Developing catalysts with excellent stability while significantly reducing the overpotential of the oxygen evolution reaction(OER) is crucial for advancing overall water splitting(OWS) systems.In this study,we synthes...Developing catalysts with excellent stability while significantly reducing the overpotential of the oxygen evolution reaction(OER) is crucial for advancing overall water splitting(OWS) systems.In this study,we synthesized the electrode material Ce-NiCo-LDHs@SnO_(2)/NF through a two-step hydrothermal reaction,where Ce-doped NiCo-LDHs are grown on nickel foam modified by a SnO_(2) layer.Ce doping adjusts the internal electronic distribution of Ni Co-LDHs,while the introduction of the SnO_(2) layer enhances electron transfer capability.Together,these factors contribute to the reduction of the OER energy barrier and experimental evidence confirms that the reaction proceeds via the lattice oxygen evolution mechanism(LOM).Consequently,Ce-NiCo-LDHs@SnO_(2)/NF exhibits high level electrochemical performance in OER,requiring only 234 m V overpotential to achieve a current density of 10 m A/cm^(2),with a Tafel slope of just 27.39 m V/dec.When paired with Pt/C/NF,an external potential of only 1.54 V is needed to drive OWS to attain a current density amounting to 10 m A/cm^(2).Furthermore,the catalyst demonstrates stability for 100 h during the OWS stability test.This study underscores the feasibility of enhancing the OER performance through Ce doping and the introduction of a conductive SnO_(2) layer.展开更多
Heteroatom-doped carbon is considered a promising alternative to commercial Pt/C as an efficient catalyst for the oxygen reduction reaction(ORR).This study presents the synthesis of iron-loaded,sulfur and nitrogen co-...Heteroatom-doped carbon is considered a promising alternative to commercial Pt/C as an efficient catalyst for the oxygen reduction reaction(ORR).This study presents the synthesis of iron-loaded,sulfur and nitrogen co-doped carbon(Fe/SNC)via in situ incorporation of 2-aminothiazole molecules into zeolitic imidazolate framework-8(ZIF-8)through coordination between metal ions and organic ligands.Sulfur and nitrogen doping in carbon supports effectively modulates the electronic structure of the catalyst,increases the Brunauer-Emmett-Teller surface area,and exposes more Fe-N_(x)active centers.Fe-loaded,S and N co-doped carbon with Fe/S molar ratio of 1:10(Fe/SNC-10)exhibits a half-wave potential of 0.902 V vs.RHE.After 5000 cycles of cyclic voltammetry,its half-wave potential decreases by only 20 mV vs.RHE,indicating excellent stability.Due to sulfur s lower electronegativity,the electronic structure of the Fe-N_(x)active center is modulated.Additionally,the larger atomic radius of sulfur introduces defects into the carbon support.As a result,Fe/SNC-10 demonstrates superior ORR activity and stability in alkaline solution compared with Fe-loaded N-doped carbon(Fe/NC).Furthermore,the zinc-air battery assembled with the Fe/SNC-10 catalyst shows enhanced performance relative to those assembled with Fe/NC and Pt/C catalysts.This work offers a novel design strategy for advanced energy storage and conversion applications.展开更多
Photocatalytic nitrogen fixation has emerged as a sustainable alternative for ammonia synthesis,playing a crucial role in alleviating energy shortages and environmental pollution.In this study,PbBiO_(2)Br was applied ...Photocatalytic nitrogen fixation has emerged as a sustainable alternative for ammonia synthesis,playing a crucial role in alleviating energy shortages and environmental pollution.In this study,PbBiO_(2)Br was applied to photocatalytic nitrogen fixation for the first time,and its photocatalytic performance was effectively enhanced through Cu doping.The catalyst was synthesized via a simple reduction method,and its morphology,structure,and physicochemical properties were systematically investigated using various characterization techniques and density functional theory calculations.The results revealed that the incorporation of Cu2+partially replaced Pb2+,inducing lattice distortion in PbBiO_(2)Br,promoting the formation of oxygen vacancies,and modifying its electronic band structure.Specifically,Cu doping led to a slight bandgap narrowing,a reduction in work function,and a significant upward shift in the conduction band position.These changes enhanced light absorption,facilitated charge carrier migration and separation,and improved the reduction ability of photogenerated electrons.Moreover,Cu doping promoted N_(2)adsorption and activation.Consequently,the photocatalytic nitrogen fixation performance of Cu-doped PbBiO_(2)Br was significantly enhanced,achieving an optimal nitrogen fixation rate of 293μmol L^(−1)g^(−1)h^(−1),which is 3.6 times higher than that of pristine PbBiO_(2)Br.Additionally,Cu–PbBiO_(2)Br also showed good activity in the photocatalytic degradation of RhB,with a degradation rate 4.6 times higher than that of PbBiO_(2)Br.This work offers new insights into the application of PbBiO_(2)Br in photocatalytic nitrogen fixation and offers valuable guidance for the development of highly efficient nitrogen fixation materials in the future.展开更多
