Since the first discovery of gold deposits on the northeastern margin of the Jiaolai Basin in Shandong Province at the end of the 20^(th) century,seven medium-sized to large/super-large gold deposits have been identif...Since the first discovery of gold deposits on the northeastern margin of the Jiaolai Basin in Shandong Province at the end of the 20^(th) century,seven medium-sized to large/super-large gold deposits have been identified in this region,with cumulative proven gold resources of 223 t.This study reviewed the metallogenic and geochemical characteristics of various gold deposits in this region,examined the sources of their ore-forming fluids and materials,as well as their gold metallogenic epochs and processes,and developed a gold metallogenic model.The gold deposits in this region are governed by both dense fractures and detachment structural systems along basin margins,primarily categorized into the altered rock type and the pyrite-bearing carbonate vein type.The latter type,a recently discovered mineralization type in the Jiaodong Peninsula,enjoys high gold grade,a large scale,and high gold mineral fineness,suggesting considerable prospecting potential.Both types of gold deposits show metallogenic epochs ranging from 116 Ma to 119 Ma.Their ore-forming fluids are identified as a CO_(2)-NaCl-H_(2)O fluid system characterized by moderate to low temperatures,moderate to low salinity,and low density,with the pyrite-bearing carbonate vein-type gold deposits manifesting slightly higher salinity.The C-H-O,S,and Pb isotopes of hydrothermal minerals reveal that the ore-forming fluids and materials are characteristic of crust-mantle mixing.Specifically,they were derived from mantle fluids in the early stages,mixed with stratum water and meteoric water in the later stages for mineralization.The gold metallogenic process is identified as follows:During the Early Cretaceous,the subduction of the Pacific Plate and the destruction of the North China Craton led to asthenospheric upwelling.The resulting fluids,after metasomatizing the enriched mantle,differentiated and evolved into C-H-O ore-bearing fluids,which were then mixed with crustal fluids.The mixed fluids migrated to the shallow crust,where they mingled with stratum water and meteoric water.Then,the fluids underwent unloading and final mineralization in detachment fault tectonic systems on basin margins.Due to differences in mixed crustal materials or the surrounding rocks involved in water-rock interactions,altered rock-and pyrite-bearing carbonate vein-type gold deposits were formed in acidic and alkaline fluid environments,respectively.展开更多
Throughout the globe,diabetes mellitus（DM） is increasing in incidence with limited therapies presently available to prevent or resolve the significant complications of this disorder.DM impacts multiple organs and af...Throughout the globe,diabetes mellitus（DM） is increasing in incidence with limited therapies presently available to prevent or resolve the significant complications of this disorder.DM impacts multiple organs and affects all components of the central and peripheral nervous systems that can range from dementia to diabetic neuropathy.The mechanistic target of rapamycin（m TOR） is a promising agent for the development of novel regenerative strategies for the treatment of DM.m TOR and its related signaling pathways impact multiple metabolic parameters that include cellular metabolic homeostasis,insulin resistance,insulin secretion,stem cell proliferation and differentiation,pancreatic β-cell function,and programmed cell death with apoptosis and autophagy.m TOR is central element for the protein complexes m TOR Complex 1（m TORC1） and m TOR Complex 2（m TORC2） and is a critical component for a number of signaling pathways that involve phosphoinositide 3-kinase（PI 3-K）,protein kinase B（Akt）,AMP activated protein kinase（AMPK）,silent mating type information regulation 2 homolog 1（Saccharomyces cerevisiae）（SIRT1）,Wnt1 inducible signaling pathway protein 1（WISP1）,and growth factors.As a result,m TOR represents an exciting target to offer new clinical avenues for the treatment of DM and the complications of this disease.Future studies directed to elucidate the delicate balance m TOR holds over cellular metabolism and the impact of its broad signaling pathways should foster the translation of these targets into effective clinical regimens for DM.展开更多
Reactive oxygen species(ROS),including singlet oxygen(^(1)O_(2)),hydroxyl radicals(·OH),and superoxide anions(O_(2)^(·-)),are highly reactive molecules that play central roles in many chemical,biological,and...Reactive oxygen species(ROS),including singlet oxygen(^(1)O_(2)),hydroxyl radicals(·OH),and superoxide anions(O_(2)^(·-)),are highly reactive molecules that play central roles in many chemical,biological,and environmental processes due to their strong oxidative power[1].Generating ROS in a controlled manner under mild conditions is essential for achieving selective oxidation reactions.Light-driven methods are especially appealing for this purpose,as they offer precise control over where and when ROS are produced.展开更多
Non-O1/non-O139 Vibrio cholerae(NOVC)has multiple pathogenic pathways in humans.The cause of disease in influenced by the virulence genes carried by the infecting strain and the health condition of the host.[1-2]When ...Non-O1/non-O139 Vibrio cholerae(NOVC)has multiple pathogenic pathways in humans.The cause of disease in influenced by the virulence genes carried by the infecting strain and the health condition of the host.[1-2]When seafood,food and water sources are contaminated with feces,people are prone to gastroenteritis,and direct exposure to contaminated water may cause wound infection.展开更多
The growth of single-crystalα-Al_(2)O_(3) is crucial for a variety of applications in electronics and other fields,while the synthesis of its two-dimensional(2D)form is not easy due to the high activation energy.Here...The growth of single-crystalα-Al_(2)O_(3) is crucial for a variety of applications in electronics and other fields,while the synthesis of its two-dimensional(2D)form is not easy due to the high activation energy.Here,we demonstrate the growth of single-crystal 2Dα-Al_(2)O_(3) by high temperature(high-T)annealing of Ni foils.Tens of micrometers of 2Dα-Al_(2)O_(3) flakes grow on the surface of Ni foils,which is attributed to the precipitation of Al atoms from the Ni foil bulk to its surface,followed by the oxidation of Al atoms on the surface.In principle,the Ni foil acts as a solvent,where diluted metal atoms precipitate onto the surface and react with oxygen from the atmosphere to grow single-crystal 2D metal oxides.Our findings may also provide a promising method for synthesizing other single-crystal 2D metal oxides.展开更多
