A novel Co-B amorphous alloy catalyst in the form of ultrafine particles was prepared by chemical reduction of CoCl2 with aqueous NaBH4, which exhibited excellent activity and selectivity during the hydrogenation of c...A novel Co-B amorphous alloy catalyst in the form of ultrafine particles was prepared by chemical reduction of CoCl2 with aqueous NaBH4, which exhibited excellent activity and selectivity during the hydrogenation of cinnamaldehyde to cinnamyl alcohol in liquid phase. The optimum yield of cinnamyl alcohol was 87.6%, much better than the yield of using Raney Ni, Raney Co and other Co-based catalysts.展开更多
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 H_(2)-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
Amorphous materials represent a promising platform for advancing CO_(2)electrochemical reduction due to their inherently diverse coordination environments.In this study,we demonstrate computationally the superior perf...Amorphous materials represent a promising platform for advancing CO_(2)electrochemical reduction due to their inherently diverse coordination environments.In this study,we demonstrate computationally the superior performance of amorphous CuNi alloys for CO_(2)electrochemical reduction.By integrating machine learning forcefields for efficient structure generation and density functional theory for subsequent structural refinement and property calculations,we reveal the potential of these disordered systems to outperform their crystalline counterparts.Machine learning forcefields can generate a bulk structure containing a mixture of Cu and Ni atoms,resulting in enhanced catalytic performance.Effective screening of the amorphous surfaces is used to identify undercoordinated Cu and Ni sites in the amorphous structure to synergistically promote selective CO production and favor ethanol formation over ethylene via the stabilization of the*COCHO intermediate,resulting in significantly lower Gibbs free energy changes compared to the crystalline counterpart.The varying atomic coordination environments on amorphous surfaces promote both C–C bond formation and subsequent proton-electron transfer,leading to ethanol formation.These findings demonstrate the superior catalytic performance of amorphous CuNi,highlighting its potential for efficient and selective electroreduction of CO_(2).展开更多
Transition metal selenides as sodium-ion hybrid capacitor(SIHC)anodes still suffer from amorphization difficulties and capacity degradation triggered by polyselenide dissolution.Herein,an atomistic amorphous strategy ...Transition metal selenides as sodium-ion hybrid capacitor(SIHC)anodes still suffer from amorphization difficulties and capacity degradation triggered by polyselenide dissolution.Herein,an atomistic amorphous strategy is proposed to construct adjacent Nb-Nb diatomic pairs with Se/O-coordination(Se4-Nb2-O2)in N-doped carbon-confined amorphous selenide clusters(a-Nb-Se/O@NC).Synergistic carbon confinement and hydrothermal oxygenation induce amorphization of Nb–Se bonds,eliminating crystalline rigidity while creating isotropic dual-ion transport channels and high-density active sites enriched with dangling bonds,thereby enhancing structural integrity and Na+storage capacity.The unique Se/O-coordinated Nb-Nb diatomic configuration establishes an electron-delocalized system,where the low electronegativity of Se counterbalances electron withdrawal from coordinated O at Nb centers.These strengthen d-p orbital hybridization,reduce Na+adsorption energy,and optimize charge transfer pathways and reaction kinetics in the amorphous clusters.Electrochemical tests reveal that the a-Nb-Se/O@NC anode delivers a high reversible capacity of 312.57 mAh g^(−1)and exceptional cyclic stability(103%capacity retention)after 5000 cycles at 10.0 A g^(−1).Assembled SIHCs achieve outstanding energy/power densities(207.1 Wh kg^(−1)/18966 W kg^(−1)),surpassing most amorphous and crystalline counterparts.This work provides methodological insights for the design of electrodes in high-power storage devices through atomic modulation and electronic optimization of amorphous selenides.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
Five Co-B amorphous alloy catalysts were prepared by chemical reduction in different media, including pure water and pure ethanol as well as the mixture of ethanol and water with variable ethanol content, Their cataly...Five Co-B amorphous alloy catalysts were prepared by chemical reduction in different media, including pure water and pure ethanol as well as the mixture of ethanol and water with variable ethanol content, Their catalytic properties were evaluated using liquid phase furfural hydrogenation to furfuryl alcohol as the probe reaction. It was found that the reaction media had no significant influence on either the amorphous structure of the Co-B catalyst or the electronic interaction between metallic Co and alloying B. This could successfully account for the fact that all the as-prepared Co-B catalysts exhibited almost the same selectivity to furfuryl alcohol and the same activity per surface area （ Rs ）, which could be considered as the intrinsic activity, since the nature of active sites remained unchanged. However, the activity per gram of Co （ R^mH ） of the as-prepared Co-B catalysts increased rapidly when the ethanol content in the water-ethanol mixture used as the reaction medium for catalyst preparation increased. This could be attributed to the rapid increase in the surface area possibly owing to the presence of more oxidized boron species which could serve as a support for dispersing the Co-B amorphous alloy particles.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
