Recent advances in geoscience have underscored the critical role of abiogenic processes in petroleum formation,especially the formation and polymerization of methane.However,whether a direct carbon-H_(2) reaction can ...Recent advances in geoscience have underscored the critical role of abiogenic processes in petroleum formation,especially the formation and polymerization of methane.However,whether a direct carbon-H_(2) reaction can produce C_(2+)hydrocarbons(e.g.,ethane and propane)beyond methane remains an open question.Here,we demonstrate the direct synthesis of ethane and propane via reactions between amorphous carbon and H_(2) under upper mantle conditions(2-10 GPa and 800-1200℃).A systematic investigation reveals that increasing structural disorder in carbon precursors,from graphite to glassy carbon-Ⅱ and carbon black,enhances the production of C_(2)-C_(3) hydrocarbons.Through integrated X-ray diffraction and reverse Monte Carlo simulations,we establish that the continuous random atomic network structures in amorphous carbon enable one-step synthesis of heavy hydrocarbons with H_(2).These models establish a direct link between atomic-scale carbon structures and the one-step synthesis of C_(2+)hydrocarbons under H2-rich,high-pressure,and high-temperature conditions—potentially revealing an efficient mechanism for the abiotic production of C_(2+)hydrocarbons in the upper mantle.展开更多
High‐entropy amorphous catalysts(HEACs)integrate multielement synergy with structural disorder,making them promising candidates for water splitting.Their distinctive features—including flexible coordination environm...High‐entropy amorphous catalysts(HEACs)integrate multielement synergy with structural disorder,making them promising candidates for water splitting.Their distinctive features—including flexible coordination environments,tunable electronic structures,abundant unsaturated active sites,and dynamic structural reassembly—collectively enhance electrochemical activity and durability under operating conditions.This review summarizes recent advances in HEACs for hydrogen evolution,oxygen evolution,and overall water splitting,highlighting their disorder-driven advantages over crystalline counterparts.Catalytic performance benchmarks are presented,and mechanistic insights are discussed,focusing on how multimetallic synergy,amorphization effect,and in‐situ reconstruction cooperatively regulate reaction pathways.These insights provide guidance for the rational design of next‐generation amorphous high‐entropy electrocatalysts with improved efficiency and durability.展开更多
The introduction of two-dimensional(2D)perovskite layers on top of three-dimensional(3D)perovskite films enhances the performance and stability of perovskite solar cells(PSCs).However,the electronic effect of the spac...The introduction of two-dimensional(2D)perovskite layers on top of three-dimensional(3D)perovskite films enhances the performance and stability of perovskite solar cells(PSCs).However,the electronic effect of the spacer cation and the quality of the 2D capping layer are critical factors in achieving the required results.In this study,we compared two fluorinated salts:4-(trifluoromethyl)benzamidine hydrochloride(4TF-BA·HCl)and 4-fluorobenzamidine hydrochloride(4F-BA·HCl)to engineer the 3D/2D perovskite films.Surprisingly,4F-BA formed a high-performance 3D/2D heterojunction,while4TF-BA produced an amorphous layer on the perovskite films.Our findings indicate that the balanced intramolecular charge polarization,which leads to effective hydrogen bonding,is more favorable in 4F-BA than in 4TF-BA,promoting the formation of a crystalline 2D perovskite.Nevertheless,4TF-BA managed to improve efficiency to 24%,surpassing the control device,primarily due to the natural passivation capabilities of benzamidine.Interestingly,the devices based on 4F-BA demonstrated an efficiency exceeding 25%with greater longevity under various storage conditions compared to 4TF-BA-based and the control devices.展开更多
Metal hydrides with high hydrogen density provide promising hydrogen storage paths for hydrogen transportation.However,the requirement of highly pure H_(2)for re-hydrogenation limits its wide application.Here,amorphou...Metal hydrides with high hydrogen density provide promising hydrogen storage paths for hydrogen transportation.However,the requirement of highly pure H_(2)for re-hydrogenation limits its wide application.Here,amorphous Al_(2)O_(3)shells(10 nm)were deposited on the surface of highly active hydrogen storage material particles(MgH_(2)-ZrTi)by atomic layer deposition to obtain MgH_(2)-ZrTi@Al_(2)O_(3),which have been demonstrated to be air stable with selective adsorption of H_(2)under a hydrogen atmosphere with different impurities(CH_(4),O_(2),N_(2),and CO_(2)).About 4.79 wt%H_(2)was adsorbed by MgH_(2)-ZrTi@10nmAl_(2)O_(3)at 75℃under 10%CH_(4)+90%H_(2)atmosphere within 3 h with no kinetic or density decay after 5 cycles(~100%capacity retention).Furthermore,about 4 wt%of H_(2)was absorbed by MgH_(2)-ZrTi@10nmAl_(2)O_(3)under 0.1%O_(2)+0.4%N_(2)+99.5%H_(2)and 0.1%CO_(2)+0.4%N_(2)+99.5%H_(2)atmospheres at 100℃within 0.5 h,respectively,demonstrating the selective hydrogen absorption of MgH_(2)-ZrTi@10nmAl_(2)O_(3)in both oxygen-containing and carbon dioxide-containing atmospheres hydrogen atmosphere.The absorption and desorption curves of MgH_(2)-ZrTi@10nmAl_(2)O_(3)with and without absorption in pure hydrogen and then in 21%O_(2)+79%N_(2)for 1 h were found to overlap,further confirming the successful shielding effect of Al_(2)O_(3)shells against O_(2)and N_(2).The MgH_(2)-ZrTi@10nmAl_(2)O_(3)has been demonstrated to be air stable and have excellent selective hydrogen absorption performance under the atmosphere with CH_(4),O_(2),N_(2),and CO_(2).展开更多
Beryllium-containing sludge(BCS)is a typical hazardous waste from Be smelting,which can cause serious harm to ecology and human health by releasing harmful Be if it is stored long-term in environment.Nonetheless,the o...Beryllium-containing sludge(BCS)is a typical hazardous waste from Be smelting,which can cause serious harm to ecology and human health by releasing harmful Be if it is stored long-term in environment.Nonetheless,the occurrence of Be in BCS is unclear,which seriously hinders the development of pollution control technologies.In order to enhance the understanding of BCS,the occurrence of Be and the microscale interactions with coexisting phases were investigated for the first time.It was found that CaSO_(4)·2H_(2)O and amorphous SiO_(2) are the primary phases of BCS.The simulated experiments of purified materials showed that Be interacted with CaSO_(4)·2H_(2)O and amorphous SiO_(2).Be can enter into the lattice of CaSO_(4)·2H_(2)O mainly as free Be2+.Amorphous SiO_(2) can adsorb Be2+particularly at a pH range of 3–5.The dissolution behavior experiment of BCS shows that about 52%of the Be is readily extracted under acidic conditions,which refers to the Be of independent occurrence.In contrast,the remaining 48%of Be can be extracted only after the CaSO_(4)·2H_(2)O has completely dissolved.Hence,CaSO_(4)·2H_(2)O is identified as the key occurrence phase which determines the highly efficient dissolution of Be.As a result,this study enhances the understanding of BCS and lays the foundation for the development of Be separation technologies.展开更多
Guided bone regeneration in the alveolar bone relies on the colonization and differentiation of immune cells within the defect area.The absence of osteoinductive and osteoimmune properties of currently available scaff...Guided bone regeneration in the alveolar bone relies on the colonization and differentiation of immune cells within the defect area.The absence of osteoinductive and osteoimmune properties of currently available scaffolds hinders to achieve optimal repair outcomes in clinical settings.Thus,we aimed to enhance the bone repair ability of polycaprolactone(PCL)scaffolds by incorporating osteoinductive amorphous calcium phosphate(ACP)with immune-regulating zinc ions(ACP(Zn),ACZP),to create a favorable immunomodulatory microenvironment.After one day of co-culture with PCL-ACZP,the spreading area of macrophage cells was significantly higher than that from the original PCL scaffold.Additionally,over 32.1%of macrophages exhibited M2 polarization within three days of co-culture.The PCLACZP/macrophage-conditioned medium significantly boosted osteogenic gene expression in MC3T3-E1 cells.After eight weeks of implantation in a rat femoral condyle defect,the BV/TV from the PCL-ACZP group reached 32.9%,1.4 times of that from the PCL group.Furthermore,the PCL-ACZP-GelMA biphasic module as prepared successfully achieved complete regeneration of three-walled alveolar bone defects in rabbits,resulting in arch-shaped alveolar bone repair and providing greater convenience in the clinical settings.This study showcased the effectiveness of PCL-ACZP-GelMA biphasic module as bioactive scaffolds in the morphological restoration of alveolar bone.展开更多