For the new subclass B of the bi-univalent functions constructed with the help of the(u,v)-Chebyshev polynomials of the second type,we get estimates for the first two initial coefficients and upper bounds of the Feket...For the new subclass B of the bi-univalent functions constructed with the help of the(u,v)-Chebyshev polynomials of the second type,we get estimates for the first two initial coefficients and upper bounds of the Fekete-Szeg o functional.展开更多
Artificial photosynthesis presents a sustainable and cost-effective approach to harnessing solar energy to produce value-added chemicals[1,2].In particular,the simultaneous photocatalytic conversion of CO_(2)and H_(2)...Artificial photosynthesis presents a sustainable and cost-effective approach to harnessing solar energy to produce value-added chemicals[1,2].In particular,the simultaneous photocatalytic conversion of CO_(2)and H_(2)O into formic acid(HCOOH)and hydrogen peroxide(H2O2)has emerged as a promising strategy to mitigate global warming driven by CO_(2)emissions.HCOOH is a versatile chemical and hydrogen carrier,offering economic and practical advantages due to its compatibility with existing industrial processes and energy storage/conversion systems.Meanwhile,H_(2)O_(2)is among the world’s top 100 essential chemicals,with a global market valued at$4.0 billion in 2020 and projected to grow to$5.2 billion by 2026.展开更多
To the Editor:Acute cholangitis,also known as ascending cholangitis,is a po-tentially life-threatening condition resulting from the infection and obstruction of the biliary tract[1].Choledocholithiasis,which in-volves...To the Editor:Acute cholangitis,also known as ascending cholangitis,is a po-tentially life-threatening condition resulting from the infection and obstruction of the biliary tract[1].Choledocholithiasis,which in-volves stones in the common bile duct,is the most frequent cause of such infections,leading to partial or complete blockage of the biliary system[2].During acute episodes,patients may present with abdominal pain,high fever,and jaundice,known as Charcot’s triad,and in severe cases,patients may also exhibit signs of shock and depression[3].An episode of cholangitis can be fatal,and if the underlying obstruction is not addressed,the condition may recur,potentially leading to hepatic abscesses or biliary cirrhosis.Other etiologies of cholangitis include benign biliary strictures,bil-iary malignancies,congenital factors,postoperative complications,inflammatory conditions,and rare causes such as pancreatitis,par-asitic invasion of the biliary tract,external compression,thrombo-sis,and iatrogenic factors.Acute cholecystitis due to the migration of Hem-o-lok clips postoperation is rare.Herein we reported a case of acute cholangitis caused by the migration of surgical Hem-o-lok clips into the bile duct six years after laparoscopic left hemihepa-tectomy.展开更多
Solar-driven H_(2)O_(2) production through artificial photosynthesis presents a promising alternative to anthraquinone,given its lower energy consumption and eco-friendly nature[1-3].However,its catalytic performance ...Solar-driven H_(2)O_(2) production through artificial photosynthesis presents a promising alternative to anthraquinone,given its lower energy consumption and eco-friendly nature[1-3].However,its catalytic performance is severely restricted by the inefficient separation of photogenerated carriers and interface reactions[4,5].展开更多
The discovery of high-temperature superconductivity in bilayer nickelate La_(3)Ni_(2)O_(7)under high-pressure conditions has spurred extensive efforts to stabilize superconductivity at ambient pressure.Recently,the re...The discovery of high-temperature superconductivity in bilayer nickelate La_(3)Ni_(2)O_(7)under high-pressure conditions has spurred extensive efforts to stabilize superconductivity at ambient pressure.Recently,the realization of superconductivity in compressively strained La_(3)Ni_(2)O_(7)thin films grown on the SrLaAlO_(4)substrates,with a T_(c)exceeding 40 K,represents a significant step toward this goal.Here,we investigate the influence of film thickness and carrier doping on the electronic structure of La_(3)Ni_(2)O_(7)thin films,ranging from 0.5 to 3 unit cells,using first-principles calculations.For a 2 unit-cell film with an optimal doping concentration of 0.3 hole per formula unit(0.15 hole/Ni),the Ni-d_(z^(2))interlayer bonding state crosses the Fermi level,resulting in the formation ofγpockets at the Fermi surface.These findings align with angle-resolved photoemission spectroscopy experimental data.Our results provide theoretical validation for the recent experimental discovery of ambient-pressure superconductivity in La_(3)Ni_(2)O_(7)thin films and underscore the significant impact of film thickness and carrier doping on electronic property modulation.展开更多
The cubic pyrochlore Tl_(2)Ru_(2)O_(7) undergoes concurrently a metal–insulator transition (MIT) and a first-order structural transition at T_(MIT)≈120 K,below which the system was found to form one-dimensional spin...The cubic pyrochlore Tl_(2)Ru_(2)O_(7) undergoes concurrently a metal–insulator transition (MIT) and a first-order structural transition at T_(MIT)≈120 K,below which the system was found to form one-dimensional spin-one Haldane chains associated with an orbital ordering of Ru-4d electrons.With an aim to tune and access distinct ground states with strong entanglements of multiple degrees of freedom,i.e.,spin,orbital,charge,and lattice,we utilize a high-pressure approach to regulate the MIT of this system.Our detailed resistivityρ(T) measurements on the polycrystalline Tl_(2)Ru_(2)O_(7) samples under various hydrostatic pressures indeed reveal an unusual evolution of the electronic ground states.At first,the MIT is suppressed monotonically from 120 K at ambient to about 70 K at 1.5 GPa and then vanishes suddenly at about 1.8 GPa without achieving a metallic ground state.Meanwhile,the system evolves into a semiconducting ground state with magnitude ofρ(T) in the entire temperature range enhanced gradually by further increasing pressure.Prior to the abrupt disappearance of MIT,a new electronic order manifested as a kink-like anomaly inρ(T) emerges at T_(0)>T_(MIT) at 1.2 GPa and it continues to increase with pressure,producing a tricritical-point-like behavior in the T–P phase diagram of Tl_(2)Ru_(2)O_(7).The presence of two successive transitions at T_(0 )and T_(MIT )in the pressure range 1.2–1.5 GPa indicates an inhomogeneous electronic state nearby the tricritical point.At P≥3 GPa,another broad anomaly emerges inρ(T) at T_(1)>T_(0),and T_(1)continuously increases with pressure,dividing the semiconductingρ(T) into distinct thermally activated regions.These rich phenomena in the pressurized Tl_(2)Ru_(2)O_(7) should originate from the complex interplay of strongly entangled multiple quantum degrees of freedom in the system near the localized-to-itinerant crossover regime.展开更多