Abiotic oxygen formation predates photosynthesis,sustaining early chemical evolution,yet its elementary mechanisms remain contested.Here,we show the production pathways for molecular oxygen from doubly ionized carbon ...Abiotic oxygen formation predates photosynthesis,sustaining early chemical evolution,yet its elementary mechanisms remain contested.Here,we show the production pathways for molecular oxygen from doubly ionized carbon dioxide upon electron-impact.Through fragment ions and electron coincidence momentum imaging,we unambiguously determine the ionization mechanism by measuring the projectile energy loss in association with the C^(+) +O_(2)^(+) channel.Further potential energy and trajectory calculations enable us to elucidate the dynamical details of this fragmentation process,in which a bond rearrangement pathway is found to proceed via the structural deformation to a triangular intermediate.Moreover,we demonstrate a further roaming pathway for the formation of O_(2)^(+) from CO_(2)^(+) 2,in which a frustrated C-O bond cleavage leaves the O atom without sufficient energy to escape.The O atom then wanders around varied configuration spaces of the flat potential energy regions and forms a C-O-O_(2)^(+) intermediate prior to the final products C^(+) +O_(2)^(+).Considering the large quantities of free electrons in interstellar space,the processes revealed here are expected to be significant and should be incorporated into atmospheric evolution models.展开更多
The objective of this study was to investigate the nitritation performance in a biofilm reactor for treating domestic wastewater.The reactor was operated in continuous feed mode from phases 1 to 3.The dissolved oxygen...The objective of this study was to investigate the nitritation performance in a biofilm reactor for treating domestic wastewater.The reactor was operated in continuous feed mode from phases 1 to 3.The dissolved oxygen（DO）was controlled at 3.5–7 mg/L throughout the experiment.The biofilm reactor showed excellent nitritation performance after the inoculation of nitrifying sludge,with the hydraulic retention time being reduced from 24 to 7 hr.Above 90%nitrite accumulation ratio（NAR）was maintained in phase 1.Afterwards,nitratation occurred with the low NH4^＋–N concentration in the reactor.The improvement of NH4^＋–N concentration to 20–35 mg/L had a limited effect on the recovery of nitritation.However,nitritation recovered rapidly when sequencing batch feed mode was adopted in phase 4,with the effluent NH4^＋-N concentration above 7 mg/L.The improvement of ammonia oxidizing bacteria（AOB）activity and the combined inhibition effect of free ammonia（FA）and free nitrous acid（FNA）on the nitrite oxidizing bacteria（NOB）were two key factors for the rapid recovery of nitritation.Sludge activity was obtained in batch tests.The results of batch tests had a good relationship with the long term operation performance of the biofilm reactor.展开更多
Binary composites(ZIF-67/rGO)were synthesized by one-step precipitation method using cobalt nitrate hexahydrate as metal source,2-methylimidazole as organic ligand,and reduced graphene oxide(rGO)as carbon carrier.Then...Binary composites(ZIF-67/rGO)were synthesized by one-step precipitation method using cobalt nitrate hexahydrate as metal source,2-methylimidazole as organic ligand,and reduced graphene oxide(rGO)as carbon carrier.Then Ru3+was introduced for ion exchange,and the porous Ru-doped Co_(3)O_(4)/rGO(Ru-Co_(3)O_(4)/rGO)composite electrocatalyst was prepared by annealing.The phase structure,morphology,and valence state of the catalyst were analyzed by X-ray powder diffraction(XRD),scanning electron microscope(SEM),transmission electron microscopy(TEM),and X-ray photoelectron spectroscopy(XPS).In 1 mol·L^(-1)KOH,the oxygen evolution reaction(OER)performance of the catalyst was measured by linear sweep voltammetry,cyclic voltammetry,and chronoamperometry.The results show that the combination of Ru doping and rGO provides a fast channel for collaborative electron transfer.At the same time,rGO as a carbon carrier can improve the electrical conductivity of Ru-Co_(3)O_(4)particles,and the uniformly dispersed nanoparticles enable the reactants to diffuse freely on the catalyst.The results showed that the electrochemical performance of Ru-Co_(3)O_(4)/rGO was much better than that of Co_(3)O_(4)/rGO,and the overpotential of Ru-Co_(3)O_(4)/rGO was 363.5 mV at the current density of 50 mA·cm^(-2).展开更多