The unique high-entropy and sluggish diffusion effects of amorphous high-entropy alloys endow them with excellent thermal stability and plastic deformation.In this work,the near-equiatomic TaTiZr amorphous medium-entr...The unique high-entropy and sluggish diffusion effects of amorphous high-entropy alloys endow them with excellent thermal stability and plastic deformation.In this work,the near-equiatomic TaTiZr amorphous medium-entropy alloy(AMEA)was prepared via the magnetron sputtering to investigate the microstructural thermostability and nanoindentation creep behavior.Thermal annealing below the glass transition temperature gave rise to the microstructural heterogeneity due to the positive mixing enthalpy in TaTiZr AMEA,which became increasingly enhanced with raising the annealing temperature.Correspondingly,there appeared a monotonic increase in hardness as well as the elastic/shear modulus,yet a reduction in strain-rate sensitivity m or an increment in shear transformation zone volume with annealing temperature.Meanwhile,the indentation morphology measured by atomic force microscope exhibited a significant transformation from pile-up to sink-in,demonstrating the degradation of plastic deformability with enhancing the microstructural heterogeneity.Based on the relaxation time spectra for Maxwell-Voigt model,the microstructural heterogeneity can restrain the activation of internal defects associated with the operation of flow units during creeping,further triggering the strain-strengthening behavior and improved creep resistance in the annealed samples.This work provides significant guidance for the structural design of high-performance amorphous alloys.展开更多
In general,the rapid growth of α-Fe clusters is a challenge in high Fe-content Fe-based amorphous alloys,negatively affecting their physical properties.Herein,we introduce an efficient and rapid post-treatment techni...In general,the rapid growth of α-Fe clusters is a challenge in high Fe-content Fe-based amorphous alloys,negatively affecting their physical properties.Herein,we introduce an efficient and rapid post-treatment technique known as ultrasonic vibration rapid processing(UVRP),which enables the formation of high-density strong magnetic α-Fe clusters,thereby enhancing the soft magnetic properties of Fe_(78)Si(13)B_(9) amorphous alloy ribbon.展开更多
Lithium-ion batteries with LiCoO_(2)(LCO)cathodes are widely used in various electronic devices,resulting in a large amount of spent LCO(SLCO).Therefore,there is an urgent need for an efficient technique for recycling...Lithium-ion batteries with LiCoO_(2)(LCO)cathodes are widely used in various electronic devices,resulting in a large amount of spent LCO(SLCO).Therefore,there is an urgent need for an efficient technique for recycling SLCO.However,due to the presence of cobalt oxide with a spinel phase on the surface of highly-degraded LCO,the strong electrostatic repulsion from the transition metal octahedron poses a high Li replenishment barrier,making the regeneration of highly-degraded LCO a challenge.Herein,we propose a structural transformation strategy for reconstructing Li replenishment channels to aid the direct regeneration of highly-degraded LCO.In this approach,ball milling is employed to disrupt the inherent structure of highly-degraded LCO,thereby releasing the internal stress and converting the surface spinel phase into a homogeneous amorphous structure,which promotes Li insertion and regeneration.The regenerated LCO(RLCO)exhibits an outstanding discharge capacity of 179.10 mAh·g^(−1) in the voltage range of 3.0–4.5 V at 0.5 C.The proposed strategy is an effective regeneration approach for highly-degraded LCO,thereby facilitating the efficient recycling of spent lithium-ion battery cathode materials.展开更多
Ruthenium dioxide(RuO_(2))is one of the most promising acidic oxygen evolution reaction(OER)catalysts to replace the expensive and prevalent iridium(Ir)-based materials.However,the lattice oxygen oxidation induced Ru ...Ruthenium dioxide(RuO_(2))is one of the most promising acidic oxygen evolution reaction(OER)catalysts to replace the expensive and prevalent iridium(Ir)-based materials.However,the lattice oxygen oxidation induced Ru dissolution during OER compromises the activity and stability.Amorphous materials have been identified as a viable strategy to promote the stability of RuO_(2)in acidic OER applications.This study reported a nanoporous amorphous-rich RuMnO_(x)(A-RuMnO_(x))aerogel for efficient and stable acidic OER.Compared with highly crystalline RuMnO_(x),the weakened Ru–O covalency of A-RuMnO_(x)by forming amorphous structure is favorable to inhibiting the oxidation of lattice oxygen.Meanwhile,this also optimizes the electronic structure of Ru sites from overoxidation and reduces the reaction energy barrier of the rate-determining step.As a result,A-RuMnO_(x)aerogel exhibits an ultra-low overpotential of 145 mV at 10 mA cm^(-2)and durability exceeding 100 h,as well as high mass activity up to 153 mA mg^(-1)_(Ru)at 1.5 V vs.reversible hydrogen electrode(RHE).This work provides valuable guidance for preparing highly active and stable Ru-based catalysts for acidic OER.展开更多
A suction casting experiment was conducted on Zr_(55)Cu_(30)Al_(10)Ni_(5)(at%)amorphous alloy.Using ProCAST software,numerical simulations were performed to analyze the filling and solidification processes.The velocit...A suction casting experiment was conducted on Zr_(55)Cu_(30)Al_(10)Ni_(5)(at%)amorphous alloy.Using ProCAST software,numerical simulations were performed to analyze the filling and solidification processes.The velocity field during the filling process and the temperature field during the solidification process of the alloy melt under different process parameters were obtained.Based on the simulation results,a Zr-based amorphous alloy micro-gear was prepared via casting.The results indicate that increasing the suction casting temperature enhances the fluidity of alloy melt but induces unstable flow rate during filling,which is detrimental to complete filling.Zr-based amorphous micro-gears with a module of 0.6 mm,a tooth top diameter of 8 mm,and 10 teeth were prepared through the suction casting.X-ray diffraction and differential scanning calorimetry analyses confirm that the fabricated micro-gear exhibits characteristic amorphous structural features,demonstrating well-defined geometrical contours and satisfactory forming completeness.展开更多
Short process forming techniques for brazing and soldering materials can shorten the process,improve product quality,and increase production efficiency,which has received much attention from welding researchers.This r...Short process forming techniques for brazing and soldering materials can shorten the process,improve product quality,and increase production efficiency,which has received much attention from welding researchers.This review mainly summarized the research reports on short process forming techniques for brazing and soldering materials.Firstly,the traditional process and its shortcomings were presented.Secondly,the latest research of short process forming technologies,such as continuous casting technique,atomization powder technique,solder ball forming technique,and rapid solidification technique,was summarized,and the traditional forming performance of several brazing and soldering materials was introduced.Finally,the current restrictions and research trends of short process forming technique for brazing and solder materials were put forward,providing theoretical guidance and reference for related research and technique development in brazing and soldering field.展开更多