Recent studies have successfully demonstrated high-Tc superconductivity in bilayer nickelate La3Ni2O7.However,research on modulating the structural and transport characteristics of La3Ni2O7 films by applying“chemical...Recent studies have successfully demonstrated high-Tc superconductivity in bilayer nickelate La3Ni2O7.However,research on modulating the structural and transport characteristics of La3Ni2O7 films by applying“chemical”compressive pressure through cation substitution is still limited.Here,we address this issue in the La_(3−x)Nd_(x)Ni_(2)O_(7)(x=0,1.0,1.5,2.0,and 2.5)thin film samples.It was found that using Nd3+with a smaller radius instead of La3+can reduce the c-axis lattice constant and shift the metal-insulator transition(MIT)temperature TMIT.To probe the origin of the MIT at cryogenic temperatures,experimental measurements of magnetoresistance were conducted,and theoretical analysis was carried out using the Kondo model,Hikami-Larkin-Nagaoka equation,and other methods.The results indicate that as Nd doping rises,the contributions of the Kondo effect and two-dimensional weak localization(WL)first decrease and then increase.The total contribution of WL and the Kondo effect in the mid-doped La_(1.5)Nd_(1.5)Ni_(2)O_(7)sample was the smallest,which to some extent explains the changes in TMIT.The Kondo effect dominates in other La_(3−x)Nd_(x)Ni_(2)O_(7)(x=0,1.0,2.0,and 2.5)samples.This work demonstrates that cation doping has a significant impact on bilayer nickelates,providing experimental evidence for understanding the physical mechanism of the MIT in bilayer nickelates.展开更多
Flash drought is characterized by a period of rapid drought intensification with impacts on agriculture,water resources,ecosystems,and human environment.In the Qilian Mountains,northwestern China,flash droughts are be...Flash drought is characterized by a period of rapid drought intensification with impacts on agriculture,water resources,ecosystems,and human environment.In the Qilian Mountains,northwestern China,flash droughts are becoming more frequently due to the global climate warming.However,the spatiotemporal variations and their driving factors of flash droughts are not clear in this region.In this study,the European Centre for Medium-range Weather Forecasts(ECMWF)Reanalysis v5-Land(ERA5-Land)dataset was utilized to identify two types of flash drought events(heatwave-induced and water scarcity-induced flash drought events)that occurred in the growing season(April‒September)during 1981-2020 in this area.The results showed that the frequency of heatwave-induced flash droughts has decreased since 2010,while the frequency of water scarcity-induced flash droughts has declined markedly.Spatially,heatwave-induced flash droughts were predominantly concentrated in the western Qilian Mountains,whereas water scarcity-induced flash droughts were primarily concentrated in the central and eastern Qilian Mountains.A significantly increasing temporal trend in both types of flash droughts in the eastern Qilian Mountains was found.Meanwhile,there was a decreasing temporal trend of heatwave-induced flash droughts in the southwestern part of the region.Additionally,the influence of two major atmospheric modes,i.e.,the El Niño‒Southern Oscillation(ENSO)and North Atlantic Oscillation(NAO),on these two types of flash droughts was explored by the Superposed Epoch Analysis.The ENSO mainly influences flash droughts in the central and eastern parts of the Qilian Mountains by altering the strength of the East Asian monsoon,while the NAO mainly affects flash droughts in the entire parts of the Qilian Mountains by inducing anomalous westerlies activity.Our findings have important implications for predicting the evolution of flash drought events in the Qilian Mountains region under continued climate warming.展开更多
In this work,the TiO_(2)/Sb_(2)S_(3) nanorod arrays(NRAs)were synthesized through a two-stage hydrothermal route for photoelectrochemical(PEC)water splitting.The effect of annealing treatment in Ar ambience on the PEC...In this work,the TiO_(2)/Sb_(2)S_(3) nanorod arrays(NRAs)were synthesized through a two-stage hydrothermal route for photoelectrochemical(PEC)water splitting.The effect of annealing treatment in Ar ambience on the PEC activity of TiO_(2)/Sb_(2)S_(3) composite sample was investigated by electrochemical impedance analysis,including Nyquist and Mott-Schottky(M-S)plots.It was demonstrated that vacuum annealing could crystallize Sb_(2)S_(3) component and change its color from red to black,leading to an increment of photocurrent density from 1.9 A/m^(2) to 4.25 A/m^(2) at 0 V versus saturated calomel electrode(VSCE).The enhanced PEC performance was mainly attributed to the improved visible light absorption.Moreover,annealing treatment facilitated retarding the electron-hole recombination occurred at the solid/liquid interfaces.Our work might provide a novel strategy for enhancing the PEC performance of a semiconductor electrode.展开更多
Here we report that the presence of MgCO_(3) stimulates the extracellular polymeric substance (EPS) secretion of Microcystis Aeruginosa (M. Aeruginosa). This stimulation led to a significant reduction in the total con...Here we report that the presence of MgCO_(3) stimulates the extracellular polymeric substance (EPS) secretion of Microcystis Aeruginosa (M. Aeruginosa). This stimulation led to a significant reduction in the total concentration of NH_(4)^(+)‒N by more than 86%, and effective recovery of PO_(4)^(3-)‒P within three days from concentrated wastewater (WW), although the secreted EPS inhibited the conversion of MgCO_(3) to specific crystal forms (MgNH4PO4.6H2O or MgHPO4.7H2O). Moreover, with an increase in PO_(4)^(3-) concentration in WW, these crystals appeared, thus the removal of NH_(4)^(+)‒N and PO_(4)^(3-)‒P nutrients can be attributed to the combined effect of M. Aeruginosa and MgCO_(3). We used Surface-Enhanced Raman Spectroscopy (SERS) combined with X-ray Diffraction (XRD), Field Emission Scanning Electron Microscopy with Energy-Dispersive X-ray Spectroscopy (FESEM-EDS), and X-ray Photoelectron Spectroscopy (XPS) to investigate the mechanism for competitive interactions between M. Aeruginosa and MgCO_(3) in removing NH_(4)^(+)‒N and PO_(4)^(3-)‒P. We identified that the bound EPS accumulated amorphous Mg–P–O dense particles on M. Aeruginosa, while soluble EPS, containing –COOH groups of humic-like substances decreased the pH of the solution and coordinated with Mg^(2+) ions. Therefore, both secreted bound and soluble EPS play a vital role in hindering the transformation of Mg^(2+) ions or MgCO_(3) to MgNH4PO4.6H2O or MgHPO4.7H2O crystals within WW, and they enhanced M. Aeruginosa 's ability in absorbing nutrients of NH_(4)^(+)‒N and PO_(4)^(3-)‒P. This mechanism plays a crucial role in the efficient recovery of NH_(4)^(+)‒N and PO_(4)^(3-)‒P from concentrated wastewater sources such as aerobically or anaerobically digested effluent from various sources like agriculture, livestock, and domestic wastewaters.展开更多
