Layered oxides have attracted significant attention as cathodes for sodium-ion batteries(SIBs)due to their compositional versatility and tuneable electrochemical performance.However,these materials still face challeng...Layered oxides have attracted significant attention as cathodes for sodium-ion batteries(SIBs)due to their compositional versatility and tuneable electrochemical performance.However,these materials still face challenges such as structural phase transitions,Na^(+)/vacancy ordering,and Jahn–Teller distortion effect,resulting in severe capacity decay and sluggish ion kinetics.We develop a novel Cu/Y dual-doping strategy that leads to the formation of"Na–Y"interlayer aggregates,which act as structural pillars within alkali metal layers,enhancing structural stability and disrupting the ordered arrangement of Na^(+)/vacancies.This disruption leads to a unique coexistence of ordered and disordered Na^(+)/vacancy states with near-zero strain,which significantly improves Na^(+)diffusion kinetics.This structural innovation not only mitigates the unfavorable P2–O2 phase transition but also facilitates rapid ion transport.As a result,the doped material demonstrates exceptional electrochemical performance,including an ultra-long cycle life of 3000 cycles at 10 C and an outstanding high-rate capability of~70 mAh g^(−1)at 50 C.The discovery of this novel interlayer pillar,along with its role in modulating Na^(+)/vacancy arrangements,provides a fresh perspective on engineering layered oxides.It opens up promising new pathways for the structural design of advanced cathode materials toward efficient,stable,and high-rate SIBs.展开更多
The Ti-Al alloy was synthesized using the aluminothermic reduction of TiO_(2),with CaO and MgF_(2)serving as flux components.Investigations were conducted to ascertain the effects of MgF_(2)content on the alloy-slag s...The Ti-Al alloy was synthesized using the aluminothermic reduction of TiO_(2),with CaO and MgF_(2)serving as flux components.Investigations were conducted to ascertain the effects of MgF_(2)content on the alloy-slag separation,alloy microstructure,composition,phase constitution,overall alloy yield,and aluminothermic reduction of TiO_(2).Results indicate that MgF_(2)enhances the separation of the alloy from slag and promotes the formation of the TiAl phase within the alloy matrix.Nevertheless,an overabundance of MgF_(2)reduces the interfacial tension between the Al reductant and the slag,leading to significant loss of Al.This adversely affects alloy-slag separation,escalates the incorporation of oxide inclusions in the alloy,and severely reduces the recovery rate of alloy.Concurrently,the alloy has a phase transition from TiAl to Ti_(3)Al.The optimum condition for alloy-slag separation and alloy integrity is realized at the MgF_(2)content of 10wt%.Kinetic analysis at this flux ratio determines the activating energy for the Al-TiO_(2)-CaO-MgF_(2)system,which is 409.729 kJ/mol,and the order of kinetics is n=0.38.展开更多
Layered transition metal oxides have emerged as promising cathode materials for sodium ion batteries.However,irreversible phase transitions cause structural distortion and cation rearrangement,leading to sluggish Na+d...Layered transition metal oxides have emerged as promising cathode materials for sodium ion batteries.However,irreversible phase transitions cause structural distortion and cation rearrangement,leading to sluggish Na+dynamics and rapid capacity decay.In this study,we propose a medium-entropy cathode by simultaneously introducing Fe,Mg,and Li dopants into a typical P2-type Na_(0.75)Ni_(0.25)Mn_(0.75)O_(2)cathode.The modified Na_(0.75)Ni_(0.2125)Mn_(0.6375)Fe_(0.05)Mg_(0.05)Li_(0.05)O_(2)cathode predominantly exhibits a main P2 phase(93.5%)with a minor O3 phase(6.5%).Through spectroscopy techniques and electrochemical investigations,we elucidate the redox mechanisms of Ni^(2+/3+/4+),Mn^(3+/4+),Fe^(3+/4+),and O_(2)-/O_(2)^(n-)during charging/discharging.The medium-entropy doping mitigates the detrimental P2-O_(2)phase transition at high-voltage,replacing it with a moderate and reversible structural evolution(P2-OP4),thereby enhancing structural stability.Consequently,the modified cathode exhibits a remarkable rate capacity of 108.4 mAh·g^(-1)at 10C,with a capacity retention of 99.0%after 200 cycles at 1C,82.5%after 500 cycles at 5C,and 76.7%after 600 cycles at 10C.Furthermore,it also demonstrates superior electrochemical performance at high cutoff voltage of 4.5 V and extreme temperature(55 and 0℃).This work offers solutions to critical challenges in sodium ion batteries cathode materials.展开更多
CO_(2)hydrogenation to value-added light olefins(C_(2-4)=)is crucial for the utilization and cycling of global carbon resource.Moderate CO_(2)activation and carbon chain growth ability are key factors for iron-based c...CO_(2)hydrogenation to value-added light olefins(C_(2-4)=)is crucial for the utilization and cycling of global carbon resource.Moderate CO_(2)activation and carbon chain growth ability are key factors for iron-based catalysts for efficient CO_(2)conversion to target C_(2-4)=products.The electronic interaction and confinement effect of electron-deficient graphene inner surface on the active phase are effective to improve surface chemical properties and enhance the catalytic performance.Here,we report a core-shell FeCo alloy catalyst with graphene layers confinement prepared by a simple sol-gel method.The electron transfer from Fe species to curved graphene inner surface modifies the surface electronic structure of the active phaseχ-(Fe_(x)Co_(1-x))_(5)C_(2)and improves CO_(2)adsorption capacity,enhancing the efficient conversion of CO_(2)and moderate C-C coupling.Therefore,the catalyst FeCoK@C exhibits C_(2-4)=selectivity of 33.0%while maintaining high CO_(2)conversion of 52.0%.The high stability without obvious deactivation for over 100 h and unprecedented C_(2-4)=space time yield(STY)up to 52.9 mmolCO_(2)·g^(-1)·h^(-1)demonstrate its potential for practical application.This work provides an efficient strategy for the development of high-performance CO_(2)hydrogenation catalysts.展开更多