The hydrazine oxidation reaction(HzOR)has garnered significant attention as a feasible approach to replace sluggish anodic reactions to save energy.Nevertheless,there are still difficulties in developing highly effici...The hydrazine oxidation reaction(HzOR)has garnered significant attention as a feasible approach to replace sluggish anodic reactions to save energy.Nevertheless,there are still difficulties in developing highly efficient catalysts for the HzOR.Herein,we report amorphous ruthenium nanosheets(a-Ru NSs)with a thickness of approximately 9.6 nm.As a superior bifunctional electrocatalyst,a-Ru NSs exhibited enhanced electrocatalytic performance toward both the HzOR and hydrogen evolution reaction(HER),outperforming benchmark Pt/C catalysts,where the a-Ru NSs achieved a work-ing potential of merely-76 mV and a low overpotential of only 17 mV to attain a current density of 10 mA·cm^(-2) for the HzOR and HER,respectively.Furthermore,a-Ru NSs displayed a low cell voltage of 28 mV at 10 mA·cm^(-2) for overall hy-drazine splitting in a two-electrode electrolyzer.In situ Raman spectra revealed that the a-Ru NSs can efficiently promote N‒N bond cleavage,thereby producing more*NH_(2)and accelerating the progress of the reaction.展开更多
[Background and purposes]Proton exchange membrane fuel cells(PEMFCs),which convert hydrogen energy directly into electrical energy and water,have received overwhelming attention,owing to their potential to significant...[Background and purposes]Proton exchange membrane fuel cells(PEMFCs),which convert hydrogen energy directly into electrical energy and water,have received overwhelming attention,owing to their potential to significantly reduce energy consumption,pollution emissions and reliance on fossil fuels.Bipolar plates are the major part and key component of PEMFCs stack,which provide mechanical strength,collect and conduct current segregate oxidants and reduce agents.They contribute 70-80%weight and 20-30%cost of a whole stack,while significantly affecting the power density.There are three types plates,including metal bipolar plate,graphite bipolar plate and composite bipolar plate.Stainless steel bipolar plates,as one of metal bipolar plate,exhibit promising manufacturability,competitive cost and durability among various metal materials.However,stainless steel would be corroded in the harsh acid(pH 2-5)and humid PEMFCs environment,whereas the leached ions will contaminate the membrane.In addition,the passivated film formed on the surface will increase the interfacial contact resistance(ICR).In order to improve the corrosion resistance and electrical conductivity of steel bipolar plates,surface coatings are essential.Metal nitride coatings,metal carbide coatings,polymer coatings and carbon-based coatings have been introduced in recent years.Carbon-based coatings,mainly including a-C(amorphous Carbon),Ta-C(Tetrahedral amorphous carbon)and DLC(diamond-like carbon),have attracted considerable attention from both academia and industry,owing to their superior performance,such as chemical inertness,mechanical hardness and electrical conductivity.However,Ta-C films as protective coating of PEMFCs have been rarely reported,due to the difficulty in production for industrial application.In this paper,multi-layer Ta-C composite films were produced by using customized industrial-scale vacuum equipment to address those issues.[Methods]Multiple layered Ta-C coatings were prepared by using PIS624 equipment,which assembled filtered cathodic arc evaporation,ion beam and magnetron sputtering into one equipment,while SS304 and silicon specimens were used as substrate for testing and analysis.Adhesion layer and intermediate layer were deposited by using magnetron sputtering at deposition temperature of 150℃and pressure of 3×10^(−1) Pa,while the sputtering current was set to be 5 A and bias power to be 300 V.The Ta-C layer was coated at arc current of 80-100 A,bias voltage of 1500 V and gas flow of 75 sccm.A scanning electron microscope(CIQTEK SEM3200)was used to characterize surface morphology,coating structure and cross-section profile of the coatings.Raman spectrometer(LabRam HR Evolution,HORIBA JOBIN YVON)was used to identify the bonding valence states.Electrochemical tests were performed by using an electrochemical work station(CHI760,Shanghai Chenhua Instrument Co.,Ltd.),with the traditional three electrode system,where saturated Ag/AgCl and platinum mesh were used as the reference electrode and counter electrode,respectively.All samples were mounted in plastic tube and sealed with epoxy resin,with an exposure area of 2.25 cm^(2),serving as the working electrode.Electrochemical measurements were carried out in simulated PEMFCs cathode environment in 0.5 mol·L^(−1) H_(2)SO_(4)+5 ppm F−solution,at operating temperature of 70℃.As the cathode environment was harsher than the anode environment,all the samples are stabilized at the open-circuit potential(OCP)for approximately 30 min before the EIS measurements.ICR between bipolar plates and GDL was a key parameter affecting performance of the PEMFCs stack.The test sample sandwiched between 2 pieces of carbon paper(simulate gas diffusion layer,GDL)was placed between 2 gold-plated copper electrodes at a compaction pressure of 1.4 MPa,which was considered to be the conventional compaction pressure in the PEMFCs.Under the same conditions,the resistance of a single carbon paper was measured as well.The ICR was calculated according to the formula ICR=1/2(R2−R1)×S,where S was the contact area between GDL and coated stainless steel BPPs.All data of ICR were measured three times for averaging.[Results]The coatings deposited by filtered cathodic arc technology were compact and smooth,which reduced coating porosity and favorable to corrosion resistance.The coating thickness of adhesion and intermediate layers were 180 nm,while the protective Ta-C coating thickness was about 300 nm,forming multiple coating to provide stronger protection for metal bipolar plates.Cr,Ti,Nb and Ta coatings were selected as adhesion layers for comparison.According to electrochemical test,Ta and Nb coatings have higher corrosion resistance.However,Ta and Nb materials would be costly when they are used for mass production.Relatively,Cr and Ti materials were cost effective.Hence,a comprehensive assessment was indispensable to decide the materials to be selected as adhesion layer.Ta-TiN and Ti-TiN combined adhesion and intermediate layer exhibited stronger corrosion resistance,with the corrosion current to be less than 10^(−6) A·cm^(−2).Ta-C protective coating deposited by using filtered cathodic arc technology indicated displayed higher corrosion resistance,with the average corrosion density to be about 1.26×10^(−7) A·cm^(−2).Ta-C coating also shown larger contact angle,with the highest hydrophobicity,which was one of the important advantages for Ta-C,in terms of corrosion resistance.According to Raman spectroscopy,the I(D)/I(G)=549.8/1126.7=0.487,with the estimated fraction of sp^(3) bonding to be in the range of 5154%.The intermediate layer TiN has higher conductivity than the CrN layer.Considering cost,corrosion performance and ICR result,the Ti-TiN layer combination is recommended for industrial scale application.[Conclusions]Multiple layer coating structure of Ta-C film had stronger corrosion resistance;with more than 50%sp^(3) content,while it also had larger water contact angle and higher corrosion resistance than DLC film.The filtered arcing deposition technology was able to make the film to be more consistent and stable than normal arcing technology in terms of the preparation of Ta-C.The coating displayed corrosion density of 1.26×10^(−7) A·cm^(−2) and ICR of less than 5 mΩ·cm^(2),far beyond technical target of 2025 DOE(US Department of Energy).This indicated that the mass-production scale coating technology for PEMFC bipolar plates is highly possible.展开更多
Amorphous Ga_(2)O_(3)(a-Ga_(2)O_(3))thin films were prepared on flexible polyimide,rigid quartz glass,and Si substrates via radio frequency magnetron sputtering at room temperature.The effect of oxygen/Ar flow rate ra...Amorphous Ga_(2)O_(3)(a-Ga_(2)O_(3))thin films were prepared on flexible polyimide,rigid quartz glass,and Si substrates via radio frequency magnetron sputtering at room temperature.The effect of oxygen/Ar flow rate ratio on the structure,optical property,surface morphology,and chemical bonding properties of the a-Ga_(2)O_(3) films was investigated.Results show that the average optical transmittance of the a-Ga_(2)O_(3) films is over 80%within the wavelength range of 300-2000 nm.The extracted optical band gap of the a-Ga_(2)O_(3) films is increased from 4.97 eV to 5.13 eV with the increase in O_(2)/Ar flow rate ratio from 0 to 0.25,due to the decrease in concentration of oxygen vacancy defects in the film.Furthermore,the optical refractive index and surface roughness of the a-Ga_(2)O_(3) films are optimized when the O_(2)/Ar flow rate ratio reaches 0.25.X-ray photoelectron spectroscopy analysis also shows that the proportion of oxygen vacancies(VO)and Ga-O chemical bonds in the O 1s peak is gradually decreased with the increase in O_(2)/Ar flow rate ratio from 0 to 0.25,proving that increasing the O_(2)/Ar flow rate ratio during film growth can reduce the concentration of oxygen vacancy defects in a-Ga_(2)O_(3) films.In this case,a-Ga_(2)O_(3) with optimal properties can be obtained.This work provides a research basis for high-performance flexible and rigid deep ultraviolet solar-blind detection devices based on a-Ga_(2)O_(3) films.展开更多