Mg_(x)(Ni_(0.8)La_(0.2))_(100-x),where x=60,70,80,exhibiting a nanocrystalline microstructure,were prepared through the crystallization of amorphous alloys.The investigation encompassed the phase constitution,grain si...Mg_(x)(Ni_(0.8)La_(0.2))_(100-x),where x=60,70,80,exhibiting a nanocrystalline microstructure,were prepared through the crystallization of amorphous alloys.The investigation encompassed the phase constitution,grain size,microstructural stability,and hydrogen storage properties.Crystallization kinetics,along with in-situ high-energy XRD characterization,revealed a concentrated and synchronous crystallization of Mg_(2)Ni and RE-Mg-Ni ternary phases with the increase in La and Ni content.The attributed synchronous crystallization process was found to be a result of the close local affinity of Mg_(2)Ni and RE-Mg-Ni ternary phases,as assessed by the thermodynamic Miedema model.Significant secondary phase pinning effect,arising from the high likelihood of well-matching phase structures between Mg_(2)Ni,LaMg_(2)Ni,and LaMgNi_(4),was validated through both the edge-to-edge matching model prediction and experimental observation.Thefine and homogeneous microstructure was shown to be a consequence of fast crystallization kinetics and the secondary phase pinning effect.Improved activation performance and cycling stability were observed,stemming from grain refinement and excellent microstructural stability.Our study provides insights into mechanism of grain refinement of nanocrystalline microstructure tailored by phase constitution and crystallization kinetics in the amorphous-crystallization route.We also demonstrate the potential of material design guided by phase equilibria and crystallographic predictions to improve nanocrystalline with excellent microstructural stability.展开更多
Cobalt-based amorphous/nanocrystalline composite coatings have been grown by arc ion plating together with a specimen cooling system. With decreasing substrate temperature, the coatings undergo significant structure e...Cobalt-based amorphous/nanocrystalline composite coatings have been grown by arc ion plating together with a specimen cooling system. With decreasing substrate temperature, the coatings undergo significant structure evolution. The degree of crystallization first decreases and subsequently increases as confirmed by X-ray diffraction. The cluster size first decreases and then remains constant as confirmed by transmission electron microscopy. The effect of substrate temperature on the evolution of the structure has been studied as a result of a competition between nucleation thermodynamics and kinetics of crystalline growth. With decreasing the substrate temperature, the microhardness and the critical load of the composite coatings firstly increased, and then remained almost constant. And the saturation magnetization revealed the opposite trend over the same range. The essence of these phenomena was ascribed to the microstructural variations caused by the decrease of the substrate temperature.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
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
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
Annealing temperatures and applied magnetic fields are two important parameters for the performance modification of magnetic alloys.This article investigated the effect of different annealing temperatures on crystalli...Annealing temperatures and applied magnetic fields are two important parameters for the performance modification of magnetic alloys.This article investigated the effect of different annealing temperatures on crystallization condition,magnetic properties and thermal stability of the amorphous magnetic alloy Co_(36)Fe_(36)Si_(4.8)B1_(9.2)Nb_(4)(at%).Results indicate that the annealing temperature can significantly affect the size and content of precipitated nanocrystals in the amorphous alloy,and the precipitation of nanocrystalline phases can result in the distinct change of magnetic properties and Curie temperature.When the annealing was performed at 595 ℃ for 30 min under an applied transverse external magnetic field of 9550.0A·m^(-1),the amorphous alloy shows excellent soft magnetic properties with the saturation magnetization of alloy reaching 110.00 mA·m^(2)·g^(-1),the residual magnetic induction intensity of 4 × 10^(-6) T and the coercivity as low as57.3 A·m^(-1).Furthermore,the Curie temperature of the field-annealed samples can reach up to 440 0C,approximately 58℃ higher than that of the as-quenched species.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
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
Measurements of the Doppler broadening S-lineshape parameter of positron annihilation and brittleness have been performed for two Co-based amorphous alloy prior to crystallization. It is shown that the brittleness is ...Measurements of the Doppler broadening S-lineshape parameter of positron annihilation and brittleness have been performed for two Co-based amorphous alloy prior to crystallization. It is shown that the brittleness is related to the S-parameter, that is, microdefects may be one of the important factors affecting the embrittlement of the Co-based amorphous alloys.展开更多
基金This work was supported by the National Natural Science Foundation of China (29973025) and the Natural Science Foundation of Shanghai Science and Technology Committee (98QMA11402).