Broadband transparent films play a pivotal role in various applications such as lenses and solar cells,particularly porous structured transparent films exhibit significant potential.This study investigates a porous Si...Broadband transparent films play a pivotal role in various applications such as lenses and solar cells,particularly porous structured transparent films exhibit significant potential.This study investigates a porous SiO_(2) refractive index gradient anti-reflective film prepared by atomic layer deposition(ALD).A porous SiO_(2) film with gradual porosity was obtained by phosphoric acid etching of Al_(2)O_(3)/SiO_(2) multilayers with gradient Al2O3 ratios,achieving a gradual decrease in refractive index from the substrate to the surface.The film exhibited an average transmittance as high as 97.8%within the wavelength range from 320 nm to 1200 nm.The environmental adaptability was further enhanced by surface modification using rare earth oxide(REO)La_(2)O_(3),resulting in formation of a lotus leaf-like structure and achieving a water contact angle of 100.0°.These data proved that the modification significantly improved hydrophobic self-cleaning capability while maintaining exceptional transparency of the film.The surface structure of the modified film remained undamaged even after undergoing wipe testing,demonstrating its excellent surface durability.展开更多
Modulating the interface between the electron transport layer(ETL)and perovskite to minimize interfacial recombination is pivotal for developing efficient and stable perovskite solar cells.Here,we introduce an ultra-t...Modulating the interface between the electron transport layer(ETL)and perovskite to minimize interfacial recombination is pivotal for developing efficient and stable perovskite solar cells.Here,we introduce an ultra-thin ZrO_(2)insulating interface layer onto the inner surface of the mesoporous TiO_(2)ETL via the chemical bath deposition in the zirconium n-butoxide solution,which alters the interface characteristics between TiO_(2)and perovskite for the printable hole-conductor-free mesoscopic perovskite solar cells(p-MPSCs).The insulating ZrO_(2)interface layer reduces interface defects and suppresses interfacial non-radiative recombination.Furthermore,the ZrO_(2)interface layer improves the wettability of the mesoporous TiO_(2)ETL,which favors the crystallization of perovskite within the mesoporous scaffold.Meanwhile,the device performance presents thickness dependence on the interface layer.While increased thickness improves the open-circuit voltage,excessive thickness negatively impacts both the short-circuit current density and fill factor.Consequently,an improved power conversion efficiency of 19.9% was achieved for p-MPSCs with the ZrO_(2)interface layer at its optimized thickness.展开更多
The rapid evolution of hypersonic vehicle technologies necessitates robust thermal protection systems capable of withstanding extreme oxidative ablation.This study introduces a novel gradient-architected ZrB_(2)-MoSi_...The rapid evolution of hypersonic vehicle technologies necessitates robust thermal protection systems capable of withstanding extreme oxidative ablation.This study introduces a novel gradient-architected ZrB_(2)-MoSi_(2)-SiC dense layer embedded within a lightweight three-dimensional(3D)needled carbon fiber composite.Utilizing the volatility of ethanol and polycarbosilane,the ceramic slurry is selectively infused into targeted regions of the fibrous structure,optimizing the ZrB_(2)to MoSi_(2)ratio to enhance performance.The resulting dense layer exhibits exceptional emissivity,surpassing 0.90 in the 1-3μm range and exceeding 0.87 in the 2-14μm range.Moreover,it demonstrates remarkable oxidative ablation resistance.Specifically,at an optimized ZrB_(2)to MoSi_(2)ratio of 6:4,the dense layer achieves a minimal linear ablation rate of 0.015μm·s^(-1) under a 1.5 MW·m^(-2)oxyacetylene flame for 1000 s.Even after exposure to oxyacetylene ablation at surface temperatures of approximately 1750℃for 1000 s,the dense layer retains its structural integrity,highlighting its enduring oxidation resistance.The incorporation of MoSi_(2)not only enhances emissivity but also fortifies the ZrO_(2)and SiO_(2)oxide layers,crucial for environments with elevated oxygen levels,thereby mitigating the active oxidation of SiC.This combination of high emissivity and long-term oxidation resistance at ultra-high temperatures positions the ZrB_(2)-MoSi_(2)-SiC dense layer as an exceptionally promising candidate for advanced thermal protection in hypersonic vehicles.展开更多
Given the limited exposure of active sites and the retarded separation of photogenerated charge carriers in those developed photocata-lysts,photocatalyticCO_(2)splitting into value-added chemicals has suffered from th...Given the limited exposure of active sites and the retarded separation of photogenerated charge carriers in those developed photocata-lysts,photocatalyticCO_(2)splitting into value-added chemicals has suffered from the poor activity and remained in great challenge for real application.Herein,hydrothermally synthesized BiOCl with layered structure(BOC-NSs)was exfoliated into thickness reduced nanosheets(BOCNSs-w)and even atomic layers(BOCNSs-i)via ultrasonication in water and isopro-panol,respectively.In comparison with the pristine BOCNSs,the exfoli-ated BiOCl,especially BOCNSs-i with atomically layered structure,exhibits much improved photocatalytic activity forCO_(2)overall splitting to produce CO andO_(2) at a stoichiometric ratio of 2:1,with CO evolution rate reaching 134.8µmolg^(-1)h^(-1) under simulated solar light(1.7 suns).By surpassing the photocatalytic performances of the state-of-the-artBi_(l)O_(m)X_(n)(X:Cl,Br,I)based photocatalysts,the CO evolution rate is further increased by 99 times,reaching 13.3 mmolg^(-1)h^(-1) under concentrated solar irradiation(34 suns).This excellent photocatalytic performance achieved over BOCNSs-i should be benefited from the shortened transfer distance and the increased built-in electric field intensity,which acceler-ates the migration of photogenerated charge carriers to surface.Moreover,with oxygen vacancies(VO)introduced into the atomic layers,BOCNSs-i is exposed with the electrons enriched Bi active sites that could transfer electrons to activateCO_(2)molecules for highly efficient and selective CO production,by lowering the energy barrier of rate-determining step(RDS),*OH+*CO_(2)-→HCO_(3)-.It is also realized that theH_(2)O vapor supplied during photocatalytic reaction would exchange oxygen atoms withCO_(2),which could alter the reaction path-ways and further reduce the energy barrier of RDS,contributing to the dramatically improved photocatalytic performance forCO_(2)overall splitting to CO andO_(2).展开更多