Sulfur-doped iron-cobalt tannate nanorods(S-FeCoTA)derived from metal-organic frameworks(MOFs)as electrocatalysts were synthesized via a one-step hydrothermal method.The optimized S-FeCoTA was interlaced by loose nano...Sulfur-doped iron-cobalt tannate nanorods(S-FeCoTA)derived from metal-organic frameworks(MOFs)as electrocatalysts were synthesized via a one-step hydrothermal method.The optimized S-FeCoTA was interlaced by loose nanorods,which had many voids.The S-FeCoTA catalysts exhibited excellent electrochemical oxygen evolution reaction(OER)performance with a low overpotential of 273 mV at 10 mA·cm^(-2)and a small Tafel slope of 36 mV·dec^(-1)in 1 mol·L^(-1)KOH.The potential remained at 1.48 V(vs RHE)at 10 mA·cm^(-2)under continuous testing for 15 h,implying that S-FeCoTA had good stability.The Faraday efficiency of S-FeCoTA was 94%.The outstanding OER activity of S-FeCoTA is attributed to the synergistic effects among S,Fe,and Co,thus promoting electron transfer,reducing the reaction kinetic barrier,and enhancing the OER performance.展开更多
Oceanic dissolved oxygen(DO)in the ocean has an indispensable role on supporting biological respiration,maintaining ecological balance and promoting nutrient cycling.According to existing research,the total DO has dec...Oceanic dissolved oxygen(DO)in the ocean has an indispensable role on supporting biological respiration,maintaining ecological balance and promoting nutrient cycling.According to existing research,the total DO has declined by 2%of the total over the past 50 a,and the tropical Pacific Ocean occupied the largest oxygen minimum zone(OMZ)areas.However,the sparse observation data is limited to understanding the dynamic variation and trend of ocean using traditional interpolation methods.In this study,we applied different machine learning algorithms to fit regression models between measured DO,ocean reanalysis physical variables,and spatiotemporal variables.We demonstrate that extreme gradient boosting(XGBoost)model has the best performance,hereby reconstructing a four-dimensional DO dataset of the tropical Pacific Ocean from 1920 to 2023.The results reveal that XGBoost significantly improves the reconstruction performance in the tropical Pacific Ocean,with a 35.3%reduction in root mean-squared error and a 39.5%decrease in mean absolute error.Additionally,we compare the results with three Coupled Model Intercomparison Project Phase 6(CMIP6)models data to confirm the high accuracy of the 4-dimensional reconstruction.Overall,the OMZ mainly dominates the eastern tropical Pacific Ocean,with a slow expansion.This study used XGBoost to efficiently reconstructing 4-dimensional DO enhancing the understanding of the hypoxic expansion in the tropical Pacific Ocean and we foresee that this approach would be extended to reconstruct more ocean elements.展开更多
Oceanic dissolved oxygen(DO)concentration is crucial for assessing the status of marine ecosystems.Against the backdrop of global warming,DO shows a general decrease,posing a threat to the health of marine ecosystems....Oceanic dissolved oxygen(DO)concentration is crucial for assessing the status of marine ecosystems.Against the backdrop of global warming,DO shows a general decrease,posing a threat to the health of marine ecosystems.Therefore,there is an urgent need to develop advanced tools to characterize the spatio-temporal variations of three-dimensional(3D)DO.To address this challenge,this study introduces the Light Gradient Boosting Machine(Light-GBM),combining satellite remote sensing and reanalysis data with Biogeochemical Argo data to accurately reconstruct the 3D DO structure in the Mediterranean Sea from 2010 to 2022.Various environmental parameters are incorporated as inputs,including spatiotemporal features,meteorological characteristics,and ocean color properties.The LightGBM model demonstrates excellent performance on the testing dataset with R^(2) of 0.958.The modeled DO agrees better with in-situ measurements than products from numerical models.Using the Shapley Additive exPlanations method,the contributions of input features are assessed.Sea surface temperatures provide a correlation with DO at the sea surface,while spatial coordinates supplement the view of the ocean interior.Based on the reconstructed 3D DO structure,we identify an oxygen minimum zone in the western Mediterranean that expands continuously,reaching depths of approximately 300–800 m.The western Mediterranean exhibits a significant declining trend.This study enhances marine environmental evidence by proposing a precise and cost-effective approach for reconstructing 3D DO,thereby offering insights into the dynamics of DO variations under changing climatic conditions.展开更多
