradation rate and excellent osteogenic properties.All these results provide a basis for selecting process parameters to optimize the comprehensive properties of LPBF-processed Zn parts for biodegradable applications.

Magnetocaloric properties of phenolic resin bonded La(Fe,Si)13-based plates and its use in a hybrid magnetic refrigerator

We present a simple hot press-based method for processing La(Fe,Si)13-based compounds consisting of La–Fe–Co–Si–C particles and phenolic resin. The magnetic entropy change △S per unit mass for the La Fe_(10.87)Co_(0.63)Si_(1.5)C_(0.2)/phenolic resin compounds have nearly the same magnitude with the base materials. With the content of phenolic resin of 5.0 wt%, the compound conductivity is 3.13 W·m^(-1)·K^(-1). In order to measure the cooling performance of La(Fe,Si)13-based compounds,the La(Fe_(11.6-x)Co_(x))Si_(1.4)C_(0.15)(x =0.60, 0.65, 0.75, 0.80, 0.85)/phenolic resin compounds were pressed into thin plates and tested in a hybrid refrigerator that combines the active magnetic refrigeration effect with the Stirling cycle refrigeration effect. The test results showed that a maximum cooling power of 41 W was achieved over a temperature span of 30 K.

Optimization of the grain boundary diffusion process by doping gallium and zirconium in Nd–Fe–B sintered magnets

As the channel for grain boundary diffusion(GBD)in Nd–Fe–B magnets,grain boundary(GB)phases have a very important effect on GBD.As doping elements that are commonly used to regulate the GB phases in Nd–Fe–B sintered magnets,the influences of Ga and Zr on GBD were investigated in this work.The results show that the Zr-doped magnet has the highest coercivity increment(7.97 kOe)by GBD,which is almost twice that of the Ga-doped magnet(4.32 kOe)and the magnet without Ga and Zr(3.24 kOe).Microstructure analysis shows that ZrB_(2)formed in the Zr-doped magnet plays a key role in increasing the diffusion depth.A continuous diffusion channel in the magnet can form because of the presence of ZrB_(2).ZrB_(2)can also increase the defect concentration in GB phases,which can facilitate GBD.Although Ga can also improve the diffusion depth,its effect is not very obvious.The micromagnetic simulation based on the experimental results also proves that the distribution of Tb in the Zr-doped magnet after GBD is beneficial to coercivity.This study reveals that the doping elements Ga and Zr in Nd–Fe–B play an important role in GBD,and could provide a new perspective for researchers to improve the effects of GBD.

Conductive path and local oxygen-vacancy dynamics:Case study of crosshatched oxides

By employing scanning probe microscopy,conductive path and local oxygen-vacancy dynamics have been investigated in crosshatched La_(0.7)Sr_(0.3)MnO_(3) thin films grown onto flat and vicinal LaAlO_(3)(001)single crystal substrates.Consistent with prior studies,the crosshatch topography was observed first by dynamical force microscopy as the epi-stain started to release with increasing film thickness.Second,by using conductive atomic force microscopy(CAFM),conductive crosshatch and dots(locally aligned or random)were unravelled,however,not all of which necessarily coincided with that shown in the in situ atomic force microscopy.Furthermore,the current-voltage responses were probed by CAFM,revealing the occurrence of threshold and/or memristive switchings.Our results demonstrate that the resistive switching relies on the evolution of the local profile and concentration of oxygen vacancies,which,in the crosshatched films,are modulated by both the misfit and threading dislocations.

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.