Normally,a transparent inert film is coated on the surface of TiO_(2) particles to enhance the weatherability of the pigment.Liquid-phase coating process is mainly used in industry,which difficult to get really unifor...Normally,a transparent inert film is coated on the surface of TiO_(2) particles to enhance the weatherability of the pigment.Liquid-phase coating process is mainly used in industry,which difficult to get really uniform films.This work combining nanoparticle fluidization technology with atomic layer deposition(ALD) technology to achieve precise surface modification of a large number of micro-nano particles.First,we explored the fluidization characteristics of TiO_(2) nanoparticles in a home-made atmospheric fluidized bed ALD reactor(FB-ALD) to ensure the uniform fluidization of a large number of nanoparticles.Then TiCl_(4) and H_(2)O were used as precursors to deposit amorphous TiO_(2) films on the surface of TiO_(2) nanoparticles at 80℃ under atmospheric pressure,and the growth per cycle was about 0.109 nm per cycle.After 30 ALD cycles,the film thickness was about 3.1 nm,which could almost fully suppress the photocatalytic activity of TiO_(2).Compared with other traditional coating materials,amorphous TiO_(2) has higher light refractive index,and realizes the suppression of the photocatalytic activity of TiO_(2) without introducing other substances,demonstrating greater application potential in TiO_(2) pigment coating field.The process is a gas-phase coating method,which is efficient,no waste water,and easy to scale up.This work shown the excellent property of interface engineering in improving pigment weatherability and can also provide guidance for the nanoparticle surface modification.展开更多
Synergistic interplays involving multiple active centers originating from TiO2 nanotube layers(TNT)and ruthenium(Ru)species comprising of both single atoms(SAs)and nanoparticles(NPs)augment the alkaline hydrogen evolu...Synergistic interplays involving multiple active centers originating from TiO2 nanotube layers(TNT)and ruthenium(Ru)species comprising of both single atoms(SAs)and nanoparticles(NPs)augment the alkaline hydrogen evolution reaction(HER)by enhancing Volmer kinetics from rapid water dissociation and improving Tafel kinetics from efficient H*desorption.Atomic layer deposition of Ru with 50 process cycles results in a mixture of Ru SAs and 2.8-0.4 nm NPs present on TNT layers,and it emerges with the highest HER activity among all the electrodes synthesized.A detailed study of the Ti and Ru species using different high-resolution techniques confirmed the presence of Ti^(3+)states and the coexistence of Ru SAs and NPs.With insights from literature,the role of Ti^(3+),appropriate work functions of TNT layers and Ru,and the synergistic effect of Ru SAs and Ru NPs in improving the performance of alkaline HER were elaborated and justified.The aforementioned characteristics led to a remarkable performance by having 9mV onset potentials and 33 mV dec^(-1) of Tafel slopes and a higher turnover frequency of 1.72 H2 s^(-1) at 30 mV.Besides,a notable stability from 28 h staircase chronopotentiometric measurements for TNT@Ru surpasses TNT@Pt in comparison.展开更多
As artificial intelligence and big data become increasingly prevalent, resistive random-access memory (RRAM) has become one of the most promising alternatives for storing massive amounts of data. In this study, we emp...As artificial intelligence and big data become increasingly prevalent, resistive random-access memory (RRAM) has become one of the most promising alternatives for storing massive amounts of data. In this study, we employed high-quality crystalline TiN/Al_(2)O_(3)/BaTiO_(3)/Pt RRAM with an optimized thin Al_(2)O_(3) interlayer around 12 nm thick prepared using atomic layer deposition since the thickness of the interlayer affects the memory window size. After insertion of the Al_(2)O_(3) interlayer, the novel RRAM exhibited outstanding uniform resistive switching voltage and the ON/OFF memory window drastically increased from 10 to 103 without any discernible decline in performance. Moreover, the low-resistance state and high-resistance state operating current values decreased by almost one order and three orders of magnitude, respectively, thereby decreasing the power consumption for the RESET and SET processes by more than three and almost one order of magnitude, respectively. The device also exhibits multilevel resistive switching behavior when varying the applied voltage. Finally, we also developed a 6 6 crossbar array which demonstrated consistent and reliable resistive switching behavior with minimal variation. Hence, our approach holds great promise for producing state-of-the-art non-volatile resistive switching devices.展开更多