文摘A novel Co-B amorphous alloy catalyst in the form of ultrafine particles was prepared by chemical reduction of CoCl2 with aqueous NaBH4, which exhibited excellent activity and selectivity during the hydrogenation of cinnamaldehyde to cinnamyl alcohol in liquid phase. The optimum yield of cinnamyl alcohol was 87.6%, much better than the yield of using Raney Ni, Raney Co and other Co-based catalysts.
基金mainly supported by the Natural Science Foundation of China (Grant Nos. 52288102, 52090020, and 52372261)the Natural Science Foundation of Hebei Province (Grant No. E202403045)+1 种基金the S&T Program of Hebei (Grant No. 225A1102D)the Ministry of Education Chang Jiang Scholar Professor Program (Grant No. T2022241)
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 H_(2)-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partially funded by EPSRC (EP/T022213/1, EP/W032260/1 and EP/P020194/1) via our membership of the UK’s HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202)part of the “Advancing Solid Interface and Lubricants by First Principles Material Design (SLIDE)” project that has received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation program (Grant agreement No. 865633)
文摘Amorphous materials represent a promising platform for advancing CO_(2)electrochemical reduction due to their inherently diverse coordination environments.In this study,we demonstrate computationally the superior performance of amorphous CuNi alloys for CO_(2)electrochemical reduction.By integrating machine learning forcefields for efficient structure generation and density functional theory for subsequent structural refinement and property calculations,we reveal the potential of these disordered systems to outperform their crystalline counterparts.Machine learning forcefields can generate a bulk structure containing a mixture of Cu and Ni atoms,resulting in enhanced catalytic performance.Effective screening of the amorphous surfaces is used to identify undercoordinated Cu and Ni sites in the amorphous structure to synergistically promote selective CO production and favor ethanol formation over ethylene via the stabilization of the*COCHO intermediate,resulting in significantly lower Gibbs free energy changes compared to the crystalline counterpart.The varying atomic coordination environments on amorphous surfaces promote both C–C bond formation and subsequent proton-electron transfer,leading to ethanol formation.These findings demonstrate the superior catalytic performance of amorphous CuNi,highlighting its potential for efficient and selective electroreduction of CO_(2).
基金supported by the National Natural Science Foundation of China(Grant No.52573299)the Natural Science Foundation of Jiangxi province(No.20242BAB25223,20232BCJ23025,20232BCJ25040,20232BAB214024)the Special Funding Program for Graduate Student Innovation of Jiangxi Province(No.YC2024-S594).
文摘Transition metal selenides as sodium-ion hybrid capacitor(SIHC)anodes still suffer from amorphization difficulties and capacity degradation triggered by polyselenide dissolution.Herein,an atomistic amorphous strategy is proposed to construct adjacent Nb-Nb diatomic pairs with Se/O-coordination(Se4-Nb2-O2)in N-doped carbon-confined amorphous selenide clusters(a-Nb-Se/O@NC).Synergistic carbon confinement and hydrothermal oxygenation induce amorphization of Nb–Se bonds,eliminating crystalline rigidity while creating isotropic dual-ion transport channels and high-density active sites enriched with dangling bonds,thereby enhancing structural integrity and Na+storage capacity.The unique Se/O-coordinated Nb-Nb diatomic configuration establishes an electron-delocalized system,where the low electronegativity of Se counterbalances electron withdrawal from coordinated O at Nb centers.These strengthen d-p orbital hybridization,reduce Na+adsorption energy,and optimize charge transfer pathways and reaction kinetics in the amorphous clusters.Electrochemical tests reveal that the a-Nb-Se/O@NC anode delivers a high reversible capacity of 312.57 mAh g^(−1)and exceptional cyclic stability(103%capacity retention)after 5000 cycles at 10.0 A g^(−1).Assembled SIHCs achieve outstanding energy/power densities(207.1 Wh kg^(−1)/18966 W kg^(−1)),surpassing most amorphous and crystalline counterparts.This work provides methodological insights for the design of electrodes in high-power storage devices through atomic modulation and electronic optimization of amorphous selenides.
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).
文摘Five Co-B amorphous alloy catalysts were prepared by chemical reduction in different media, including pure water and pure ethanol as well as the mixture of ethanol and water with variable ethanol content, Their catalytic properties were evaluated using liquid phase furfural hydrogenation to furfuryl alcohol as the probe reaction. It was found that the reaction media had no significant influence on either the amorphous structure of the Co-B catalyst or the electronic interaction between metallic Co and alloying B. This could successfully account for the fact that all the as-prepared Co-B catalysts exhibited almost the same selectivity to furfuryl alcohol and the same activity per surface area （ Rs ）, which could be considered as the intrinsic activity, since the nature of active sites remained unchanged. However, the activity per gram of Co （ R^mH ） of the as-prepared Co-B catalysts increased rapidly when the ethanol content in the water-ethanol mixture used as the reaction medium for catalyst preparation increased. This could be attributed to the rapid increase in the surface area possibly owing to the presence of more oxidized boron species which could serve as a support for dispersing the Co-B amorphous alloy particles.