This study examines the potential impacts o climate change on Lake Biwa,Japan’s largest freshwate lake,with a focus on temperature,wind speed,and pre cipitation variations.Leveraging data from the IPCC Sixth Assessme...This study examines the potential impacts o climate change on Lake Biwa,Japan’s largest freshwate lake,with a focus on temperature,wind speed,and pre cipitation variations.Leveraging data from the IPCC Sixth Assessment Report,including CCP scenarios,projecting a significant temperature rise of 3.3–5.7℃in the case o very high GHG emission power,the research investigates how these shifts may influence dissolved oxygen levels in Lake Biwa.Through a one-dimensional model incorporat ing sediment redox reactions,various scenarios where ai temperature and wind speed are changed are simulated.I is revealed that a 5℃increase in air temperature leads to decreasing 1-2 mg/L of dissolved oxygen concentrations from the surface layer to the bottom layer,while a decrease in air temperature tends to elevate 1–3 mg/L of oxygen lev els.Moreover,doubling wind speed enhances surface laye oxygen but diminishes it in deeper layers due to increased mixing.Seasonal variations in wind effects are noted with significant surface layer oxygen increases from 0.4to 0.8 mg/L during summer to autumn,increases from 0.4 to 0.8 mg/L in autumn to winter due to intensified vertica mixing.This phenomenon impacts the lake’s oxygen cycle year-round.In contrast,precipitation changes show limited impact on oxygen levels,suggesting minor influence com pared to other meteorological factors.The study suggests the necessity of comprehensive three-dimensional models that account for lake-specific and geographical factors fo accurate predictions of future water conditions.A holistic approach integrating nutrient levels,water temperature,and river inflow is deemed essential for sustainable management of Lake Biwa’s water resources,particularly in addressing precipitation variations.展开更多
To investigate the influence of oxygen content in a physiological liquid environment on the corrosion behavior of biomedical zinc-based alloys,a simulated bodily fluid environment with varying dissolved oxygen was est...To investigate the influence of oxygen content in a physiological liquid environment on the corrosion behavior of biomedical zinc-based alloys,a simulated bodily fluid environment with varying dissolved oxygen was established in vitro using external oxygen supply equipment.The influence of dissolved oxygen concentration on the corrosion behavior of pure Zn and Zn−Cu alloys was studied with scanning electron microscopy,energy dispersive spectroscopy,Fourier transform infrared spectrometry,and electrochemical analysis.Due to oxygen absorption corrosion,the increase in dissolved oxygen concentration increases the pH value of the solution and promotes the accumulation of corrosion product layer.Compared with the environment without additional oxygen supply,the corrosion rate of the sample under the continuous oxygen supply condition is increased by one order of magnitude.Because the Zn−Cu alloy has micro-galvanic corrosion,its corrosion rate is about 1.5 times that of pure zinc under different dissolved oxygen conditions.展开更多
Lake Baiyangdian is one of China’s largest macrophyte-derived lakes,facing severe challenges related to water quality maintenance and eutrophication prevention.Dissolved organic matter(DOM)was a huge carbon pool and ...Lake Baiyangdian is one of China’s largest macrophyte-derived lakes,facing severe challenges related to water quality maintenance and eutrophication prevention.Dissolved organic matter(DOM)was a huge carbon pool and its abundance,property,and transformation played important roles in the biogeochemical cycle and energy flow in lake ecosystems.In this study,Lake Baiyangdian was divided into four distinct areas:Unartificial Area(UA),Village Area(VA),Tourism Area(TA),and Breeding Area(BA).We examined the diversity of DOM properties and sources across these functional areas.Our findings reveal that DOM in this lake is predominantly composed of protein-like substances,as determined by excitation-emission matrix and parallel factor analysis(EEM-PARAFAC).Notably,the exogenous tyrosine-like component C1 showed a stronger presence in VA and BA compared to UA and TA.Ultrahigh-resolution mass spectrometry(FT-ICR MS)unveiled a similar DOM molecular composition pattern across different functional areas due to the high relative abundances of lignan compounds,suggesting that macrophytes significantly influence the material structure of DOM.DOM properties exhibited specific associations with water quality indicators in various functional areas,as indicated by the Mantel test.The connections between DOM properties and NO_(3)-N andNH3-Nwere more pronounced in VA and BA than in UA and TA.Our results underscore the viability of using DOM as an indicator for more precise and scientific water quality management.展开更多