Establishing the structure-property relationship in amorphous materials has been a long-term grand challenge due to the lack of a unified description of the degree of disorder.In this work,we develop SPRamNet,a neural...Establishing the structure-property relationship in amorphous materials has been a long-term grand challenge due to the lack of a unified description of the degree of disorder.In this work,we develop SPRamNet,a neural network based machine-learning pipeline that effectively predicts structure-property relationship of amorphous material via global descriptors.Applying SPRamNet on the recently discovered amorphous monolayer carbon,we successfully predict the thermal and electronic properties.More importantly,we reveal that a short range of pair correlation function can readily encode sufficiently rich information of the structure of amorphous material.Utilizing powerful machine learning architectures,the encoded information can be decoded to reconstruct macroscopic properties involving many-body and long-range interactions.Establishing this hidden relationship offers a unified description of the degree of disorder and eliminates the heavy burden of measuring atomic structure,opening a new avenue in studying amorphous materials.展开更多
This study explores a novel strategy to enhance the hydrogen evolution reaction(HER)activity of carbon-supported rock salt-type NiCo_(2)(O,F)_(3) nanorods through lattice modifications induced by fluorine and excess a...This study explores a novel strategy to enhance the hydrogen evolution reaction(HER)activity of carbon-supported rock salt-type NiCo_(2)(O,F)_(3) nanorods through lattice modifications induced by fluorine and excess amorphous carbon.X-ray absorption near-edge structure(XANES)analysis confirmed that Co and Ni predominantly exist in the+2 oxidation state,whereas extended X-ray absorption fine structure(EXAFS)analysis revealed shortened Co-O and Co-Co bond lengths,indicating lattice distortions.Rietveld refinement and electron microscopy confirmed the formation of a homogeneous solid solution(NixCo_(2-x)(O,F)_(3))rather than a simple CoO/NiO composite.The optimized material(AH-2)exhibited the lowest overpotential(145 mV at 10 mA cm^(-1))and the smallest Tafel slope(98 mV dec^(-1)),attributed to its balanced phase composition,enhanced electronic conductivity,and synergistic effects of carbon and fluorine incorporation.Electrochemical impedance spectroscopy(EIS)confirmed improved charge transfer efficiency,correlating with enhanced catalytic activity.These findings provide critical insights into the tunability of transition metal oxide catalysts via controlled lattice modifications,offering a promising avenue for developing cost-effective and efficient electrocatalysts for sustainable hydrogen production.展开更多
Silicon,a leading candidate for electrode material for lithium-ion batteries,has garnered significant attention.During the initial lithiation process,the alloying reaction between silicon and lithium transforms the pr...Silicon,a leading candidate for electrode material for lithium-ion batteries,has garnered significant attention.During the initial lithiation process,the alloying reaction between silicon and lithium transforms the pristine silicon microstructure from crystalline to amorphous,resulting in plastic deformation of the amorphous phase.This study proposes the free volume theory to develop a fully coupled Cahn-Hilliard phase-field model that integrates viscoplastic deformation,free volume evolution,and diffusion.This model investigates the chemophysical phenomenon of self-limiting behavior occurring during the initial lithiation of silicon anodes.Unlike most existing models,the proposed model considers free volume-dependent diffusion using a physically-based approach.The model’s temporal variation in the lithiated phase thickness aligns well with experimental results,confirming the model’s accuracy.Stress field calculations reveal the coexistence of compressive and tensile stresses within the lithiated phase,which may not cause the limiting effect under the frame of the stress-induced diffusion.Analyses indicate that high effective stress increases free volume,enhancing lithium diffusion and augmenting the diffusion coefficient.Reducing the diffusion coefficient in the lithiated phase due to free volume evolution is the primary cause of self-limiting lithiation.展开更多
With the development of vanadium redox flow battery technology,the demand for pure vanadium is rapidly increasing.The separation of vanadium from vanadium-chromium leaching solutions are critical step in the productio...With the development of vanadium redox flow battery technology,the demand for pure vanadium is rapidly increasing.The separation of vanadium from vanadium-chromium leaching solutions are critical step in the production of purity-vanadium.This study presents an innovative adsorption process that utilizes amorphous ZrO_(2)(AZrO) for the selective separation of V(Ⅴ) and Cr(Ⅵ).In this process,a high adsorption capacity for V(V) at 64.5 mg·g^(-1) was achieved,while the capacity for Cr(Ⅵ) is relatively low at 24.1 mg·g^(-1),demonstrating good separation performance.This is mainly caused by the large specific surface area and mesoporous structure,which are favorable for molecular diffusion and mass transfer.The kinetic analysis shows that the adsorption process follows pseudo-second-order kinetic process with chemisorption being the rate-controlling process.AZrO showed excellent separation performance in mixed solutions over a wide range of concentrations.After five cycles,AZrO retained over 73% of its capacity,indicating good stability.In mixed solutions containing up to 40 g·L^(-1) of V(Ⅴ) and 3 g·L^(-1) of Cr(Ⅵ),the innovative adsorption process successfully achieved effective separation and purification.By an adsorption-desorption process using 0.1 mol·L^(-1) NaOH,a 99.02% V(Ⅴ)-rich solution was obtained from a high concentration sodium vanadium slag leaching solution,demonstrating its effectiveness for practical industrial applications.展开更多
Carbon nanotubes(CNTs)reinforced copper(CNTs/Cu)is one of the most promising and extensively researched materials for replacing traditional Cu-based materials in high-load and high-current applications,particularly wi...Carbon nanotubes(CNTs)reinforced copper(CNTs/Cu)is one of the most promising and extensively researched materials for replacing traditional Cu-based materials in high-load and high-current applications,particularly within the aerospace industry.Amorphous carbon nanotubes(aCNTs)are a type of carbon nanotubes characterized by the presence of mesopores distributed across their amorphous sidewalls,facilitating connectivity between the hollow core and the external environment.Therefore,we propose utilizing aCNTs as a reinforcing agent for Cu.The mesoporous structure of aCNTs facilitates the interpenetration of Cu into the aCNTs,thereby maintaining the continuity of the matrix properties.Experimental results demonstrate that Cu effectively penetrates the mesoporous sidewalls of aCNTs.Both pure Cu and aCNTs-reinforced Cu exhibit comparable electrical conductivity,while the hardness of the aCNTs/Cu composite is significantly enhanced.Additionally,both the density and porosity of aCNTs/Cu are lower than those of pure Cu,and the introduction of aCNTs helps to reduce the sintering temperature.展开更多
基金supported by the Natural Science Foundation of China(Grant Nos.52288102,52090020,and 52372261)the Natural Science Foundation of Hebei Province(Grant No.E202403045)+2 种基金the S&T Program of Hebei(Grant No.225A1102D)the Ministry of Education Chang Jiang Scholar Professor Program(Grant No.T2022241)supported by the User Experiment Assist System at SSRF.