Giant low-field cryogenic magnetocaloric effect in polycrystalline LiErF4 compound

Antiferromagnetic LiErF4has attracted extensive attention due to its dipolar interaction domination and quantum fluctuations action. In the present work, the crystal structure, cryogenic magnetic properties, and magnetocaloric effect(MCE) of polycrystalline LiErF4compound are investigated. Crystallographic study shows that the compound crystallizes in the tetragonal scheelite structure with I41/a space group. It exhibits an antiferromagnetic(AFM) phase transition around 0.4 K, accompanied by a giant cryogenic MCE. At 1.3 K, the maximum values of magnetic entropy changes are 24.3 J/kg·K,33.1 J/kg·K, and 49.0 J/kg·K under the low magnetic field change of 0–0.6 T, 0–1 T, and 0–2 T, respectively. The giant MCE observed above Néel temperature TNis probably due to the strong quantum fluctuations, which cause a large ratio of the unreleased magnetic entropy existing above the phase transition temperature. The outstanding low-field MCE below 2 K makes the LiErF4compound an attractive candidate for the magnetic refrigeration at the ultra-low temperature.

Direct atomic-level insight into oxygen reduction reaction on size-dependent Pt-based electrocatalysts from density functional theory calculations

Developing novel oxygen reduction reaction(ORR)catalysts with high activity is urgent for proton exchange membrane fuel cells.Herein,we investigated a group of size-dependent Pt-based catalysts as promising ORR catalysts by density functional theory calculations,ranging from single-atom,nanocluster to bulk Pt catalysts.The results showed that the ORR overpotential of these Pt-based catalysts increased when its size enlarged to the nanoparticle scale or reduced to the single-atom scale,and the Pt_(38)cluster had the lowest ORR overpotential(0.46 V)compared with that of Pt_(111)(0.57 V)and single atom Pt(0.7 V).Moreover,we established a volcano curve relationship between the ORR overpotential and binding energy of O*(ΔE_(O*),confirming the intermediate species anchored on Pt38cluster with suitable binding energy located at top of volcano curve.The interaction between intermediate species and Pt-based catalysts were also investigated by the charge distribution and projected density of state and which further confirmed the results of volcano curve.

Structural Determination,Unstable Antiferromagnetism and Transport Properties of Fe-Kagome Y_(0.5)Fe_(3)Sn_(3) Single Crystals

Kagome materials have been studied intensively in condensed matter physics.With rich properties,various Kagome materials emerge during this process.Here,we grew single crystals of Y_(0.5)Fe_(3)Sn_(3)and confirmed an YCo_(6)Ge_(6)-type Kagome-lattice structure by detailed crystal structure characterizations.This compound bears an antiferromagnetic ordering at T_(N)= 551 K,and shows a weak ferromagnetism at low temperatures,where an anomalous Hall effect was observed,suggesting the non-zero Berry curvature.With the unstable antiferromagnetic ground state,our systematic investigations make Y_(0.5)Fe_(3)Sn_(3)a potential Kagome compound for Kagome or topological physics.

Improve titanate reduction by electro-deoxidation of Ca_(3)Ti_(2)O_(7) precursor in molten CaCl_(2)

The low O^(2-)diffusion rate in the electro-deoxidation of titanium containing compounds by either the OS process or the FFC process leads to a low reaction speed and a low current efficiency.In this study,Ca_(3)Ti_(2)O_(7) was used as a precursor to improve the reduction speed of titanium.Because of the greater number of"diffusion channels"created in cathode as Ca^(2+) liberates from Ca_(3)Ti_(2)O_(7) precursor in the electrodeoxidation process,the O^(2-)diffusion rate was improved significantly by using Ca_(3)Ti_(2)O_(7) instead of CaTiO3 as precursor.Parallel constant voltage electrolysis(3.2 V)confirms that Ca_(3)Ti_(2)O_(7) and CaTiO3 are reduced simultaneously because of their similar crystal structures.However,the reduction area of Ca_(3)Ti_(2)O_(7) spreads much faster than that of CaTiO3,indicating a difference in the O^(2-) diffusion rate.Constant voltage cyclic voltammetry(CV)and theoretical analysis of the crystal structure were also conducted to compare the differences between Ca_(3)Ti_(2)O_(7) and CaTiO3.The results indicate that using a precursor with a greater number of soluble cations,titanium reduction speed can be greatly improved in the electro-deoxidation process.Finally,a new electrolysis method for converting and recycling excess CaO from the Ca_(3)Ti_(2)O_(7) precursor was proposed.