Optimizing the orientation of β-Ga_(2)O_(3) has emerged as an effective strategy to design high-performance β-Ga_(2)O_(3) device,but the orientation growth mechanism and approach have not been revealed yet.Herein,by...Optimizing the orientation of β-Ga_(2)O_(3) has emerged as an effective strategy to design high-performance β-Ga_(2)O_(3) device,but the orientation growth mechanism and approach have not been revealed yet.Herein,by employing AlN buffer layer,the highly preferred orientation of β-Ga_(2)O_(3)(100)film rather than(-201)film is realized on 4H-SiC substrate at low sputtering power and temperature.Because β-Ga_(2)O_(3)(100)film exhibits a slower growth speed than(-201)film,the former possesses the higher dangling bond density and the lower nucleation energy,and a large conversion barrier exists between these two ori-entations.Moreover,the AlN buffer layer can suppress the surface oxidation of the 4H-SiC substrate and eliminate the strain of β-Ga_(2)O_(3)(100)film,which further reduces the nucleation energy and en-larges the conversion barrier.Meanwhile,the AlN buffer layer can increase the oxygen vacancy formation energy and decrease the oxygen vacancy concentration of β-Ga_(2)O_(3)(100)film.Consequently,the solar-blind photodetector based on the oriented film exhibits the outstanding detectivity of 1.22×10^(12) Jones and photo-to-dark current ratio of 1.11×10^(5),which are the highest among the reported β-Ga_(2)O_(3) solar-blind photodetector on the SiC substrate.Our results offer in-depth insights into the preferred orientation growth mechanism,and provide an effective way to design high-quality β-Ga_(2)O_(3)(100)orientation film and high-performance solar-blind photodetector.展开更多
Spinel LiNi_(0.5)Mn_(1.5)O_(4)(LNMO)cathode draws significant attention in the field of energy storage due to its unique voltage plateau.To further enhance the long-term electrochemical stability of LNMO,the LNMO cath...Spinel LiNi_(0.5)Mn_(1.5)O_(4)(LNMO)cathode draws significant attention in the field of energy storage due to its unique voltage plateau.To further enhance the long-term electrochemical stability of LNMO,the LNMO cathode covered with an ultrathin ZrO_(2)layer was prepared through atomic layer deposition(ALD).It is found that the LNMO cathode deposited with 20 layers of ZrO_(2)(LNMOZ20)exhibits the best electrochemical performance,achieving a high discharge capacity of 117.1 mA·h/g,with a capacity retention of 87.4%after 600 cycles at a current density of 1C.Furthermore,even at higher current densities of 5C and 10C,the LNMOZ20 electrode still demonstrates excellent stability with discharge capacities reaching 111.7 and 103.6 mA·h/g,and capacity retentions maintaining at 81.0%and 101.4%after 2000 cycles,respectively.This study highlights that the incorporation of an ultrathin ZrO_(2)layer by ALD is an effective strategy for enhancing the long-term cycling stability of LNMO cathodes.展开更多
The practical applications of aqueous Zn metal batteries are currently restricted by the inherent drawbacks of Zn such as the hydrogen evolution reaction,sluggish kinetics,and dendrite formation.To address these probl...The practical applications of aqueous Zn metal batteries are currently restricted by the inherent drawbacks of Zn such as the hydrogen evolution reaction,sluggish kinetics,and dendrite formation.To address these problems,herein,a limitedly Zn-doped MgF_(2)interphase comprising an upper region of pure,porous MgF_(2)and a lower region of gradient Zn-doped MgF_(2)is achieved via radio frequency sputtering technique.The porous MgF_(2)region is a polar insulator whose high corrosion resistance facilitates the de-solvation of the solvated Zn ions and suppression of hydrogen evolution,resulting in Zn metal electrodes with a low interfacial resistance.The Zn-doped MgF_(2)region facilitates fast transfer kinetics and homogeneous deposition of Zn ions owing to the interfacial polarization between the Zn dopant and MgF_(2)matrix,and the high concentration of the Zn dopant on the surface of the metal substrate as fine nuclei.Consequently,a symmetric cell incorporating the proposed Zn metal exhibits low overpotentials of~27.2 and~99.7 mV without Zn dendrites over 250 to 8000 cycles at current densities of 1.0 and 10.0 mA cm−2,respectively.The developed Zn/MnO2 full cell exhibits superior capacity retentions of 97.5%and 84.0%with average Coulombic efficiencies of 99.96%after 1000 and 3000 cycles,respectively.展开更多
This article provides a review of current research activities that concentrate on Ti3SiC2. We begin with an overview of the crystal and electronic structures, which are the basis to understand this material. Following...This article provides a review of current research activities that concentrate on Ti3SiC2. We begin with an overview of the crystal and electronic structures, which are the basis to understand this material. Followings are the synthetic strategies that have been exploited to achieve, and the formation mechanism of Ti3SiC2. Then we devote much attentions to the mechanical properties and oxidation/hot corrosion behaviors of Ti3SiC2 as well as some advances achieved recently. At the end of this paper, we elaborate on some new discoveries in the Ti3SiC2 system, and also give a brief discussion focused on the ＂microstructure -property＂ relationship.展开更多
基金supported by the“Pioneer”and“Leading Goose”R&D Program of Zhejiang Province of China(No.2024C01056)。
文摘Layered oxides have attracted significant attention as cathodes for sodium-ion batteries(SIBs)due to their compositional versatility and tuneable electrochemical performance.However,these materials still face challenges such as structural phase transitions,Na^(+)/vacancy ordering,and Jahn–Teller distortion effect,resulting in severe capacity decay and sluggish ion kinetics.We develop a novel Cu/Y dual-doping strategy that leads to the formation of"Na–Y"interlayer aggregates,which act as structural pillars within alkali metal layers,enhancing structural stability and disrupting the ordered arrangement of Na^(+)/vacancies.This disruption leads to a unique coexistence of ordered and disordered Na^(+)/vacancy states with near-zero strain,which significantly improves Na^(+)diffusion kinetics.This structural innovation not only mitigates the unfavorable P2–O2 phase transition but also facilitates rapid ion transport.As a result,the doped material demonstrates exceptional electrochemical performance,including an ultra-long cycle life of 3000 cycles at 10 C and an outstanding high-rate capability of~70 mAh g^(−1)at 50 C.The discovery of this novel interlayer pillar,along with its role in modulating Na^(+)/vacancy arrangements,provides a fresh perspective on engineering layered oxides.It opens up promising new pathways for the structural design of advanced cathode materials toward efficient,stable,and high-rate SIBs.