文摘Recent advances in geoscience have underscored the critical role of abiogenic processes in petroleum formation,especially the formation and polymerization of methane.However,whether a direct carbon-H_(2) reaction can produce C_(2+)hydrocarbons(e.g.,ethane and propane)beyond methane remains an open question.Here,we demonstrate the direct synthesis of ethane and propane via reactions between amorphous carbon and H_(2) under upper mantle conditions(2-10 GPa and 800-1200℃).A systematic investigation reveals that increasing structural disorder in carbon precursors,from graphite to glassy carbon-Ⅱ and carbon black,enhances the production of C_(2)-C_(3) hydrocarbons.Through integrated X-ray diffraction and reverse Monte Carlo simulations,we establish that the continuous random atomic network structures in amorphous carbon enable one-step synthesis of heavy hydrocarbons with H_(2).These models establish a direct link between atomic-scale carbon structures and the one-step synthesis of C_(2+)hydrocarbons under H2-rich,high-pressure,and high-temperature conditions—potentially revealing an efficient mechanism for the abiotic production of C_(2+)hydrocarbons in the upper mantle.
基金supported by the Australian Research Council(ARC)Projects(DP220101139,DP220101142,and LP240100542).
文摘High‐entropy amorphous catalysts(HEACs)integrate multielement synergy with structural disorder,making them promising candidates for water splitting.Their distinctive features—including flexible coordination environments,tunable electronic structures,abundant unsaturated active sites,and dynamic structural reassembly—collectively enhance electrochemical activity and durability under operating conditions.This review summarizes recent advances in HEACs for hydrogen evolution,oxygen evolution,and overall water splitting,highlighting their disorder-driven advantages over crystalline counterparts.Catalytic performance benchmarks are presented,and mechanistic insights are discussed,focusing on how multimetallic synergy,amorphization effect,and in‐situ reconstruction cooperatively regulate reaction pathways.These insights provide guidance for the rational design of next‐generation amorphous high‐entropy electrocatalysts with improved efficiency and durability.
基金supported by the National Key Research and Development Programs-Intergovernmental International Cooperation in Science and Technology Innovation Project(Grant No.2022YFE0118400)the Natural Science Foundation of Hunan Province(2023JJ50132)+1 种基金Shenzhen Science and Technology Innovation Committee(Grants Nos.JCYJ20220818100211025,and KCXST20221021111616039)Shenzhen Science and Technology Program(No.20231128110928003)。
文摘The introduction of two-dimensional(2D)perovskite layers on top of three-dimensional(3D)perovskite films enhances the performance and stability of perovskite solar cells(PSCs).However,the electronic effect of the spacer cation and the quality of the 2D capping layer are critical factors in achieving the required results.In this study,we compared two fluorinated salts:4-(trifluoromethyl)benzamidine hydrochloride(4TF-BA·HCl)and 4-fluorobenzamidine hydrochloride(4F-BA·HCl)to engineer the 3D/2D perovskite films.Surprisingly,4F-BA formed a high-performance 3D/2D heterojunction,while4TF-BA produced an amorphous layer on the perovskite films.Our findings indicate that the balanced intramolecular charge polarization,which leads to effective hydrogen bonding,is more favorable in 4F-BA than in 4TF-BA,promoting the formation of a crystalline 2D perovskite.Nevertheless,4TF-BA managed to improve efficiency to 24%,surpassing the control device,primarily due to the natural passivation capabilities of benzamidine.Interestingly,the devices based on 4F-BA demonstrated an efficiency exceeding 25%with greater longevity under various storage conditions compared to 4TF-BA-based and the control devices.
基金supported by the National Natural Science Foundation of China(22175136)the State Key Laboratory of Electrical Insulation and Power Equipment(EIPE23127)the Fundamental Research Funds for the Central Universities(xtr052024009).
文摘Metal hydrides with high hydrogen density provide promising hydrogen storage paths for hydrogen transportation.However,the requirement of highly pure H_(2)for re-hydrogenation limits its wide application.Here,amorphous Al_(2)O_(3)shells(10 nm)were deposited on the surface of highly active hydrogen storage material particles(MgH_(2)-ZrTi)by atomic layer deposition to obtain MgH_(2)-ZrTi@Al_(2)O_(3),which have been demonstrated to be air stable with selective adsorption of H_(2)under a hydrogen atmosphere with different impurities(CH_(4),O_(2),N_(2),and CO_(2)).About 4.79 wt%H_(2)was adsorbed by MgH_(2)-ZrTi@10nmAl_(2)O_(3)at 75℃under 10%CH_(4)+90%H_(2)atmosphere within 3 h with no kinetic or density decay after 5 cycles(~100%capacity retention).Furthermore,about 4 wt%of H_(2)was absorbed by MgH_(2)-ZrTi@10nmAl_(2)O_(3)under 0.1%O_(2)+0.4%N_(2)+99.5%H_(2)and 0.1%CO_(2)+0.4%N_(2)+99.5%H_(2)atmospheres at 100℃within 0.5 h,respectively,demonstrating the selective hydrogen absorption of MgH_(2)-ZrTi@10nmAl_(2)O_(3)in both oxygen-containing and carbon dioxide-containing atmospheres hydrogen atmosphere.The absorption and desorption curves of MgH_(2)-ZrTi@10nmAl_(2)O_(3)with and without absorption in pure hydrogen and then in 21%O_(2)+79%N_(2)for 1 h were found to overlap,further confirming the successful shielding effect of Al_(2)O_(3)shells against O_(2)and N_(2).The MgH_(2)-ZrTi@10nmAl_(2)O_(3)has been demonstrated to be air stable and have excellent selective hydrogen absorption performance under the atmosphere with CH_(4),O_(2),N_(2),and CO_(2).
基金supported by the National Natural Science Foundation of China(No.22276219)the foundation for Innovative Research Groups of the National Natural Science Foundation of China(No.52121004)+1 种基金the major program Natural Science Foundation of Hunan Province of China(No.2021JC0001)the Fundamental Research Funds for the Central Universities of Central South University(No.2024ZZTS0063).
文摘Beryllium-containing sludge(BCS)is a typical hazardous waste from Be smelting,which can cause serious harm to ecology and human health by releasing harmful Be if it is stored long-term in environment.Nonetheless,the occurrence of Be in BCS is unclear,which seriously hinders the development of pollution control technologies.In order to enhance the understanding of BCS,the occurrence of Be and the microscale interactions with coexisting phases were investigated for the first time.It was found that CaSO_(4)·2H_(2)O and amorphous SiO_(2) are the primary phases of BCS.The simulated experiments of purified materials showed that Be interacted with CaSO_(4)·2H_(2)O and amorphous SiO_(2).Be can enter into the lattice of CaSO_(4)·2H_(2)O mainly as free Be2+.Amorphous SiO_(2) can adsorb Be2+particularly at a pH range of 3–5.The dissolution behavior experiment of BCS shows that about 52%of the Be is readily extracted under acidic conditions,which refers to the Be of independent occurrence.In contrast,the remaining 48%of Be can be extracted only after the CaSO_(4)·2H_(2)O has completely dissolved.Hence,CaSO_(4)·2H_(2)O is identified as the key occurrence phase which determines the highly efficient dissolution of Be.As a result,this study enhances the understanding of BCS and lays the foundation for the development of Be separation technologies.
基金financially supported by the National Natural Science Foundation of China(Nos.82203680 and 52273278)the Natural Scientific Foundation of Liaoning Province(No.2021-MS-176)+1 种基金Shenyang Bureau of Science and Technology(No.RC230527)the Central Guidance Funding for Local Scientific and Techno-logical Development in Liaoning(No.2023JH6/100100029).