Magnetic properties and magnetocaloric effects of Tm_(1-x)Er_(x)CuAl(x=0.25,0.5,and 0.75)compounds

We investigate the structural,magnetic,and magnetocaloric effects(MCE)of Tm_(1-x)Er_(x)CuAl(x=0.25,0.5,and 0.75)compounds.The compounds undergo a second-order phase transition originating from the ferromagnetic to paramagnetic transition around 3.2 K,5 K,and 6 K,respectively.The maximum magnetic entropy changes(-△S_(M)^(max))of Tm_(1-x)Er_(x)CuAl(x=0.25,0.5,and 0.75)are 17.1 J·kg^(-1)·K^(-1),18.1 J·kg^(-1)·K^(-1),and 17.5 J·kg^(-1)·K^(-1)under the magnetic field in the range of 0-2 T,with the corresponding refrigerant capacity(RC)values of 131 J·kg^(-1),136 J·kg^(-1),and 126 J·kg^(-1),respectively.The increase of-△S_(M)^(max)for Tm0.5Er0.5CuAl may be relevant to the change of magnetic moment distribution of Er and stress coming from element substitution.This work provides several compounds that can enrich the family of giant MCE materials in the cryogenic region.

Magnetic properties and magnetocaloric effect in RE_(55)Co_(30)Al_(10)Si_(5)(RE=Er and Tm)amorphous ribbons

The magnetic and magnetocaloric effects(MCE)of the amorphous RE_(55)Co_(30)Al_(10)Si_(5)(RE=Er and Tm)ribbons were systematically investigated in this paper.Compounds with R=Er and Tm undergo a second-order magnetic phase transition from ferromagnetic(FM)to paramagnetic(PM)around Curie temperature T_(C)~9.3 K and 3 K,respectively.For Er_(55)Co_(30)Al_(10)Si_(5) compound,an obvious magnetic hysteresis and thermal hysteresis were observed at low field below 6 K,possibly due to spin-glass behavior.Under the field change of 0 T–5 T,the maximum values of magnetic entropy change(-△S_(M)^(max))reach as high as 15.6 J/kg·K and 15.7 J/kg·K for Er_(55)Co_(30)Al_(10)Si_(5) and Tm_(55)Co_(30)Al_(10)Si_(5) compounds,corresponding refrigerant capacity(RC)values are estimated as 303 J/kg and 189 J/kg,respectively.The large MCE makes amorphous RE_(55)Co_(30)Al_(10)Si_(5)(RE=Er and Tm)alloys become very attractive magnetic refrigeration materials in the low-temperature region.

A review of low-carbon technologies and projects for the global cement industry

Carbon dioxide(CO_(2))emissions from the cement industry account for 26%of the total industrial emissions,and the need to develop low-carbon techniques within the cement industry is extremely urgent.Low-carbon projects and technologies for the cement industry in different regions and countries have been thoroughly reviewed in this manuscript,and the low-carbon development concept for each county has been analyzed.For developing countries such as China and India,energy saving and efficiency enhancement are currently the key points,while for developed countries and regions such as Europe,more efforts have been focused on carbon capture,utilization,and storage(CCUS).Global CCUS projects have been previously conducted,and the majority of CCUS projects are currently performed in Europe where major projects such as the CEMCAP,CLEANKER,and IEILAC projects represent the latest research progress in cement production technologies and low-carbon technologies for the global cement industry.The development of low-carbon cement technologies has changed from focusing on the end point to instead focusing on the source and process through the exploration of hydrogen and solar energies,and more disruptive and original technologies are expected to be developed,particularly in the cement industry in China.