The development of an e fficacious and easily prepared no nprecious metal electrocatalyst is crucial for the oxygen reduction reaction(ORR).This work used a dual template method to prepare the amorphous rare earth-bas...The development of an e fficacious and easily prepared no nprecious metal electrocatalyst is crucial for the oxygen reduction reaction(ORR).This work used a dual template method to prepare the amorphous rare earth-based catalyst PrO_(x)-NC,and optimized the calcination temperature and proportion.The PrO_(x)-NC-900 catalyst has high durability and activity and exhibits superior ORR performance in alkaline electrolytes with an onset potential(E_(0))of 0.96 V and a half-wave potential(E_(1/2))of 0.85 V.The research results indicate that the ORR performance of rare earth oxide composite carbon catalysts can be improved by adjusting oxygen vacancies(Ov).In addition,high specific surface area,N rich defect carbon.increased oxygen vacancies,and the synergistic effect of oxygen vacancies and N-doped carbon interfacial layer play a significant part in the enhancement of ORR.The performance of the zinc air battery assembled with PrO_(x)-NC-900 is significantly improved,and rare earth oxides and carbon frameworks originating from metal organic frameworks(MOFs)contribute to the oxygen electrocatalyst and electron transfer rate of the zinc air battery.This catalyst provides promising information for the development of rare earth metal oxide nanostructures as potential candidate materials for ORR in alkaline media.展开更多
Oxygen release and electrolyte decomposition under high voltage endlessly exacerbate interfacial ramifications and structu ral degradation of high energy-density Li-rich layered oxide(LLO),leading to voltage and capac...Oxygen release and electrolyte decomposition under high voltage endlessly exacerbate interfacial ramifications and structu ral degradation of high energy-density Li-rich layered oxide(LLO),leading to voltage and capacity fading.Herein,the dual-strategy of Cr,B complex coating and local gradient doping is simultaneously achieved on LLO surface by a one-step wet chemical reaction at room temperature.Density functional theory(DFT)calculations prove that stable B-O and Cr-O bonds through the local gradient doping can significantly reduce the high-energy O 2p states of interfacial lattice O,which is also effective for the near-surface lattice O,thus greatly stabilizing the LLO surface,Besides,differential electrochemical mass spectrometry(DEMS)indicates that the Cr_(x)B complex coating can adequately inhibit oxygen release and prevents the migration or dissolution of transition metal ions,including allowing speedy Li^(+)migration,The voltage and capacity fading of the modified cathode(LLO-C_(r)B)are adequately suppressed,which are benefited from the uniformly dense cathode electrolyte interface(CEI)composed of balanced organic/inorganic composition.Therefore,the specific capacity of LLO-CrB after 200 cycles at 1C is 209.3 mA h g^(-1)(with a retention rate of 95.1%).This dual-strategy through a one-step wet chemical reaction is expected to be applied in the design and development of other anionic redox cathode materials.展开更多
Multicomponent Gd_(1−x)Sm_(x)Ba_(0.5)Sr_(0.5)CoCuO_(5+δ)double perovskites are optimized for application in terms of chemical composi-tion and morphology for the use as oxygen electrodes in solid oxide cells.Structur...Multicomponent Gd_(1−x)Sm_(x)Ba_(0.5)Sr_(0.5)CoCuO_(5+δ)double perovskites are optimized for application in terms of chemical composi-tion and morphology for the use as oxygen electrodes in solid oxide cells.Structural studies of other physicochemical properties are con-ducted on a series of materials obtained by the sol-gel method with different ratios of Gd and Sm cations.It is documented that changing the x value,and the resulting adjustment of the average ionic radius,have a significant impact on the crystal structure,stability,as well as on the total conductivity and thermomechanical properties of the materials,with the best results obtained for the Gd_(0.75)Sm_(0.2)5Ba_(0.5)Sr_(0.5)CoCuO_(5+δ)composition.Oxygen electrodes are prepared using the selected compound,allowing to obtain low polarization resistance values,such as 0.086Ω·cm^(2)at 800℃.Systematic studies of electrocatalytic activity are conducted using La_(0.8)Sr_(0.2)Ga_(0.8)Mg_(_(0.2))O_(3−δ)as the electrolyte for all electrodes,and Ce_(0.8)Gd_(0.2)O_(2−δ)electrolyte for the best performing Gd_(0.75)Sm_(0.2)5Ba_(0.5)Sr_(0.5)CoCuO_(5+δ)electrodes.The electrochemical data are analyzed using the distribution of relaxation times method.Also,the influence of the preparation method of the electrode material is in-ve`stigated using the electrospinning technique.Finally,the performance of the Gd_(0.75)Sm_(0.2)5Ba_(0.5)Sr_(0.5)CoCuO_(5+δ)electrodes is tested in a Ni-YSZ(yttria-stabilized zirconia)anode-supported cell with a Ce_(0.8)Gd_(0.2)O_(2−δ)buffer layer,in the fuel cell and electrolyzer operating modes.With the electrospun electrode,a power density of 462 mW·cm^(−2)is obtained at 700℃,with a current density of ca.0.2 A·cm^(−2)at 1.3 V for the electrolysis at the same temperature,indicating better performance compared to the sol-gel-based electrode.展开更多