Secondary pollutant ozone (O3) formation in a particular area is often influenced by various factors. Source of emissions is one of the factors. In south east Texas, Houston-Galveston-Brazoria (HGB) is a marginal non-...Secondary pollutant ozone (O3) formation in a particular area is often influenced by various factors. Source of emissions is one of the factors. In south east Texas, Houston-Galveston-Brazoria (HGB) is a marginal non-attainment area for ozone (O3). A summer episode of May 28 to July 2, 2006 is simulated using Comprehensive Air Quality Model with extensions (CAMx). During this period O3 concentration in HGB often exceeds the National Ambient Air Quality Standards (NAAQS) 0.075 ppm of average 8 hour O3 concentration. HGB area has numerous point sources. Various studies found that some specific volatile organic compounds are very reactive in atmosphere. The objective of this study is to analyze the influence of volatile organic compounds present in point source emissions on the air quality of HGB area. For this purpose ozone sensitivity for HGB area is analyzed by the ratio of hydrogen peroxides (H2O2) to nitric acid (HNO3). HGB area is found NOx limited but reactive VOCs are found to be influential too. From (1-4 June, 2006) maximum O3 concentration was found on weekend, June 3. VOCs such as Acetaldehyde (ALD2), Formaldehyde (FORM) and Alkane (ETHA) showed good correlation with O3 concentrations on that day. In addition, Peroxyacetyl nitrate (PAN) formation was found correlated to higher ozone production. Criteria pollutant Sulfur dioxide (SO2) was found to influence the ALD2 and ETHA concentrations, and thus indirectly influenced O3 production.展开更多
Electrochemical carbon dioxide reduction reaction(CO_(2)RR)produces valuable chemicals by consuming gaseous CO_(2)as well as protons from the electrolyte.Protons,produced by water dissociation in alkaline electrolyte,...Electrochemical carbon dioxide reduction reaction(CO_(2)RR)produces valuable chemicals by consuming gaseous CO_(2)as well as protons from the electrolyte.Protons,produced by water dissociation in alkaline electrolyte,are critical for the reaction kinetics which involves multiple proton coupled electron transfer steps.Herein,we demonstrate that the two key steps(CO_(2)-^(*)COOH and^(*)CO-^(*)COH)efficiency can be precisely tuned by introducing proper amount of water dissociation center,i.e.,Fe single atoms,locally surrounding the Cu catalysts.In alkaline electrolyte,the Faradaic efficiency(FE)of multi-carbon(C^(2+))products exhibited a volcano type plot depending on the density of water dissociation center.A maximum FE for C^(2+)products of 73.2%could be reached on Cu nanoparticles supported on N-doped Carbon nanofibers with moderate Fe single atom sites,at a current density of 300 mA cm^(–2).Experimental and theoretical calculation results reveal that the Fe sites facilitate water dissociation kinetics,and the locally generated protons contribute significantly to the CO_(2)activation and^(*)CO protonation process.On the one hand,in-situ attenuated total reflection surface-enhanced infrared absorption spectroscopy(in-situ ATR-SEIRAS)clearly shows that the^(*)COOH intermediate can be observed at a lower potential.This phenomenon fully demonstrates that the optimized local water dissociation kinetics has a unique advantage in guiding the hydrogenation reaction pathway of CO₂molecules and can effectively reduce the reaction energy barrier.On the other hand,abundant^(*)CO and^(*)COH intermediates create favorable conditions for the asymmetric^(*)CO-^(*)COH coupling,significantly increasing the selectivity of the reaction for C^(2+)products and providing strong support for the efficient conversion of related reactions to the target products.This work provides a promising strategy for the design of a dual sites catalyst to achieve high FE of C^(2+)products through the optimized local water dissociation kinetics.展开更多
Layered transition metal hydroxides show distinct advantages in separately co-catalyzing CO_(2)reduction and H_(2)O oxidation at the electron-accumulating and hole-accumulating sites of wrapped heterojunction photocat...Layered transition metal hydroxides show distinct advantages in separately co-catalyzing CO_(2)reduction and H_(2)O oxidation at the electron-accumulating and hole-accumulating sites of wrapped heterojunction photocatalysts,while concurrently preventing side reactions and photocorrosion on the semiconductor surface.Herein,Ni-Co bimetallic hydroxides with varying Ni/Co molar ratios(Ni_(x)Co_(1-x)(OH)_(2),x=1,0.75,0.5,0.25,and 0)were grown in situ on a model 2D/2D S-scheme heterojunction composed of Cu_(2)O nanosheets and Fe_(2)O_(3)nanoplates to form a series of Cu_(2)O/Fe_(2)O_(3)@Ni_(x)Co_(1-x)(OH)_(2)(CF@NiCo)photocatalysts.The combined experimental and theoretical investigation demonstrates that incorporating an appropriate amount of Co into Ni(OH)_(2)not only modulates the energy band structure of Ni_(x)Co_(1-x)(OH)_(2),balances the electron-and hole-trapping abilities of the bifunctional cocatalyst and maximizes the charge separation efficiency of the heterojunction,but also regulates the d-band center of Ni_(x)Co_(1-x)(OH)_(2),reinforcing the adsorption and activation of CO_(2)and H_(2)O on the cocatalyst surface and lowering the rate-limiting barriers in the CO_(2)-to-CO and H_(2)O-to-O_(2)conversion.Benefiting from the Ni-Co synergy,the redox reactions proceed stoichiometrically.The optimized CF@Ni_(0.75)Co_(0.25)achieves CO and O_(2)yields of 552.7 and 313.0μmol gcat^(-1)h^(-1),respectively,11.3/9.9,1.6/1.7,and 4.5/5.9-fold higher than those of CF,CF@Ni,and CF@Co.This study offers valuable insights into the design of bifunctional noble-metal-free cocatalysts for high-performance artificial photosynthesis.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