文摘Guided bone regeneration in the alveolar bone relies on the colonization and differentiation of immune cells within the defect area.The absence of osteoinductive and osteoimmune properties of currently available scaffolds hinders to achieve optimal repair outcomes in clinical settings.Thus,we aimed to enhance the bone repair ability of polycaprolactone(PCL)scaffolds by incorporating osteoinductive amorphous calcium phosphate(ACP)with immune-regulating zinc ions(ACP(Zn),ACZP),to create a favorable immunomodulatory microenvironment.After one day of co-culture with PCL-ACZP,the spreading area of macrophage cells was significantly higher than that from the original PCL scaffold.Additionally,over 32.1%of macrophages exhibited M2 polarization within three days of co-culture.The PCLACZP/macrophage-conditioned medium significantly boosted osteogenic gene expression in MC3T3-E1 cells.After eight weeks of implantation in a rat femoral condyle defect,the BV/TV from the PCL-ACZP group reached 32.9%,1.4 times of that from the PCL group.Furthermore,the PCL-ACZP-GelMA biphasic module as prepared successfully achieved complete regeneration of three-walled alveolar bone defects in rabbits,resulting in arch-shaped alveolar bone repair and providing greater convenience in the clinical settings.This study showcased the effectiveness of PCL-ACZP-GelMA biphasic module as bioactive scaffolds in the morphological restoration of alveolar bone.
基金financially supported by the National Natural Science Foundation of China(Nos.U2067219,52371118,92163201,U23A6013,92360301,and U2330203)Shaanxi Province Innovation Team Project(No.2024RS-CXTD-58)the Fundamental Research Funds for the Central Universities(Nos.xtr042024014 and xtr062024006).
文摘The unique high-entropy and sluggish diffusion effects of amorphous high-entropy alloys endow them with excellent thermal stability and plastic deformation.In this work,the near-equiatomic TaTiZr amorphous medium-entropy alloy(AMEA)was prepared via the magnetron sputtering to investigate the microstructural thermostability and nanoindentation creep behavior.Thermal annealing below the glass transition temperature gave rise to the microstructural heterogeneity due to the positive mixing enthalpy in TaTiZr AMEA,which became increasingly enhanced with raising the annealing temperature.Correspondingly,there appeared a monotonic increase in hardness as well as the elastic/shear modulus,yet a reduction in strain-rate sensitivity m or an increment in shear transformation zone volume with annealing temperature.Meanwhile,the indentation morphology measured by atomic force microscope exhibited a significant transformation from pile-up to sink-in,demonstrating the degradation of plastic deformability with enhancing the microstructural heterogeneity.Based on the relaxation time spectra for Maxwell-Voigt model,the microstructural heterogeneity can restrain the activation of internal defects associated with the operation of flow units during creeping,further triggering the strain-strengthening behavior and improved creep resistance in the annealed samples.This work provides significant guidance for the structural design of high-performance amorphous alloys.
基金supported by the Major Science and Technology Project of Zhongshan City(No.2022AJ004)the Key Basic and Applied Research Program of Guangdong Province(Nos.2019B030302010 and 2022B1515120082)Guangdong Science and Technology Innovation Project(No.2021TX06C111).
文摘In general,the rapid growth of α-Fe clusters is a challenge in high Fe-content Fe-based amorphous alloys,negatively affecting their physical properties.Herein,we introduce an efficient and rapid post-treatment technique known as ultrasonic vibration rapid processing(UVRP),which enables the formation of high-density strong magnetic α-Fe clusters,thereby enhancing the soft magnetic properties of Fe_(78)Si(13)B_(9) amorphous alloy ribbon.
基金supported by a project of the Tsinghua Shenzhen International Graduate School-Shenzhen Pengrui Young Faculty Program of Shenzhen Pengrui Foundation(Grant No.SZPR2023007)Natural Science Foundation of Sichuan Province(Grant No.2025ZNSFSC0449)Shenzhen Science and Technology Program(Grant No.RCBS20231211090637065).
文摘Lithium-ion batteries with LiCoO_(2)(LCO)cathodes are widely used in various electronic devices,resulting in a large amount of spent LCO(SLCO).Therefore,there is an urgent need for an efficient technique for recycling SLCO.However,due to the presence of cobalt oxide with a spinel phase on the surface of highly-degraded LCO,the strong electrostatic repulsion from the transition metal octahedron poses a high Li replenishment barrier,making the regeneration of highly-degraded LCO a challenge.Herein,we propose a structural transformation strategy for reconstructing Li replenishment channels to aid the direct regeneration of highly-degraded LCO.In this approach,ball milling is employed to disrupt the inherent structure of highly-degraded LCO,thereby releasing the internal stress and converting the surface spinel phase into a homogeneous amorphous structure,which promotes Li insertion and regeneration.The regenerated LCO(RLCO)exhibits an outstanding discharge capacity of 179.10 mAh·g^(−1) in the voltage range of 3.0–4.5 V at 0.5 C.The proposed strategy is an effective regeneration approach for highly-degraded LCO,thereby facilitating the efficient recycling of spent lithium-ion battery cathode materials.
基金financial support from the National Natural Science Foundation of China(22478278,22308246)the Central Government Guides the Local Science and Technology Development Special Fund(YDZJSX20231A015)the Fundamental Research Program of Shanxi Province(202203021212266)。
文摘Ruthenium dioxide(RuO_(2))is one of the most promising acidic oxygen evolution reaction(OER)catalysts to replace the expensive and prevalent iridium(Ir)-based materials.However,the lattice oxygen oxidation induced Ru dissolution during OER compromises the activity and stability.Amorphous materials have been identified as a viable strategy to promote the stability of RuO_(2)in acidic OER applications.This study reported a nanoporous amorphous-rich RuMnO_(x)(A-RuMnO_(x))aerogel for efficient and stable acidic OER.Compared with highly crystalline RuMnO_(x),the weakened Ru–O covalency of A-RuMnO_(x)by forming amorphous structure is favorable to inhibiting the oxidation of lattice oxygen.Meanwhile,this also optimizes the electronic structure of Ru sites from overoxidation and reduces the reaction energy barrier of the rate-determining step.As a result,A-RuMnO_(x)aerogel exhibits an ultra-low overpotential of 145 mV at 10 mA cm^(-2)and durability exceeding 100 h,as well as high mass activity up to 153 mA mg^(-1)_(Ru)at 1.5 V vs.reversible hydrogen electrode(RHE).This work provides valuable guidance for preparing highly active and stable Ru-based catalysts for acidic OER.
基金National Natural Science Foundation of China(51971103)Key Research and Development Program in Gansu Province(20YF8GA052)。
文摘A suction casting experiment was conducted on Zr_(55)Cu_(30)Al_(10)Ni_(5)(at%)amorphous alloy.Using ProCAST software,numerical simulations were performed to analyze the filling and solidification processes.The velocity field during the filling process and the temperature field during the solidification process of the alloy melt under different process parameters were obtained.Based on the simulation results,a Zr-based amorphous alloy micro-gear was prepared via casting.The results indicate that increasing the suction casting temperature enhances the fluidity of alloy melt but induces unstable flow rate during filling,which is detrimental to complete filling.Zr-based amorphous micro-gears with a module of 0.6 mm,a tooth top diameter of 8 mm,and 10 teeth were prepared through the suction casting.X-ray diffraction and differential scanning calorimetry analyses confirm that the fabricated micro-gear exhibits characteristic amorphous structural features,demonstrating well-defined geometrical contours and satisfactory forming completeness.
基金National Key Research and Development Program(2021YFB3401101)。
文摘Short process forming techniques for brazing and soldering materials can shorten the process,improve product quality,and increase production efficiency,which has received much attention from welding researchers.This review mainly summarized the research reports on short process forming techniques for brazing and soldering materials.Firstly,the traditional process and its shortcomings were presented.Secondly,the latest research of short process forming technologies,such as continuous casting technique,atomization powder technique,solder ball forming technique,and rapid solidification technique,was summarized,and the traditional forming performance of several brazing and soldering materials was introduced.Finally,the current restrictions and research trends of short process forming technique for brazing and solder materials were put forward,providing theoretical guidance and reference for related research and technique development in brazing and soldering field.