To establish a immobilization method of oxygen sensitive dye, a dissolved oxygen sensor based on a sol-gel matrix doped with ruthenium complex ([Ru(bpy)3]2+) as the oxygen-sensitive material is reported. The results i...To establish a immobilization method of oxygen sensitive dye, a dissolved oxygen sensor based on a sol-gel matrix doped with ruthenium complex ([Ru(bpy)3]2+) as the oxygen-sensitive material is reported. The results indicate that the I0 /I100 value of the [Ru(bpy)3]2+-doped in tetraethylorthosilane (TEOS) composite films are estimated to be 10.6, where I0 and I100 correspond to the detected fluorescence intensities in pure nitrogen saturated water and pure oxygen saturated water, respectively. Also, the Stern-Volmer plot shows a very good linearity at low dissolved oxygen concentrations. The response time of the composite films is 5 s upon switching from nitrogen saturated water to oxygen saturated water and 10 s from oxygen saturated water to nitrogen saturated water. The dissolved oxygen sensors based on the ruthenium complex/TEOS composite films exhibit greater sensitivity, stability and faster response time as compared to the existing ones. Furthermore, the thin films possess greatly minimized dye leaching effect.展开更多
Facilitating anion redox chemistry is an effective strategy to increase the capacity of layered oxides for sodium-ion batteries.Nevertheless,there remains a paucity of literature pertaining to the oxygen redox chemist...Facilitating anion redox chemistry is an effective strategy to increase the capacity of layered oxides for sodium-ion batteries.Nevertheless,there remains a paucity of literature pertaining to the oxygen redox chemistry of O3-type layered oxide cathode materials.This work systematically investigates the effect of Fe doping on the anionic oxygen redox chemistry and electrochemical reactions in O3-NaNi_(0.4)Cu_(0.1)Mn_(0.4)Ti_(0.1)O_(2).The results of the density functional theory(DFT)calculations indicate that the electrons of the O 2p occupy a higher energy level.In the ex-situ X-ray photoelectron spectrometer(XPS)of O 1s,the addition of Fe facilitates the lattice oxygen(O^(n-))to exhibit enhanced activity at 4.45 V.The in-situ X-ray diffraction(XRD)demonstrates that the doping of Fe effectively suppresses the Y phase transition at high voltages.Furthermore,the Galvanostatic Intermittent Titration Technique(GITT)data indicate that Fe doping significantly increases the Na~+migration rate at high voltages.Consequently,the substitution of Fe can elevate the cut-off voltage to 4.45 V,thereby facilitating electron migration from O^(2-).The redox of O^(2-)/O^(n-)(n<2)contributes to the overall capacity.O3-Na(Ni_(0.4)Cu_(0.1)Mn_(0.4)Ti_(0.1))_(0.92)Fe_(0.08)O_(2)provides an initial discharge specific capacity of 180.55 mA h g^(-1)and71.6%capacity retention at 0.5 C(1 C=240 mA g^(-1)).This work not only demonstrates the beneficial impact of Fe substitution for promoting the redox activity and reversibility of O^(2-)in 03-type layered oxides,but also guarantees the structural integrity of the cathode materials at high voltages(>4.2 V).It offers a novel avenue for investigating the anionic redox reaction in O3-type layered oxides to design advanced cathode materials.展开更多
The adsorption of CO on different lattice oxygen sites in Cu doped CeO_(2)(111)was studied by DFT method,and the geometrical structure and electronic properties of adsorption systems were analyzed.The results showed t...The adsorption of CO on different lattice oxygen sites in Cu doped CeO_(2)(111)was studied by DFT method,and the geometrical structure and electronic properties of adsorption systems were analyzed.The results showed that CO interacted with lattice oxygen on the first layer formed CO_(2).However,when adsorbed on the second layer lattice oxygen,carbonate species were formed with the participation of first layer lattice oxygens,i.e.,CO co-adsorbed on first and second layer lattice oxygens.For the second layer adsorption,the absolute CO adsorption energy was big on the Oss nearby Cu.This kind of carbonates was thermodynamically stable,and it was attributed to the facilitation of Cu on CO adsorption,manifested by an electron migration behavior from the C 2p orbitals to the Cu 3d orbitals.However,the absolute CO adsorption energy on the Oss away from Cu was small.Compared to the formation of carbonates,the formation CO_(2)had very small absolute adsorption energy,suggesting the formed carbonates on second layer was stable.Further,when CO adsorbed on the systems with a carbonate,the absolute CO adsorption energy was significantly smaller than that of the non-carbonated system,indicating that the formation of carbonates inhibited CO oxidation on Cu/CeO_(2)(111).Therefore,the formation of carbonates was unfavorable for CO oxidation reaction on Cu/CeO_(2)(111).The results of this study provide theoretical support for the negative effect of CO_(2)on ceria-based catalysts.展开更多