基金supported by the Program of the National Natural Science Foundation of China(Nos.41973048,U2006201)the Open Project of State Key Laboratory of Geological Processes and Mineral Resources(No.GPMR202203)+1 种基金the Key R&D Program of Shandong Province(No.2023CXGC011001),the Taishan Scholars.Program(tstp20240847)the Open Project of Shandong Engineering Research Center of Application and Development of Big Data for Deep Gold Exploration(No.SDK202207)。
文摘Since the first discovery of gold deposits on the northeastern margin of the Jiaolai Basin in Shandong Province at the end of the 20^(th) century,seven medium-sized to large/super-large gold deposits have been identified in this region,with cumulative proven gold resources of 223 t.This study reviewed the metallogenic and geochemical characteristics of various gold deposits in this region,examined the sources of their ore-forming fluids and materials,as well as their gold metallogenic epochs and processes,and developed a gold metallogenic model.The gold deposits in this region are governed by both dense fractures and detachment structural systems along basin margins,primarily categorized into the altered rock type and the pyrite-bearing carbonate vein type.The latter type,a recently discovered mineralization type in the Jiaodong Peninsula,enjoys high gold grade,a large scale,and high gold mineral fineness,suggesting considerable prospecting potential.Both types of gold deposits show metallogenic epochs ranging from 116 Ma to 119 Ma.Their ore-forming fluids are identified as a CO_(2)-NaCl-H_(2)O fluid system characterized by moderate to low temperatures,moderate to low salinity,and low density,with the pyrite-bearing carbonate vein-type gold deposits manifesting slightly higher salinity.The C-H-O,S,and Pb isotopes of hydrothermal minerals reveal that the ore-forming fluids and materials are characteristic of crust-mantle mixing.Specifically,they were derived from mantle fluids in the early stages,mixed with stratum water and meteoric water in the later stages for mineralization.The gold metallogenic process is identified as follows:During the Early Cretaceous,the subduction of the Pacific Plate and the destruction of the North China Craton led to asthenospheric upwelling.The resulting fluids,after metasomatizing the enriched mantle,differentiated and evolved into C-H-O ore-bearing fluids,which were then mixed with crustal fluids.The mixed fluids migrated to the shallow crust,where they mingled with stratum water and meteoric water.Then,the fluids underwent unloading and final mineralization in detachment fault tectonic systems on basin margins.Due to differences in mixed crustal materials or the surrounding rocks involved in water-rock interactions,altered rock-and pyrite-bearing carbonate vein-type gold deposits were formed in acidic and alkaline fluid environments,respectively.
基金supported by American Diabetes Association,American Heart Association,NIH NIEHS,NIH NIA,NIH NINDS,and NIH ARRA
文摘Throughout the globe,diabetes mellitus（DM） is increasing in incidence with limited therapies presently available to prevent or resolve the significant complications of this disorder.DM impacts multiple organs and affects all components of the central and peripheral nervous systems that can range from dementia to diabetic neuropathy.The mechanistic target of rapamycin（m TOR） is a promising agent for the development of novel regenerative strategies for the treatment of DM.m TOR and its related signaling pathways impact multiple metabolic parameters that include cellular metabolic homeostasis,insulin resistance,insulin secretion,stem cell proliferation and differentiation,pancreatic β-cell function,and programmed cell death with apoptosis and autophagy.m TOR is central element for the protein complexes m TOR Complex 1（m TORC1） and m TOR Complex 2（m TORC2） and is a critical component for a number of signaling pathways that involve phosphoinositide 3-kinase（PI 3-K）,protein kinase B（Akt）,AMP activated protein kinase（AMPK）,silent mating type information regulation 2 homolog 1（Saccharomyces cerevisiae）（SIRT1）,Wnt1 inducible signaling pathway protein 1（WISP1）,and growth factors.As a result,m TOR represents an exciting target to offer new clinical avenues for the treatment of DM and the complications of this disease.Future studies directed to elucidate the delicate balance m TOR holds over cellular metabolism and the impact of its broad signaling pathways should foster the translation of these targets into effective clinical regimens for DM.
文摘Reactive oxygen species(ROS),including singlet oxygen(^(1)O_(2)),hydroxyl radicals(·OH),and superoxide anions(O_(2)^(·-)),are highly reactive molecules that play central roles in many chemical,biological,and environmental processes due to their strong oxidative power[1].Generating ROS in a controlled manner under mild conditions is essential for achieving selective oxidation reactions.Light-driven methods are especially appealing for this purpose,as they offer precise control over where and when ROS are produced.
基金supported by the National Natural Science Foundation(82372206)the Jiangsu Provincial Health Commission(H2023107)the project of basic and clinical research on cardiac arrest in the Emergency and Critical Care Department of the Second Affiliated Hospital of Soochow University(XKTJ-XK202408-2).
文摘Non-O1/non-O139 Vibrio cholerae(NOVC)has multiple pathogenic pathways in humans.The cause of disease in influenced by the virulence genes carried by the infecting strain and the health condition of the host.[1-2]When seafood,food and water sources are contaminated with feces,people are prone to gastroenteritis,and direct exposure to contaminated water may cause wound infection.
基金supported by Shenzhen Science and Technology Program(No.KQTD20200820113010022).
文摘The growth of single-crystalα-Al_(2)O_(3) is crucial for a variety of applications in electronics and other fields,while the synthesis of its two-dimensional(2D)form is not easy due to the high activation energy.Here,we demonstrate the growth of single-crystal 2Dα-Al_(2)O_(3) by high temperature(high-T)annealing of Ni foils.Tens of micrometers of 2Dα-Al_(2)O_(3) flakes grow on the surface of Ni foils,which is attributed to the precipitation of Al atoms from the Ni foil bulk to its surface,followed by the oxidation of Al atoms on the surface.In principle,the Ni foil acts as a solvent,where diluted metal atoms precipitate onto the surface and react with oxygen from the atmosphere to grow single-crystal 2D metal oxides.Our findings may also provide a promising method for synthesizing other single-crystal 2D metal oxides.