Enhancing leaching efficiency of ion adsorption rare earths by ameliorating mass transfer effect of rare earth ions by applying an electric field

Improving the seepage of leaching solution in the ore body and strengthening the mass transfer process of rare earth ions during in-situ leaching are two critical methods to improve the leaching efficiency of rare earth.In this study,2 wt%MgSO_(4)solution was used for the indoor simulated column leaching experiment on rare earth samples and an electric field was applied at both ends of the samples.Then the effects of different intensities,initial application time and duration of the electric field on the rare earth leaching system and its mechanism were investigated.The results show that compared with the single MgSO_(4)solution leaching,applying an electric field with a strength of 6 V/cm can save the leaching time of 30 min and increase the flow velocity of the rare earth leachate by 26.98%.Under the optimal conditions of applying an electric field with a strength of 6 V/cm for 20 min to the leaching system after10 min of the rare earth leachate flowing out,the leaching efficiency of sample increases from 81.20% to 86.05% with the increase of 4.85%.The mechanism analysis shows that when a direct current electric field is applied to the rare earth leaching system,rare earth ions rapidly change from disorderly movement with the seepage into faster and directional movement.In addition,the seepage of the leaching solution is also improved due to the increase of the cross-sectional area of the seepage channel,the polarized water molecules migrate directionally by force from the negative pole,and the movement of the hydrogen is generated by the electrolytic water.More impo rtantly,based on the principle of in-situ leaching process,the layout of injection holes and deflector holes in this process provides a natural site for the electrode layout of the electric field.With the simple equipme nt and the ope ration,the rare earth leaching process with the applied electric field has high feasibility in industrial application.

Giant low-field reversible magnetocaloric effect at liquid helium temperature of niobium and iron co-substituted EuTiO_(3) compounds

Giant magnetocaloric effect(MCE)materials in the liquid helium temperature region have attracted a lot of attention in the field of low-temperature magnetic refrigeration(MR).In this study,a series of niobium(Nb)and iron(Fe)co-substituted EuTiO_(3) perovskites with cubic structure(space group pm3m)was successfully fabricated,and their magnetic properties as well as cryogenic magnetocaloric effects were investigated in detail.As expected,the introduction of Nb and Fe can significantly modulate the magnetic phase transition and magnetocaloric effect of the EuTiO_(3) compounds.With increasing Fe concentration,two local minima corresponding to the AFM-FM magnetic phase transition near 5.0 K and FM-PM transition near 10 K with no hysteresis in the thermomagnetic curves are observed,which is attributed to an enhancement of FM coupling.At the same time,the gradually widened-ΔSM-T curves and the two peaks with a broad shoulder lead to considerable refrigeration capacity(RC).With the field change ofΔH=2 T,the calculated values of-ΔS_(M)^(max) for the EuTi_(0.9375-x)Nb_(0.0625)Fe_(x)O_(3)(x=0.075,0.1,0.125,0.15)compounds are 24.2,17.6,14.5 and 14.0 J/(kg·K),respectively.The corresponding RC values were calculated to be 144.6,138.3,151.2 and 159 J/kg,respectively.Especially,the values of-ΔS_(M)^(max) for EuTi_(0.8625)Nb_(0.0625)Fe_(0.075)O_(3) are 8.6 and 15.1 J/(kg·K)under low field changes of 0.5 and 1 T,respectively.The giant low-field reversible magnetocaloric effect makes them attractive candidates for magnetic refrigeration in the liquid helium temperature region.