基金National Natural Science Foundation of China(52074052)。
文摘The Ti-Al alloy was synthesized using the aluminothermic reduction of TiO_(2),with CaO and MgF_(2)serving as flux components.Investigations were conducted to ascertain the effects of MgF_(2)content on the alloy-slag separation,alloy microstructure,composition,phase constitution,overall alloy yield,and aluminothermic reduction of TiO_(2).Results indicate that MgF_(2)enhances the separation of the alloy from slag and promotes the formation of the TiAl phase within the alloy matrix.Nevertheless,an overabundance of MgF_(2)reduces the interfacial tension between the Al reductant and the slag,leading to significant loss of Al.This adversely affects alloy-slag separation,escalates the incorporation of oxide inclusions in the alloy,and severely reduces the recovery rate of alloy.Concurrently,the alloy has a phase transition from TiAl to Ti_(3)Al.The optimum condition for alloy-slag separation and alloy integrity is realized at the MgF_(2)content of 10wt%.Kinetic analysis at this flux ratio determines the activating energy for the Al-TiO_(2)-CaO-MgF_(2)system,which is 409.729 kJ/mol,and the order of kinetics is n=0.38.
基金supported by the National Natural Science Foundation of China(No.21805018)by Sichuan Science and Technology Program(Nos.2022ZHCG0018,2023NSFSC0117 and 2023ZHCG0060)Yibin Science and Technology Program(No.2022JB005)and China Postdoctoral Science Foundation(No.2022M722704).
文摘Layered transition metal oxides have emerged as promising cathode materials for sodium ion batteries.However,irreversible phase transitions cause structural distortion and cation rearrangement,leading to sluggish Na+dynamics and rapid capacity decay.In this study,we propose a medium-entropy cathode by simultaneously introducing Fe,Mg,and Li dopants into a typical P2-type Na_(0.75)Ni_(0.25)Mn_(0.75)O_(2)cathode.The modified Na_(0.75)Ni_(0.2125)Mn_(0.6375)Fe_(0.05)Mg_(0.05)Li_(0.05)O_(2)cathode predominantly exhibits a main P2 phase(93.5%)with a minor O3 phase(6.5%).Through spectroscopy techniques and electrochemical investigations,we elucidate the redox mechanisms of Ni^(2+/3+/4+),Mn^(3+/4+),Fe^(3+/4+),and O_(2)-/O_(2)^(n-)during charging/discharging.The medium-entropy doping mitigates the detrimental P2-O_(2)phase transition at high-voltage,replacing it with a moderate and reversible structural evolution(P2-OP4),thereby enhancing structural stability.Consequently,the modified cathode exhibits a remarkable rate capacity of 108.4 mAh·g^(-1)at 10C,with a capacity retention of 99.0%after 200 cycles at 1C,82.5%after 500 cycles at 5C,and 76.7%after 600 cycles at 10C.Furthermore,it also demonstrates superior electrochemical performance at high cutoff voltage of 4.5 V and extreme temperature(55 and 0℃).This work offers solutions to critical challenges in sodium ion batteries cathode materials.
文摘CO_(2)hydrogenation to value-added light olefins(C_(2-4)=)is crucial for the utilization and cycling of global carbon resource.Moderate CO_(2)activation and carbon chain growth ability are key factors for iron-based catalysts for efficient CO_(2)conversion to target C_(2-4)=products.The electronic interaction and confinement effect of electron-deficient graphene inner surface on the active phase are effective to improve surface chemical properties and enhance the catalytic performance.Here,we report a core-shell FeCo alloy catalyst with graphene layers confinement prepared by a simple sol-gel method.The electron transfer from Fe species to curved graphene inner surface modifies the surface electronic structure of the active phaseχ-(Fe_(x)Co_(1-x))_(5)C_(2)and improves CO_(2)adsorption capacity,enhancing the efficient conversion of CO_(2)and moderate C-C coupling.Therefore,the catalyst FeCoK@C exhibits C_(2-4)=selectivity of 33.0%while maintaining high CO_(2)conversion of 52.0%.The high stability without obvious deactivation for over 100 h and unprecedented C_(2-4)=space time yield(STY)up to 52.9 mmolCO_(2)·g^(-1)·h^(-1)demonstrate its potential for practical application.This work provides an efficient strategy for the development of high-performance CO_(2)hydrogenation catalysts.