The weak adsorption energy of oxygen-containing intermediates on Co center leads to a considerable performance dis-parity between Co-N-C and costly Pt benchmark in catalyzing oxygen reduction reaction(ORR).In this wor...The weak adsorption energy of oxygen-containing intermediates on Co center leads to a considerable performance dis-parity between Co-N-C and costly Pt benchmark in catalyzing oxygen reduction reaction(ORR).In this work,we strategi-cally engineer the active site structure of Co-N-C via B substitution,which is accomplished by the pyrolysis of ammonium borate.During this process,the in-situ generated NH_(3)gas plays a critical role in creating surface defects and boron atoms substituting nitrogen atoms in the carbon structure.The well-designed CoB_(1)N_(3)active site endows Co with higher charge density and stronger adsorption energy toward oxygen species,potentially accelerating ORR kinetics.As expected,the resulting Co-B/N-C catalyst exhibited superior ORR performance over Co-N-C counterpart,with 40 mV,and fivefold en-hancement in half-wave potential and turnover frequency(TOF).More importantly,the excellent ORR performance could be translated into membrane electrode assembly(MEA)in a fuel cell test,delivering an impressive peak power density of 824 mW·cm^(-2),which is currently the best among Co-based catalysts under the same conditions.This work not only demon-strates an effective method for designing advanced catalysts,but also affords a highly promising non-precious metal ORR electrocatalyst for fuel cell applications.展开更多
Dissolved black carbon(DBC)plays a crucial role in the migration and bioavailability of iron in water.However,the properties of DBC releasing under diverse pyrolysis conditions and dissolving processes have not been s...Dissolved black carbon(DBC)plays a crucial role in the migration and bioavailability of iron in water.However,the properties of DBC releasing under diverse pyrolysis conditions and dissolving processes have not been systematically studied.Here,the compositions of DBC released from biochar through redox processes dominated by bacteria and light were thoroughly studied.It was found that the DBC released from straw biochar possess more oxygen-containing functional groups and aromatic substances.The content of phenolic and carboxylic groups in DBC was increased under influence of microorganisms and light,respectively.The concentration of phenolic hydroxyl groups increased from 10.0~57.5 mmol/gC to 6.6~65.2 mmol/gC,and the concentration of carboxyl groups increased from49.7~97.5 mmol/gC to 62.1~113.3 mmol/gC.Then the impacts of DBC on pyrite dissolution andmicroalgae growth were also investigated.The complexing Fe^(3+)was proved to play a predominant role in the dissolution of ferrous mineral in DBC solution.Due to complexing between iron ion and DBC,the amount of dissolved Fe in aquatic water may rise as a result of elevated number of aromatic components with oxygen containing groups and low molecular weight generated under light conditions.Fe-DBC complexations in solution significantly promoted microalga growth,which might be attributed to the stimulating effect of dissolved Fe on the chlorophyll synthesis.The results of study will deepen our understanding of the behavior and ultimate destiny of DBC released into an iron-rich environment under redox conditions.展开更多
基金supported by the National Natural Science Foundation of China (No.52274304)。
文摘Developing catalysts with excellent stability while significantly reducing the overpotential of the oxygen evolution reaction(OER) is crucial for advancing overall water splitting(OWS) systems.In this study,we synthesized the electrode material Ce-NiCo-LDHs@SnO_(2)/NF through a two-step hydrothermal reaction,where Ce-doped NiCo-LDHs are grown on nickel foam modified by a SnO_(2) layer.Ce doping adjusts the internal electronic distribution of Ni Co-LDHs,while the introduction of the SnO_(2) layer enhances electron transfer capability.Together,these factors contribute to the reduction of the OER energy barrier and experimental evidence confirms that the reaction proceeds via the lattice oxygen evolution mechanism(LOM).Consequently,Ce-NiCo-LDHs@SnO_(2)/NF exhibits high level electrochemical performance in OER,requiring only 234 m V overpotential to achieve a current density of 10 m A/cm^(2),with a Tafel slope of just 27.39 m V/dec.When paired with Pt/C/NF,an external potential of only 1.54 V is needed to drive OWS to attain a current density amounting to 10 m A/cm^(2).Furthermore,the catalyst demonstrates stability for 100 h during the OWS stability test.This study underscores the feasibility of enhancing the OER performance through Ce doping and the introduction of a conductive SnO_(2) layer.