基金supported by the National Key R&D Program of China(2018YFA0702001)National Natural Science Foundation of China(22371268,22301287)+3 种基金Fundamental Research Funds for the Central Universities(WK2060000016)Anhui Provincial Natural Science Foundation(2208085J09,2208085QB33)Collaborative Innovation Program of Hefei Science Center,CAS(2022HSC-CIP020)Youth Innovation Promotion Association of the Chinese Academy of Science(2018494)and USTC Tang Scholar.
文摘The hydrazine oxidation reaction(HzOR)has garnered significant attention as a feasible approach to replace sluggish anodic reactions to save energy.Nevertheless,there are still difficulties in developing highly efficient catalysts for the HzOR.Herein,we report amorphous ruthenium nanosheets(a-Ru NSs)with a thickness of approximately 9.6 nm.As a superior bifunctional electrocatalyst,a-Ru NSs exhibited enhanced electrocatalytic performance toward both the HzOR and hydrogen evolution reaction(HER),outperforming benchmark Pt/C catalysts,where the a-Ru NSs achieved a work-ing potential of merely-76 mV and a low overpotential of only 17 mV to attain a current density of 10 mA·cm^(-2) for the HzOR and HER,respectively.Furthermore,a-Ru NSs displayed a low cell voltage of 28 mV at 10 mA·cm^(-2) for overall hy-drazine splitting in a two-electrode electrolyzer.In situ Raman spectra revealed that the a-Ru NSs can efficiently promote N‒N bond cleavage,thereby producing more*NH_(2)and accelerating the progress of the reaction.
基金Major Science and technology projects of Anhui Province (202103a05020003)。
文摘[Background and purposes]Proton exchange membrane fuel cells(PEMFCs),which convert hydrogen energy directly into electrical energy and water,have received overwhelming attention,owing to their potential to significantly reduce energy consumption,pollution emissions and reliance on fossil fuels.Bipolar plates are the major part and key component of PEMFCs stack,which provide mechanical strength,collect and conduct current segregate oxidants and reduce agents.They contribute 70-80%weight and 20-30%cost of a whole stack,while significantly affecting the power density.There are three types plates,including metal bipolar plate,graphite bipolar plate and composite bipolar plate.Stainless steel bipolar plates,as one of metal bipolar plate,exhibit promising manufacturability,competitive cost and durability among various metal materials.However,stainless steel would be corroded in the harsh acid(pH 2-5)and humid PEMFCs environment,whereas the leached ions will contaminate the membrane.In addition,the passivated film formed on the surface will increase the interfacial contact resistance(ICR).In order to improve the corrosion resistance and electrical conductivity of steel bipolar plates,surface coatings are essential.Metal nitride coatings,metal carbide coatings,polymer coatings and carbon-based coatings have been introduced in recent years.Carbon-based coatings,mainly including a-C(amorphous Carbon),Ta-C(Tetrahedral amorphous carbon)and DLC(diamond-like carbon),have attracted considerable attention from both academia and industry,owing to their superior performance,such as chemical inertness,mechanical hardness and electrical conductivity.However,Ta-C films as protective coating of PEMFCs have been rarely reported,due to the difficulty in production for industrial application.In this paper,multi-layer Ta-C composite films were produced by using customized industrial-scale vacuum equipment to address those issues.[Methods]Multiple layered Ta-C coatings were prepared by using PIS624 equipment,which assembled filtered cathodic arc evaporation,ion beam and magnetron sputtering into one equipment,while SS304 and silicon specimens were used as substrate for testing and analysis.Adhesion layer and intermediate layer were deposited by using magnetron sputtering at deposition temperature of 150℃and pressure of 3×10^(−1) Pa,while the sputtering current was set to be 5 A and bias power to be 300 V.The Ta-C layer was coated at arc current of 80-100 A,bias voltage of 1500 V and gas flow of 75 sccm.A scanning electron microscope(CIQTEK SEM3200)was used to characterize surface morphology,coating structure and cross-section profile of the coatings.Raman spectrometer(LabRam HR Evolution,HORIBA JOBIN YVON)was used to identify the bonding valence states.Electrochemical tests were performed by using an electrochemical work station(CHI760,Shanghai Chenhua Instrument Co.,Ltd.),with the traditional three electrode system,where saturated Ag/AgCl and platinum mesh were used as the reference electrode and counter electrode,respectively.All samples were mounted in plastic tube and sealed with epoxy resin,with an exposure area of 2.25 cm^(2),serving as the working electrode.Electrochemical measurements were carried out in simulated PEMFCs cathode environment in 0.5 mol·L^(−1) H_(2)SO_(4)+5 ppm F−solution,at operating temperature of 70℃.As the cathode environment was harsher than the anode environment,all the samples are stabilized at the open-circuit potential(OCP)for approximately 30 min before the EIS measurements.ICR between bipolar plates and GDL was a key parameter affecting performance of the PEMFCs stack.The test sample sandwiched between 2 pieces of carbon paper(simulate gas diffusion layer,GDL)was placed between 2 gold-plated copper electrodes at a compaction pressure of 1.4 MPa,which was considered to be the conventional compaction pressure in the PEMFCs.Under the same conditions,the resistance of a single carbon paper was measured as well.The ICR was calculated according to the formula ICR=1/2(R2−R1)×S,where S was the contact area between GDL and coated stainless steel BPPs.All data of ICR were measured three times for averaging.[Results]The coatings deposited by filtered cathodic arc technology were compact and smooth,which reduced coating porosity and favorable to corrosion resistance.The coating thickness of adhesion and intermediate layers were 180 nm,while the protective Ta-C coating thickness was about 300 nm,forming multiple coating to provide stronger protection for metal bipolar plates.Cr,Ti,Nb and Ta coatings were selected as adhesion layers for comparison.According to electrochemical test,Ta and Nb coatings have higher corrosion resistance.However,Ta and Nb materials would be costly when they are used for mass production.Relatively,Cr and Ti materials were cost effective.Hence,a comprehensive assessment was indispensable to decide the materials to be selected as adhesion layer.Ta-TiN and Ti-TiN combined adhesion and intermediate layer exhibited stronger corrosion resistance,with the corrosion current to be less than 10^(−6) A·cm^(−2).Ta-C protective coating deposited by using filtered cathodic arc technology indicated displayed higher corrosion resistance,with the average corrosion density to be about 1.26×10^(−7) A·cm^(−2).Ta-C coating also shown larger contact angle,with the highest hydrophobicity,which was one of the important advantages for Ta-C,in terms of corrosion resistance.According to Raman spectroscopy,the I(D)/I(G)=549.8/1126.7=0.487,with the estimated fraction of sp^(3) bonding to be in the range of 5154%.The intermediate layer TiN has higher conductivity than the CrN layer.Considering cost,corrosion performance and ICR result,the Ti-TiN layer combination is recommended for industrial scale application.[Conclusions]Multiple layer coating structure of Ta-C film had stronger corrosion resistance;with more than 50%sp^(3) content,while it also had larger water contact angle and higher corrosion resistance than DLC film.The filtered arcing deposition technology was able to make the film to be more consistent and stable than normal arcing technology in terms of the preparation of Ta-C.The coating displayed corrosion density of 1.26×10^(−7) A·cm^(−2) and ICR of less than 5 mΩ·cm^(2),far beyond technical target of 2025 DOE(US Department of Energy).This indicated that the mass-production scale coating technology for PEMFC bipolar plates is highly possible.