文摘Broadband transparent films play a pivotal role in various applications such as lenses and solar cells,particularly porous structured transparent films exhibit significant potential.This study investigates a porous SiO_(2) refractive index gradient anti-reflective film prepared by atomic layer deposition(ALD).A porous SiO_(2) film with gradual porosity was obtained by phosphoric acid etching of Al_(2)O_(3)/SiO_(2) multilayers with gradient Al2O3 ratios,achieving a gradual decrease in refractive index from the substrate to the surface.The film exhibited an average transmittance as high as 97.8%within the wavelength range from 320 nm to 1200 nm.The environmental adaptability was further enhanced by surface modification using rare earth oxide(REO)La_(2)O_(3),resulting in formation of a lotus leaf-like structure and achieving a water contact angle of 100.0°.These data proved that the modification significantly improved hydrophobic self-cleaning capability while maintaining exceptional transparency of the film.The surface structure of the modified film remained undamaged even after undergoing wipe testing,demonstrating its excellent surface durability.
基金financial support from the National Natural Science Foundation of China(22439001,52172198,51902117)supported by the Innovation Fund of Wuhan National Laboratory for Optoelectronicsthe Analytical and Testing Center of Huazhong University of Science and Technology(HUST)for performing various characterizations。
文摘Modulating the interface between the electron transport layer(ETL)and perovskite to minimize interfacial recombination is pivotal for developing efficient and stable perovskite solar cells.Here,we introduce an ultra-thin ZrO_(2)insulating interface layer onto the inner surface of the mesoporous TiO_(2)ETL via the chemical bath deposition in the zirconium n-butoxide solution,which alters the interface characteristics between TiO_(2)and perovskite for the printable hole-conductor-free mesoscopic perovskite solar cells(p-MPSCs).The insulating ZrO_(2)interface layer reduces interface defects and suppresses interfacial non-radiative recombination.Furthermore,the ZrO_(2)interface layer improves the wettability of the mesoporous TiO_(2)ETL,which favors the crystallization of perovskite within the mesoporous scaffold.Meanwhile,the device performance presents thickness dependence on the interface layer.While increased thickness improves the open-circuit voltage,excessive thickness negatively impacts both the short-circuit current density and fill factor.Consequently,an improved power conversion efficiency of 19.9% was achieved for p-MPSCs with the ZrO_(2)interface layer at its optimized thickness.
基金supported by the National Natural Science Foundation of China(Nos.52272060,51902067,51872066 and 52172041)the Key Program of National Natural Science Foundation of China(No.52032003)+5 种基金the Young Elite Scientists Sponsorship Program by CAST(No.2020QNRC001)China Postdoctoral Science Foundation(Nos.2019M651282 and 2022T150157)Heilongjiang Provincial Postdoctoral Science Foundation(Nos.LBH-Z19022 and LBH-TZ2207)Heilongjiang Touyan Innovation Team Program,Shanghai Aerospace Science and Technology Innovation Fund(No.SAST2019-012)the Fundamental Research Funds for the Central Universities(No.FRFCU5710051022)the Science Foundation of National Key Laboratory of Science and Technology on Advanced Composites in Special Environments(No.JCKYS2022603C011).
文摘The rapid evolution of hypersonic vehicle technologies necessitates robust thermal protection systems capable of withstanding extreme oxidative ablation.This study introduces a novel gradient-architected ZrB_(2)-MoSi_(2)-SiC dense layer embedded within a lightweight three-dimensional(3D)needled carbon fiber composite.Utilizing the volatility of ethanol and polycarbosilane,the ceramic slurry is selectively infused into targeted regions of the fibrous structure,optimizing the ZrB_(2)to MoSi_(2)ratio to enhance performance.The resulting dense layer exhibits exceptional emissivity,surpassing 0.90 in the 1-3μm range and exceeding 0.87 in the 2-14μm range.Moreover,it demonstrates remarkable oxidative ablation resistance.Specifically,at an optimized ZrB_(2)to MoSi_(2)ratio of 6:4,the dense layer achieves a minimal linear ablation rate of 0.015μm·s^(-1) under a 1.5 MW·m^(-2)oxyacetylene flame for 1000 s.Even after exposure to oxyacetylene ablation at surface temperatures of approximately 1750℃for 1000 s,the dense layer retains its structural integrity,highlighting its enduring oxidation resistance.The incorporation of MoSi_(2)not only enhances emissivity but also fortifies the ZrO_(2)and SiO_(2)oxide layers,crucial for environments with elevated oxygen levels,thereby mitigating the active oxidation of SiC.This combination of high emissivity and long-term oxidation resistance at ultra-high temperatures positions the ZrB_(2)-MoSi_(2)-SiC dense layer as an exceptionally promising candidate for advanced thermal protection in hypersonic vehicles.
基金the financial support from the National Key R&D Program of China(2024YFF0506100)the National Natural Science Foundation of China(52225606 and 52488201).