文摘For the new subclass B of the bi-univalent functions constructed with the help of the(u,v)-Chebyshev polynomials of the second type,we get estimates for the first two initial coefficients and upper bounds of the Fekete-Szeg o functional.
文摘Artificial photosynthesis presents a sustainable and cost-effective approach to harnessing solar energy to produce value-added chemicals[1,2].In particular,the simultaneous photocatalytic conversion of CO_(2)and H_(2)O into formic acid(HCOOH)and hydrogen peroxide(H2O2)has emerged as a promising strategy to mitigate global warming driven by CO_(2)emissions.HCOOH is a versatile chemical and hydrogen carrier,offering economic and practical advantages due to its compatibility with existing industrial processes and energy storage/conversion systems.Meanwhile,H_(2)O_(2)is among the world’s top 100 essential chemicals,with a global market valued at$4.0 billion in 2020 and projected to grow to$5.2 billion by 2026.
文摘To the Editor:Acute cholangitis,also known as ascending cholangitis,is a po-tentially life-threatening condition resulting from the infection and obstruction of the biliary tract[1].Choledocholithiasis,which in-volves stones in the common bile duct,is the most frequent cause of such infections,leading to partial or complete blockage of the biliary system[2].During acute episodes,patients may present with abdominal pain,high fever,and jaundice,known as Charcot’s triad,and in severe cases,patients may also exhibit signs of shock and depression[3].An episode of cholangitis can be fatal,and if the underlying obstruction is not addressed,the condition may recur,potentially leading to hepatic abscesses or biliary cirrhosis.Other etiologies of cholangitis include benign biliary strictures,bil-iary malignancies,congenital factors,postoperative complications,inflammatory conditions,and rare causes such as pancreatitis,par-asitic invasion of the biliary tract,external compression,thrombo-sis,and iatrogenic factors.Acute cholecystitis due to the migration of Hem-o-lok clips postoperation is rare.Herein we reported a case of acute cholangitis caused by the migration of surgical Hem-o-lok clips into the bile duct six years after laparoscopic left hemihepa-tectomy.
文摘Solar-driven H_(2)O_(2) production through artificial photosynthesis presents a promising alternative to anthraquinone,given its lower energy consumption and eco-friendly nature[1-3].However,its catalytic performance is severely restricted by the inefficient separation of photogenerated carriers and interface reactions[4,5].
基金supported by the National Key R&D Program of China(Gran Nos.2022YFA1402304 and 2022YFA1402802)the National Natural Science Foundation of China(Grant Nos.12494591,12122405,12274169,and 92165204)+4 种基金Program for Science and Technology Innovation Team in Zhejiang(Grant No.2021R01004)Guangdong Provincial Key Laboratory of Magnetoelectric Physics and Devices(Grant No.2022B1212010008)Guangdong Fundamental Research Center for Magnetoelectric Physics(2024B0303390001)Guangdong Provincial Quantum Science Strategic Initiative(Grant No.GDZX2401010)the Fundamental Research Funds for the Central Universities。
文摘The discovery of high-temperature superconductivity in bilayer nickelate La_(3)Ni_(2)O_(7)under high-pressure conditions has spurred extensive efforts to stabilize superconductivity at ambient pressure.Recently,the realization of superconductivity in compressively strained La_(3)Ni_(2)O_(7)thin films grown on the SrLaAlO_(4)substrates,with a T_(c)exceeding 40 K,represents a significant step toward this goal.Here,we investigate the influence of film thickness and carrier doping on the electronic structure of La_(3)Ni_(2)O_(7)thin films,ranging from 0.5 to 3 unit cells,using first-principles calculations.For a 2 unit-cell film with an optimal doping concentration of 0.3 hole per formula unit(0.15 hole/Ni),the Ni-d_(z^(2))interlayer bonding state crosses the Fermi level,resulting in the formation ofγpockets at the Fermi surface.These findings align with angle-resolved photoemission spectroscopy experimental data.Our results provide theoretical validation for the recent experimental discovery of ambient-pressure superconductivity in La_(3)Ni_(2)O_(7)thin films and underscore the significant impact of film thickness and carrier doping on electronic property modulation.
基金supported by the National Key Research and Development Program of China (Grant Nos. 2023YFA1406100 and 2021YFA1400200)the National Natural Science Foundation of China (Grant Nos. 12025408 and 12174424)+2 种基金the Youth Innovation Promotion Association of Chinese Academy of Scineces (Grant No. 2023007)support from the National Natural Science Foundation of China (Grant No. 11904272)the Open Fund of Hubei Provincial Key Laboratory of Metallurgical Industry Process Systems Science (Grant No. Z202202)。
文摘The cubic pyrochlore Tl_(2)Ru_(2)O_(7) undergoes concurrently a metal–insulator transition (MIT) and a first-order structural transition at T_(MIT)≈120 K,below which the system was found to form one-dimensional spin-one Haldane chains associated with an orbital ordering of Ru-4d electrons.With an aim to tune and access distinct ground states with strong entanglements of multiple degrees of freedom,i.e.,spin,orbital,charge,and lattice,we utilize a high-pressure approach to regulate the MIT of this system.Our detailed resistivityρ(T) measurements on the polycrystalline Tl_(2)Ru_(2)O_(7) samples under various hydrostatic pressures indeed reveal an unusual evolution of the electronic ground states.At first,the MIT is suppressed monotonically from 120 K at ambient to about 70 K at 1.5 GPa and then vanishes suddenly at about 1.8 GPa without achieving a metallic ground state.Meanwhile,the system evolves into a semiconducting ground state with magnitude ofρ(T) in the entire temperature range enhanced gradually by further increasing pressure.Prior to the abrupt disappearance of MIT,a new electronic order manifested as a kink-like anomaly inρ(T) emerges at T_(0)>T_(MIT) at 1.2 GPa and it continues to increase with pressure,producing a tricritical-point-like behavior in the T–P phase diagram of Tl_(2)Ru_(2)O_(7).The presence of two successive transitions at T_(0 )and T_(MIT )in the pressure range 1.2–1.5 GPa indicates an inhomogeneous electronic state nearby the tricritical point.At P≥3 GPa,another broad anomaly emerges inρ(T) at T_(1)>T_(0),and T_(1)continuously increases with pressure,dividing the semiconductingρ(T) into distinct thermally activated regions.These rich phenomena in the pressurized Tl_(2)Ru_(2)O_(7) should originate from the complex interplay of strongly entangled multiple quantum degrees of freedom in the system near the localized-to-itinerant crossover regime.