基金Research Project of Shenzhen Science and Technology Innovation Committee(JCYJ20180306170801080)。
文摘Amorphous Ga_(2)O_(3)(a-Ga_(2)O_(3))thin films were prepared on flexible polyimide,rigid quartz glass,and Si substrates via radio frequency magnetron sputtering at room temperature.The effect of oxygen/Ar flow rate ratio on the structure,optical property,surface morphology,and chemical bonding properties of the a-Ga_(2)O_(3) films was investigated.Results show that the average optical transmittance of the a-Ga_(2)O_(3) films is over 80%within the wavelength range of 300-2000 nm.The extracted optical band gap of the a-Ga_(2)O_(3) films is increased from 4.97 eV to 5.13 eV with the increase in O_(2)/Ar flow rate ratio from 0 to 0.25,due to the decrease in concentration of oxygen vacancy defects in the film.Furthermore,the optical refractive index and surface roughness of the a-Ga_(2)O_(3) films are optimized when the O_(2)/Ar flow rate ratio reaches 0.25.X-ray photoelectron spectroscopy analysis also shows that the proportion of oxygen vacancies(VO)and Ga-O chemical bonds in the O 1s peak is gradually decreased with the increase in O_(2)/Ar flow rate ratio from 0 to 0.25,proving that increasing the O_(2)/Ar flow rate ratio during film growth can reduce the concentration of oxygen vacancy defects in a-Ga_(2)O_(3) films.In this case,a-Ga_(2)O_(3) with optimal properties can be obtained.This work provides a research basis for high-performance flexible and rigid deep ultraviolet solar-blind detection devices based on a-Ga_(2)O_(3) films.
基金supported by the National Key R&D Program of China under Grant No.2021YFA1400500the Strategic Priority Research Program of the Chinese Academy of Sciences under Grant No.XDB33000000+1 种基金the National Natural Science Foundation of China under Grant No.12334003the Beijing Municipal Natural Science Foundation under Grant Nos.JQ22001 and QY23014。
文摘Establishing the structure-property relationship in amorphous materials has been a long-term grand challenge due to the lack of a unified description of the degree of disorder.In this work,we develop SPRamNet,a neural network based machine-learning pipeline that effectively predicts structure-property relationship of amorphous material via global descriptors.Applying SPRamNet on the recently discovered amorphous monolayer carbon,we successfully predict the thermal and electronic properties.More importantly,we reveal that a short range of pair correlation function can readily encode sufficiently rich information of the structure of amorphous material.Utilizing powerful machine learning architectures,the encoded information can be decoded to reconstruct macroscopic properties involving many-body and long-range interactions.Establishing this hidden relationship offers a unified description of the degree of disorder and eliminates the heavy burden of measuring atomic structure,opening a new avenue in studying amorphous materials.
基金supported by the Russian Science Foundation(project No.24-43-00215,http://rscf.ru/project/24-43-00215/).
文摘This study explores a novel strategy to enhance the hydrogen evolution reaction(HER)activity of carbon-supported rock salt-type NiCo_(2)(O,F)_(3) nanorods through lattice modifications induced by fluorine and excess amorphous carbon.X-ray absorption near-edge structure(XANES)analysis confirmed that Co and Ni predominantly exist in the+2 oxidation state,whereas extended X-ray absorption fine structure(EXAFS)analysis revealed shortened Co-O and Co-Co bond lengths,indicating lattice distortions.Rietveld refinement and electron microscopy confirmed the formation of a homogeneous solid solution(NixCo_(2-x)(O,F)_(3))rather than a simple CoO/NiO composite.The optimized material(AH-2)exhibited the lowest overpotential(145 mV at 10 mA cm^(-1))and the smallest Tafel slope(98 mV dec^(-1)),attributed to its balanced phase composition,enhanced electronic conductivity,and synergistic effects of carbon and fluorine incorporation.Electrochemical impedance spectroscopy(EIS)confirmed improved charge transfer efficiency,correlating with enhanced catalytic activity.These findings provide critical insights into the tunability of transition metal oxide catalysts via controlled lattice modifications,offering a promising avenue for developing cost-effective and efficient electrocatalysts for sustainable hydrogen production.
基金the National Natural Science Foundation of China under grant No.12372173the Natural Science Foundation of Shanghai under grant No.23ZR1468600.
文摘Silicon,a leading candidate for electrode material for lithium-ion batteries,has garnered significant attention.During the initial lithiation process,the alloying reaction between silicon and lithium transforms the pristine silicon microstructure from crystalline to amorphous,resulting in plastic deformation of the amorphous phase.This study proposes the free volume theory to develop a fully coupled Cahn-Hilliard phase-field model that integrates viscoplastic deformation,free volume evolution,and diffusion.This model investigates the chemophysical phenomenon of self-limiting behavior occurring during the initial lithiation of silicon anodes.Unlike most existing models,the proposed model considers free volume-dependent diffusion using a physically-based approach.The model’s temporal variation in the lithiated phase thickness aligns well with experimental results,confirming the model’s accuracy.Stress field calculations reveal the coexistence of compressive and tensile stresses within the lithiated phase,which may not cause the limiting effect under the frame of the stress-induced diffusion.Analyses indicate that high effective stress increases free volume,enhancing lithium diffusion and augmenting the diffusion coefficient.Reducing the diffusion coefficient in the lithiated phase due to free volume evolution is the primary cause of self-limiting lithiation.
基金supported financially by the National Natural Science Foundation of China(22178229)the Natural Science Foundation of Sichuan Province(2022NSFSC1190)。
文摘With the development of vanadium redox flow battery technology,the demand for pure vanadium is rapidly increasing.The separation of vanadium from vanadium-chromium leaching solutions are critical step in the production of purity-vanadium.This study presents an innovative adsorption process that utilizes amorphous ZrO_(2)(AZrO) for the selective separation of V(Ⅴ) and Cr(Ⅵ).In this process,a high adsorption capacity for V(V) at 64.5 mg·g^(-1) was achieved,while the capacity for Cr(Ⅵ) is relatively low at 24.1 mg·g^(-1),demonstrating good separation performance.This is mainly caused by the large specific surface area and mesoporous structure,which are favorable for molecular diffusion and mass transfer.The kinetic analysis shows that the adsorption process follows pseudo-second-order kinetic process with chemisorption being the rate-controlling process.AZrO showed excellent separation performance in mixed solutions over a wide range of concentrations.After five cycles,AZrO retained over 73% of its capacity,indicating good stability.In mixed solutions containing up to 40 g·L^(-1) of V(Ⅴ) and 3 g·L^(-1) of Cr(Ⅵ),the innovative adsorption process successfully achieved effective separation and purification.By an adsorption-desorption process using 0.1 mol·L^(-1) NaOH,a 99.02% V(Ⅴ)-rich solution was obtained from a high concentration sodium vanadium slag leaching solution,demonstrating its effectiveness for practical industrial applications.
文摘Carbon nanotubes(CNTs)reinforced copper(CNTs/Cu)is one of the most promising and extensively researched materials for replacing traditional Cu-based materials in high-load and high-current applications,particularly within the aerospace industry.Amorphous carbon nanotubes(aCNTs)are a type of carbon nanotubes characterized by the presence of mesopores distributed across their amorphous sidewalls,facilitating connectivity between the hollow core and the external environment.Therefore,we propose utilizing aCNTs as a reinforcing agent for Cu.The mesoporous structure of aCNTs facilitates the interpenetration of Cu into the aCNTs,thereby maintaining the continuity of the matrix properties.Experimental results demonstrate that Cu effectively penetrates the mesoporous sidewalls of aCNTs.Both pure Cu and aCNTs-reinforced Cu exhibit comparable electrical conductivity,while the hardness of the aCNTs/Cu composite is significantly enhanced.Additionally,both the density and porosity of aCNTs/Cu are lower than those of pure Cu,and the introduction of aCNTs helps to reduce the sintering temperature.