文摘Given the limited exposure of active sites and the retarded separation of photogenerated charge carriers in those developed photocata-lysts,photocatalyticCO_(2)splitting into value-added chemicals has suffered from the poor activity and remained in great challenge for real application.Herein,hydrothermally synthesized BiOCl with layered structure(BOC-NSs)was exfoliated into thickness reduced nanosheets(BOCNSs-w)and even atomic layers(BOCNSs-i)via ultrasonication in water and isopro-panol,respectively.In comparison with the pristine BOCNSs,the exfoli-ated BiOCl,especially BOCNSs-i with atomically layered structure,exhibits much improved photocatalytic activity forCO_(2)overall splitting to produce CO andO_(2) at a stoichiometric ratio of 2:1,with CO evolution rate reaching 134.8µmolg^(-1)h^(-1) under simulated solar light(1.7 suns).By surpassing the photocatalytic performances of the state-of-the-artBi_(l)O_(m)X_(n)(X:Cl,Br,I)based photocatalysts,the CO evolution rate is further increased by 99 times,reaching 13.3 mmolg^(-1)h^(-1) under concentrated solar irradiation(34 suns).This excellent photocatalytic performance achieved over BOCNSs-i should be benefited from the shortened transfer distance and the increased built-in electric field intensity,which acceler-ates the migration of photogenerated charge carriers to surface.Moreover,with oxygen vacancies(VO)introduced into the atomic layers,BOCNSs-i is exposed with the electrons enriched Bi active sites that could transfer electrons to activateCO_(2)molecules for highly efficient and selective CO production,by lowering the energy barrier of rate-determining step(RDS),*OH+*CO_(2)-→HCO_(3)-.It is also realized that theH_(2)O vapor supplied during photocatalytic reaction would exchange oxygen atoms withCO_(2),which could alter the reaction path-ways and further reduce the energy barrier of RDS,contributing to the dramatically improved photocatalytic performance forCO_(2)overall splitting to CO andO_(2).
基金supported by the National Natural Science Foundation of China(21808214)Research Project Supported by Shanxi Scholarship Council of China(2023-126)Fund Program for the Scientific Activities of Selected Returned Overseas Professionals in Shanxi Province(20220013)。
文摘Normally,a transparent inert film is coated on the surface of TiO_(2) particles to enhance the weatherability of the pigment.Liquid-phase coating process is mainly used in industry,which difficult to get really uniform films.This work combining nanoparticle fluidization technology with atomic layer deposition(ALD) technology to achieve precise surface modification of a large number of micro-nano particles.First,we explored the fluidization characteristics of TiO_(2) nanoparticles in a home-made atmospheric fluidized bed ALD reactor(FB-ALD) to ensure the uniform fluidization of a large number of nanoparticles.Then TiCl_(4) and H_(2)O were used as precursors to deposit amorphous TiO_(2) films on the surface of TiO_(2) nanoparticles at 80℃ under atmospheric pressure,and the growth per cycle was about 0.109 nm per cycle.After 30 ALD cycles,the film thickness was about 3.1 nm,which could almost fully suppress the photocatalytic activity of TiO_(2).Compared with other traditional coating materials,amorphous TiO_(2) has higher light refractive index,and realizes the suppression of the photocatalytic activity of TiO_(2) without introducing other substances,demonstrating greater application potential in TiO_(2) pigment coating field.The process is a gas-phase coating method,which is efficient,no waste water,and easy to scale up.This work shown the excellent property of interface engineering in improving pigment weatherability and can also provide guidance for the nanoparticle surface modification.
基金support from the European Union Horizon 2020 program(project HERMES,nr.952184)the Ministry of Education,Youth and Sports of the Czech Republic for supporting CEMNAT(LM2023037)+1 种基金Czech-NanoLab(LM2023051)infrastructures for providing ALD,SEM,EDX,XPS,TEM,and XRDCzech Science Foundation(project 23-08019X,EXPRO).
文摘Synergistic interplays involving multiple active centers originating from TiO2 nanotube layers(TNT)and ruthenium(Ru)species comprising of both single atoms(SAs)and nanoparticles(NPs)augment the alkaline hydrogen evolution reaction(HER)by enhancing Volmer kinetics from rapid water dissociation and improving Tafel kinetics from efficient H*desorption.Atomic layer deposition of Ru with 50 process cycles results in a mixture of Ru SAs and 2.8-0.4 nm NPs present on TNT layers,and it emerges with the highest HER activity among all the electrodes synthesized.A detailed study of the Ti and Ru species using different high-resolution techniques confirmed the presence of Ti^(3+)states and the coexistence of Ru SAs and NPs.With insights from literature,the role of Ti^(3+),appropriate work functions of TNT layers and Ru,and the synergistic effect of Ru SAs and Ru NPs in improving the performance of alkaline HER were elaborated and justified.The aforementioned characteristics led to a remarkable performance by having 9mV onset potentials and 33 mV dec^(-1) of Tafel slopes and a higher turnover frequency of 1.72 H2 s^(-1) at 30 mV.Besides,a notable stability from 28 h staircase chronopotentiometric measurements for TNT@Ru surpasses TNT@Pt in comparison.
基金supported by the National Research Foundation of Korea funded by the Korean Government(grant No.RS-2023-00208801).
文摘As artificial intelligence and big data become increasingly prevalent, resistive random-access memory (RRAM) has become one of the most promising alternatives for storing massive amounts of data. In this study, we employed high-quality crystalline TiN/Al_(2)O_(3)/BaTiO_(3)/Pt RRAM with an optimized thin Al_(2)O_(3) interlayer around 12 nm thick prepared using atomic layer deposition since the thickness of the interlayer affects the memory window size. After insertion of the Al_(2)O_(3) interlayer, the novel RRAM exhibited outstanding uniform resistive switching voltage and the ON/OFF memory window drastically increased from 10 to 103 without any discernible decline in performance. Moreover, the low-resistance state and high-resistance state operating current values decreased by almost one order and three orders of magnitude, respectively, thereby decreasing the power consumption for the RESET and SET processes by more than three and almost one order of magnitude, respectively. The device also exhibits multilevel resistive switching behavior when varying the applied voltage. Finally, we also developed a 6 6 crossbar array which demonstrated consistent and reliable resistive switching behavior with minimal variation. Hence, our approach holds great promise for producing state-of-the-art non-volatile resistive switching devices.