基金supported by the Natural Science Foundation of Guangdong Province of China(Grant No.2025A1515011071)the National Natural Science Foundation of China(Grant Nos.92065110,11974048,and 12074334)the Beijing Municipal Natural Science Foundation Key Research Topics(Grant No.Z230006)。
文摘Recent studies have successfully demonstrated high-Tc superconductivity in bilayer nickelate La3Ni2O7.However,research on modulating the structural and transport characteristics of La3Ni2O7 films by applying“chemical”compressive pressure through cation substitution is still limited.Here,we address this issue in the La_(3−x)Nd_(x)Ni_(2)O_(7)(x=0,1.0,1.5,2.0,and 2.5)thin film samples.It was found that using Nd3+with a smaller radius instead of La3+can reduce the c-axis lattice constant and shift the metal-insulator transition(MIT)temperature TMIT.To probe the origin of the MIT at cryogenic temperatures,experimental measurements of magnetoresistance were conducted,and theoretical analysis was carried out using the Kondo model,Hikami-Larkin-Nagaoka equation,and other methods.The results indicate that as Nd doping rises,the contributions of the Kondo effect and two-dimensional weak localization(WL)first decrease and then increase.The total contribution of WL and the Kondo effect in the mid-doped La_(1.5)Nd_(1.5)Ni_(2)O_(7)sample was the smallest,which to some extent explains the changes in TMIT.The Kondo effect dominates in other La_(3−x)Nd_(x)Ni_(2)O_(7)(x=0,1.0,2.0,and 2.5)samples.This work demonstrates that cation doping has a significant impact on bilayer nickelates,providing experimental evidence for understanding the physical mechanism of the MIT in bilayer nickelates.
基金supported by the National Natural Science Foundation of China(42477481,42477483)the Science and Technology Program in Gansu Province(23JRRA599)the Chinese Academy of Sciences(CAS)"Light of West China"Program.
文摘Flash drought is characterized by a period of rapid drought intensification with impacts on agriculture,water resources,ecosystems,and human environment.In the Qilian Mountains,northwestern China,flash droughts are becoming more frequently due to the global climate warming.However,the spatiotemporal variations and their driving factors of flash droughts are not clear in this region.In this study,the European Centre for Medium-range Weather Forecasts(ECMWF)Reanalysis v5-Land(ERA5-Land)dataset was utilized to identify two types of flash drought events(heatwave-induced and water scarcity-induced flash drought events)that occurred in the growing season(April‒September)during 1981-2020 in this area.The results showed that the frequency of heatwave-induced flash droughts has decreased since 2010,while the frequency of water scarcity-induced flash droughts has declined markedly.Spatially,heatwave-induced flash droughts were predominantly concentrated in the western Qilian Mountains,whereas water scarcity-induced flash droughts were primarily concentrated in the central and eastern Qilian Mountains.A significantly increasing temporal trend in both types of flash droughts in the eastern Qilian Mountains was found.Meanwhile,there was a decreasing temporal trend of heatwave-induced flash droughts in the southwestern part of the region.Additionally,the influence of two major atmospheric modes,i.e.,the El Niño‒Southern Oscillation(ENSO)and North Atlantic Oscillation(NAO),on these two types of flash droughts was explored by the Superposed Epoch Analysis.The ENSO mainly influences flash droughts in the central and eastern parts of the Qilian Mountains by altering the strength of the East Asian monsoon,while the NAO mainly affects flash droughts in the entire parts of the Qilian Mountains by inducing anomalous westerlies activity.Our findings have important implications for predicting the evolution of flash drought events in the Qilian Mountains region under continued climate warming.
基金supported by the Fundamental Research Funds for the Central Universities(No.2019ZDPY04).
文摘In this work,the TiO_(2)/Sb_(2)S_(3) nanorod arrays(NRAs)were synthesized through a two-stage hydrothermal route for photoelectrochemical(PEC)water splitting.The effect of annealing treatment in Ar ambience on the PEC activity of TiO_(2)/Sb_(2)S_(3) composite sample was investigated by electrochemical impedance analysis,including Nyquist and Mott-Schottky(M-S)plots.It was demonstrated that vacuum annealing could crystallize Sb_(2)S_(3) component and change its color from red to black,leading to an increment of photocurrent density from 1.9 A/m^(2) to 4.25 A/m^(2) at 0 V versus saturated calomel electrode(VSCE).The enhanced PEC performance was mainly attributed to the improved visible light absorption.Moreover,annealing treatment facilitated retarding the electron-hole recombination occurred at the solid/liquid interfaces.Our work might provide a novel strategy for enhancing the PEC performance of a semiconductor electrode.
基金supported by Cultivating Fund Project of Hubei Hongshan Laboratory(2022hspy002).