Effect of cobalt substitution for nickel on microstructural evolution and hydrogen storage properties of La_(0.66)Mg_(0.34)Ni_(3.5-x)Co_(x) alloys

Superlattice hydrogen storage alloys offer a compelling advantage with rapid hydriding rate and high storage capacity.However,its practical applications face challenges including complex structure,low dehydriding capacity,and cyclic instability.In this work,we successfully prepared La_(0.66)Mg_(0.34)Ni_(3.5-x)Co_(x) superlattice hydrogen storage alloys with enhanced dehydriding capacity and stability by partially substituting Co for Ni.X-ray diffraction(XRD)refinements analysis reveals the presence of(La,Mg)_(3)Ni_(9),(La,Mg)_5Ni_(19),and LaNi_(5) phases within the alloy.Following Co substitution in the La_(0.06)Mg_(0.34)Ni_(3.4)Co_(0.1)alloy,there is a significant increase in content of the(La,Mg)_(3)Ni_(9) phase and a reduction in the hysteresis factor,resulting in an improved reversible hydrogen storage capacity from 1.45 wt%to 1.60 wt%.The dehydriding kinetics of the alloy is controlled by diffusion model with an activation energy of 8.40 kJ/mol.Furthermore,the dehydriding enthalpy value of the Co-substituted alloy decreases from 30.84 to 29.85 kJ/mol.Impressively,the cycling performance of the alloy after Co substitution exhibits excellent stability,with a capacity retention rate of 92.3%after 100 cycles.These findings provide valuable insights for the development of cost-effective hydrogen storage materials.

Efficient Pt/KFI zeolite catalysts for the selective catalytic reduction of NOxby hydrogen

Aiming at purification of NO_(x)from hydrogen internal combustion engines(HICEs),the hydrogen selective catalytic reduction(H_(2)-SCR)reaction was investigated over a series of Pt/KFI zeolite catalysts.H_(2)can readily reduce NO_(x)to N_(2)and N_(2)O while O_(2)inhibited the deNO_(x)efficiency by consuming the reductant H_(2).The Pt/KFI zeolite catalysts with Pt loading below 0.1wt.% are optimized H_(2)-SCR catalysts due to its suitable operation temperature window since high Pt loading favors the H_(2)-O_(2)reaction which lead to the insufficient of reactants.Compared to metal Pt^(0)species,Pt^(δ+)species showed lower activation energy of H_(2)-SCR reaction and thought to be as reasonable active sites.Further,Eley-Rideal(E-R)reaction mechanism was proposed as evidenced by the reaction orders in kinetic studies.Last,the optimized reactor was designed with hybrid Pt/KFI catalysts with various Pt loading which achieve a high NO_(x)conversion in a wide temperature range.

Design of Ca-type todorokite catalysts with highly active for the selective reduction of NO_(x) by NH_(3) at low temperatures

Ca-type todorokite catalysts were designed and prepared by a simple redox method and applied to the selective reduction of NO_(x) by NH_(3)(NH_(3)-SCR)for the first time.Compared with the Na-type manjiroite prepared by the same method,the todorokite catalysts with different Mn/Ca ratios showed greatly improved catalytic activity for NO_(x) reduction.Among them,Mn8Ca4 catalyst exhibited the best NH_(3)-SCR performance,achieving 90%NO_(x) conversion within temperature range of 70-275℃ and having a high sulphur resistance.Compared to the Na-type manjiroite sample,Ca-type todorokite catalysts possessed an increased size of tunnel,resulting in a larger specific surface area.As increased the amounts of Ca doping,the Na content in Ca-type todorokite catalysts significantly decreased,providing larger amounts of Bronsted acid sites for NH_(3) adsorption to produce NH_(4)^(+).The NH_(4)^(+)species were highly active for reaction with NO+O_(2),playing a determining role in NH_(3)-SCR process at low temperatures.Meanwhile,larger amounts of surface adsorbed oxygen contained over the Ca-doping samples than that over Na-type manjiroite,promoting the oxidation of NO and fast SCR processes.Over the Ca-type todorokite catalysts,furthermore,nitrates produced during the flow of NO+O_(2),were more active for reaction with NH_(3) than that over Na-type manjiroite,benefiting the occurrence of NH_(3)-SCR process.This study provides novel insights into the design of NH_(3)-SCR catalysts with high performance.