基金supported by the National Key Research and Development Program of China(No.2021YFA0715600)the National Natural Science Foundation of China(Nos.62274125,52192611)+2 种基金the Guangdong Basic and Applied Basic Research Fund(No.2023A1515030084)the Key Research and Development Program of Shaanxi Province(Grant No.2024GX-YBXM-410)the fund of the State Key Laboratory of Solidification Processing in NWPU(No.SKLSP202220).
文摘Optimizing the orientation of β-Ga_(2)O_(3) has emerged as an effective strategy to design high-performance β-Ga_(2)O_(3) device,but the orientation growth mechanism and approach have not been revealed yet.Herein,by employing AlN buffer layer,the highly preferred orientation of β-Ga_(2)O_(3)(100)film rather than(-201)film is realized on 4H-SiC substrate at low sputtering power and temperature.Because β-Ga_(2)O_(3)(100)film exhibits a slower growth speed than(-201)film,the former possesses the higher dangling bond density and the lower nucleation energy,and a large conversion barrier exists between these two ori-entations.Moreover,the AlN buffer layer can suppress the surface oxidation of the 4H-SiC substrate and eliminate the strain of β-Ga_(2)O_(3)(100)film,which further reduces the nucleation energy and en-larges the conversion barrier.Meanwhile,the AlN buffer layer can increase the oxygen vacancy formation energy and decrease the oxygen vacancy concentration of β-Ga_(2)O_(3)(100)film.Consequently,the solar-blind photodetector based on the oriented film exhibits the outstanding detectivity of 1.22×10^(12) Jones and photo-to-dark current ratio of 1.11×10^(5),which are the highest among the reported β-Ga_(2)O_(3) solar-blind photodetector on the SiC substrate.Our results offer in-depth insights into the preferred orientation growth mechanism,and provide an effective way to design high-quality β-Ga_(2)O_(3)(100)orientation film and high-performance solar-blind photodetector.
基金supported by the National Natural Science Foundation of China(Nos.51931006,U22A20118).
文摘Spinel LiNi_(0.5)Mn_(1.5)O_(4)(LNMO)cathode draws significant attention in the field of energy storage due to its unique voltage plateau.To further enhance the long-term electrochemical stability of LNMO,the LNMO cathode covered with an ultrathin ZrO_(2)layer was prepared through atomic layer deposition(ALD).It is found that the LNMO cathode deposited with 20 layers of ZrO_(2)(LNMOZ20)exhibits the best electrochemical performance,achieving a high discharge capacity of 117.1 mA·h/g,with a capacity retention of 87.4%after 600 cycles at a current density of 1C.Furthermore,even at higher current densities of 5C and 10C,the LNMOZ20 electrode still demonstrates excellent stability with discharge capacities reaching 111.7 and 103.6 mA·h/g,and capacity retentions maintaining at 81.0%and 101.4%after 2000 cycles,respectively.This study highlights that the incorporation of an ultrathin ZrO_(2)layer by ALD is an effective strategy for enhancing the long-term cycling stability of LNMO cathodes.
基金supported by research grants from the National Research Foundation(NRF-2019H1D3A1A01069779)funded by the Ministry of Science and ICT,Republic of Korea,and by the Institutional Program(2E31863)and Bridge Program-KIST(2V09284).
文摘The practical applications of aqueous Zn metal batteries are currently restricted by the inherent drawbacks of Zn such as the hydrogen evolution reaction,sluggish kinetics,and dendrite formation.To address these problems,herein,a limitedly Zn-doped MgF_(2)interphase comprising an upper region of pure,porous MgF_(2)and a lower region of gradient Zn-doped MgF_(2)is achieved via radio frequency sputtering technique.The porous MgF_(2)region is a polar insulator whose high corrosion resistance facilitates the de-solvation of the solvated Zn ions and suppression of hydrogen evolution,resulting in Zn metal electrodes with a low interfacial resistance.The Zn-doped MgF_(2)region facilitates fast transfer kinetics and homogeneous deposition of Zn ions owing to the interfacial polarization between the Zn dopant and MgF_(2)matrix,and the high concentration of the Zn dopant on the surface of the metal substrate as fine nuclei.Consequently,a symmetric cell incorporating the proposed Zn metal exhibits low overpotentials of~27.2 and~99.7 mV without Zn dendrites over 250 to 8000 cycles at current densities of 1.0 and 10.0 mA cm−2,respectively.The developed Zn/MnO2 full cell exhibits superior capacity retentions of 97.5%and 84.0%with average Coulombic efficiencies of 99.96%after 1000 and 3000 cycles,respectively.
基金the financial support for this work from the National Natural Science Foundation of China(Nos.U1764254,51871166)the Tianjin Natural Science Foundation,China(No.20JCYBJC00620)。
基金supported by the National Outstanding Young Scientist Foundation for Y.C. Zhou under Grant No. 59925208the National Natural Science Foundation of China under Grants No. 50232040, No. 50302011 and No. 90403027"863" Project,and High-Tech Bureau of the Chinese Academy of Sciences
文摘This article provides a review of current research activities that concentrate on Ti3SiC2. We begin with an overview of the crystal and electronic structures, which are the basis to understand this material. Followings are the synthetic strategies that have been exploited to achieve, and the formation mechanism of Ti3SiC2. Then we devote much attentions to the mechanical properties and oxidation/hot corrosion behaviors of Ti3SiC2 as well as some advances achieved recently. At the end of this paper, we elaborate on some new discoveries in the Ti3SiC2 system, and also give a brief discussion focused on the ＂microstructure -property＂ relationship.