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 National Natural Science Foundation of China(51761034,51961032,51962028 and 52261041)Innovation Foundation of Inner Mongolia University of Science and Technology(2019YQL03)+2 种基金Major Science and Technology Project of Inner Mongolia(2021ZD0029)Program for Young Talents of Science and Technology in Universities of Inner Mongolia Autonomous Region(NJYT23005,NJYT23007)Program for Innovative Research Team in Universities of Inner Mongolia Autonomous Region(NMGIRT2401).
文摘Mg_(x)(Ni_(0.8)La_(0.2))_(100-x),where x=60,70,80,exhibiting a nanocrystalline microstructure,were prepared through the crystallization of amorphous alloys.The investigation encompassed the phase constitution,grain size,microstructural stability,and hydrogen storage properties.Crystallization kinetics,along with in-situ high-energy XRD characterization,revealed a concentrated and synchronous crystallization of Mg_(2)Ni and RE-Mg-Ni ternary phases with the increase in La and Ni content.The attributed synchronous crystallization process was found to be a result of the close local affinity of Mg_(2)Ni and RE-Mg-Ni ternary phases,as assessed by the thermodynamic Miedema model.Significant secondary phase pinning effect,arising from the high likelihood of well-matching phase structures between Mg_(2)Ni,LaMg_(2)Ni,and LaMgNi_(4),was validated through both the edge-to-edge matching model prediction and experimental observation.Thefine and homogeneous microstructure was shown to be a consequence of fast crystallization kinetics and the secondary phase pinning effect.Improved activation performance and cycling stability were observed,stemming from grain refinement and excellent microstructural stability.Our study provides insights into mechanism of grain refinement of nanocrystalline microstructure tailored by phase constitution and crystallization kinetics in the amorphous-crystallization route.We also demonstrate the potential of material design guided by phase equilibria and crystallographic predictions to improve nanocrystalline with excellent microstructural stability.
文摘Cobalt-based amorphous/nanocrystalline composite coatings have been grown by arc ion plating together with a specimen cooling system. With decreasing substrate temperature, the coatings undergo significant structure evolution. The degree of crystallization first decreases and subsequently increases as confirmed by X-ray diffraction. The cluster size first decreases and then remains constant as confirmed by transmission electron microscopy. The effect of substrate temperature on the evolution of the structure has been studied as a result of a competition between nucleation thermodynamics and kinetics of crystalline growth. With decreasing the substrate temperature, the microhardness and the critical load of the composite coatings firstly increased, and then remained almost constant. And the saturation magnetization revealed the opposite trend over the same range. The essence of these phenomena was ascribed to the microstructural variations caused by the decrease of the substrate temperature.
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financially supported by National S&T Major Project of China (No.2018ZX10301201)the National Natural Science Foundation of China (No.51371018)the Fundamental Research Funds for the Central Universities (No. FRF-BR-14-001B)。
文摘Annealing temperatures and applied magnetic fields are two important parameters for the performance modification of magnetic alloys.This article investigated the effect of different annealing temperatures on crystallization condition,magnetic properties and thermal stability of the amorphous magnetic alloy Co_(36)Fe_(36)Si_(4.8)B1_(9.2)Nb_(4)(at%).Results indicate that the annealing temperature can significantly affect the size and content of precipitated nanocrystals in the amorphous alloy,and the precipitation of nanocrystalline phases can result in the distinct change of magnetic properties and Curie temperature.When the annealing was performed at 595 ℃ for 30 min under an applied transverse external magnetic field of 9550.0A·m^(-1),the amorphous alloy shows excellent soft magnetic properties with the saturation magnetization of alloy reaching 110.00 mA·m^(2)·g^(-1),the residual magnetic induction intensity of 4 × 10^(-6) T and the coercivity as low as57.3 A·m^(-1).Furthermore,the Curie temperature of the field-annealed samples can reach up to 440 0C,approximately 58℃ higher than that of the as-quenched species.
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 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.
文摘Measurements of the Doppler broadening S-lineshape parameter of positron annihilation and brittleness have been performed for two Co-based amorphous alloy prior to crystallization. It is shown that the brittleness is related to the S-parameter, that is, microdefects may be one of the important factors affecting the embrittlement of the Co-based amorphous alloys.