文摘Here we report that the presence of MgCO_(3) stimulates the extracellular polymeric substance (EPS) secretion of Microcystis Aeruginosa (M. Aeruginosa). This stimulation led to a significant reduction in the total concentration of NH_(4)^(+)‒N by more than 86%, and effective recovery of PO_(4)^(3-)‒P within three days from concentrated wastewater (WW), although the secreted EPS inhibited the conversion of MgCO_(3) to specific crystal forms (MgNH4PO4.6H2O or MgHPO4.7H2O). Moreover, with an increase in PO_(4)^(3-) concentration in WW, these crystals appeared, thus the removal of NH_(4)^(+)‒N and PO_(4)^(3-)‒P nutrients can be attributed to the combined effect of M. Aeruginosa and MgCO_(3). We used Surface-Enhanced Raman Spectroscopy (SERS) combined with X-ray Diffraction (XRD), Field Emission Scanning Electron Microscopy with Energy-Dispersive X-ray Spectroscopy (FESEM-EDS), and X-ray Photoelectron Spectroscopy (XPS) to investigate the mechanism for competitive interactions between M. Aeruginosa and MgCO_(3) in removing NH_(4)^(+)‒N and PO_(4)^(3-)‒P. We identified that the bound EPS accumulated amorphous Mg–P–O dense particles on M. Aeruginosa, while soluble EPS, containing –COOH groups of humic-like substances decreased the pH of the solution and coordinated with Mg^(2+) ions. Therefore, both secreted bound and soluble EPS play a vital role in hindering the transformation of Mg^(2+) ions or MgCO_(3) to MgNH4PO4.6H2O or MgHPO4.7H2O crystals within WW, and they enhanced M. Aeruginosa 's ability in absorbing nutrients of NH_(4)^(+)‒N and PO_(4)^(3-)‒P. This mechanism plays a crucial role in the efficient recovery of NH_(4)^(+)‒N and PO_(4)^(3-)‒P from concentrated wastewater sources such as aerobically or anaerobically digested effluent from various sources like agriculture, livestock, and domestic wastewaters.
文摘Secondary pollutant ozone (O3) formation in a particular area is often influenced by various factors. Source of emissions is one of the factors. In south east Texas, Houston-Galveston-Brazoria (HGB) is a marginal non-attainment area for ozone (O3). A summer episode of May 28 to July 2, 2006 is simulated using Comprehensive Air Quality Model with extensions (CAMx). During this period O3 concentration in HGB often exceeds the National Ambient Air Quality Standards (NAAQS) 0.075 ppm of average 8 hour O3 concentration. HGB area has numerous point sources. Various studies found that some specific volatile organic compounds are very reactive in atmosphere. The objective of this study is to analyze the influence of volatile organic compounds present in point source emissions on the air quality of HGB area. For this purpose ozone sensitivity for HGB area is analyzed by the ratio of hydrogen peroxides (H2O2) to nitric acid (HNO3). HGB area is found NOx limited but reactive VOCs are found to be influential too. From (1-4 June, 2006) maximum O3 concentration was found on weekend, June 3. VOCs such as Acetaldehyde (ALD2), Formaldehyde (FORM) and Alkane (ETHA) showed good correlation with O3 concentrations on that day. In addition, Peroxyacetyl nitrate (PAN) formation was found correlated to higher ozone production. Criteria pollutant Sulfur dioxide (SO2) was found to influence the ALD2 and ETHA concentrations, and thus indirectly influenced O3 production.
文摘Electrochemical carbon dioxide reduction reaction(CO_(2)RR)produces valuable chemicals by consuming gaseous CO_(2)as well as protons from the electrolyte.Protons,produced by water dissociation in alkaline electrolyte,are critical for the reaction kinetics which involves multiple proton coupled electron transfer steps.Herein,we demonstrate that the two key steps(CO_(2)-^(*)COOH and^(*)CO-^(*)COH)efficiency can be precisely tuned by introducing proper amount of water dissociation center,i.e.,Fe single atoms,locally surrounding the Cu catalysts.In alkaline electrolyte,the Faradaic efficiency(FE)of multi-carbon(C^(2+))products exhibited a volcano type plot depending on the density of water dissociation center.A maximum FE for C^(2+)products of 73.2%could be reached on Cu nanoparticles supported on N-doped Carbon nanofibers with moderate Fe single atom sites,at a current density of 300 mA cm^(–2).Experimental and theoretical calculation results reveal that the Fe sites facilitate water dissociation kinetics,and the locally generated protons contribute significantly to the CO_(2)activation and^(*)CO protonation process.On the one hand,in-situ attenuated total reflection surface-enhanced infrared absorption spectroscopy(in-situ ATR-SEIRAS)clearly shows that the^(*)COOH intermediate can be observed at a lower potential.This phenomenon fully demonstrates that the optimized local water dissociation kinetics has a unique advantage in guiding the hydrogenation reaction pathway of CO₂molecules and can effectively reduce the reaction energy barrier.On the other hand,abundant^(*)CO and^(*)COH intermediates create favorable conditions for the asymmetric^(*)CO-^(*)COH coupling,significantly increasing the selectivity of the reaction for C^(2+)products and providing strong support for the efficient conversion of related reactions to the target products.This work provides a promising strategy for the design of a dual sites catalyst to achieve high FE of C^(2+)products through the optimized local water dissociation kinetics.
文摘Layered transition metal hydroxides show distinct advantages in separately co-catalyzing CO_(2)reduction and H_(2)O oxidation at the electron-accumulating and hole-accumulating sites of wrapped heterojunction photocatalysts,while concurrently preventing side reactions and photocorrosion on the semiconductor surface.Herein,Ni-Co bimetallic hydroxides with varying Ni/Co molar ratios(Ni_(x)Co_(1-x)(OH)_(2),x=1,0.75,0.5,0.25,and 0)were grown in situ on a model 2D/2D S-scheme heterojunction composed of Cu_(2)O nanosheets and Fe_(2)O_(3)nanoplates to form a series of Cu_(2)O/Fe_(2)O_(3)@Ni_(x)Co_(1-x)(OH)_(2)(CF@NiCo)photocatalysts.The combined experimental and theoretical investigation demonstrates that incorporating an appropriate amount of Co into Ni(OH)_(2)not only modulates the energy band structure of Ni_(x)Co_(1-x)(OH)_(2),balances the electron-and hole-trapping abilities of the bifunctional cocatalyst and maximizes the charge separation efficiency of the heterojunction,but also regulates the d-band center of Ni_(x)Co_(1-x)(OH)_(2),reinforcing the adsorption and activation of CO_(2)and H_(2)O on the cocatalyst surface and lowering the rate-limiting barriers in the CO_(2)-to-CO and H_(2)O-to-O_(2)conversion.Benefiting from the Ni-Co synergy,the redox reactions proceed stoichiometrically.The optimized CF@Ni_(0.75)Co_(0.25)achieves CO and O_(2)yields of 552.7 and 313.0μmol gcat^(-1)h^(-1),respectively,11.3/9.9,1.6/1.7,and 4.5/5.9-fold higher than those of CF,CF@Ni,and CF@Co.This study offers valuable insights into the design of bifunctional noble-metal-free cocatalysts for high-performance artificial photosynthesis.
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.