基金financial support of the National Natural Science Foundation of China(No.52472271)the National Key Research and Development Program of China(No.2023YFE0115800)。
文摘Heteroatom-doped carbon is considered a promising alternative to commercial Pt/C as an efficient catalyst for the oxygen reduction reaction(ORR).This study presents the synthesis of iron-loaded,sulfur and nitrogen co-doped carbon(Fe/SNC)via in situ incorporation of 2-aminothiazole molecules into zeolitic imidazolate framework-8(ZIF-8)through coordination between metal ions and organic ligands.Sulfur and nitrogen doping in carbon supports effectively modulates the electronic structure of the catalyst,increases the Brunauer-Emmett-Teller surface area,and exposes more Fe-N_(x)active centers.Fe-loaded,S and N co-doped carbon with Fe/S molar ratio of 1:10(Fe/SNC-10)exhibits a half-wave potential of 0.902 V vs.RHE.After 5000 cycles of cyclic voltammetry,its half-wave potential decreases by only 20 mV vs.RHE,indicating excellent stability.Due to sulfur s lower electronegativity,the electronic structure of the Fe-N_(x)active center is modulated.Additionally,the larger atomic radius of sulfur introduces defects into the carbon support.As a result,Fe/SNC-10 demonstrates superior ORR activity and stability in alkaline solution compared with Fe-loaded N-doped carbon(Fe/NC).Furthermore,the zinc-air battery assembled with the Fe/SNC-10 catalyst shows enhanced performance relative to those assembled with Fe/NC and Pt/C catalysts.This work offers a novel design strategy for advanced energy storage and conversion applications.
基金financially supported by the National Natural Science Foundation of China(No.22172144 and 22272151)Key Research and Development Program of Zhejiang Province(2023C03148).
文摘Photocatalytic nitrogen fixation has emerged as a sustainable alternative for ammonia synthesis,playing a crucial role in alleviating energy shortages and environmental pollution.In this study,PbBiO_(2)Br was applied to photocatalytic nitrogen fixation for the first time,and its photocatalytic performance was effectively enhanced through Cu doping.The catalyst was synthesized via a simple reduction method,and its morphology,structure,and physicochemical properties were systematically investigated using various characterization techniques and density functional theory calculations.The results revealed that the incorporation of Cu2+partially replaced Pb2+,inducing lattice distortion in PbBiO_(2)Br,promoting the formation of oxygen vacancies,and modifying its electronic band structure.Specifically,Cu doping led to a slight bandgap narrowing,a reduction in work function,and a significant upward shift in the conduction band position.These changes enhanced light absorption,facilitated charge carrier migration and separation,and improved the reduction ability of photogenerated electrons.Moreover,Cu doping promoted N_(2)adsorption and activation.Consequently,the photocatalytic nitrogen fixation performance of Cu-doped PbBiO_(2)Br was significantly enhanced,achieving an optimal nitrogen fixation rate of 293μmol L^(−1)g^(−1)h^(−1),which is 3.6 times higher than that of pristine PbBiO_(2)Br.Additionally,Cu–PbBiO_(2)Br also showed good activity in the photocatalytic degradation of RhB,with a degradation rate 4.6 times higher than that of PbBiO_(2)Br.This work offers new insights into the application of PbBiO_(2)Br in photocatalytic nitrogen fixation and offers valuable guidance for the development of highly efficient nitrogen fixation materials in the future.
基金supported by the National Natural Science Foundation of China (Grant Nos.12325406,92261201,12404305,and W2512072)the Shaanxi Province Natural Science Fundamental Research Project (Grant Nos.2023JC-XJ-03 and23JSQ013)the China Postdoctoral Science Foundation (Grant Nos.BX20240286 and 2024M7625)。
文摘Abiotic oxygen formation predates photosynthesis,sustaining early chemical evolution,yet its elementary mechanisms remain contested.Here,we show the production pathways for molecular oxygen from doubly ionized carbon dioxide upon electron-impact.Through fragment ions and electron coincidence momentum imaging,we unambiguously determine the ionization mechanism by measuring the projectile energy loss in association with the C^(+) +O_(2)^(+) channel.Further potential energy and trajectory calculations enable us to elucidate the dynamical details of this fragmentation process,in which a bond rearrangement pathway is found to proceed via the structural deformation to a triangular intermediate.Moreover,we demonstrate a further roaming pathway for the formation of O_(2)^(+) from CO_(2)^(+) 2,in which a frustrated C-O bond cleavage leaves the O atom without sufficient energy to escape.The O atom then wanders around varied configuration spaces of the flat potential energy regions and forms a C-O-O_(2)^(+) intermediate prior to the final products C^(+) +O_(2)^(+).Considering the large quantities of free electrons in interstellar space,the processes revealed here are expected to be significant and should be incorporated into atmospheric evolution models.
基金funded by the National Water Pollution Control and Management Technology Major Projects(No.2014ZX 07201-011)the Beijing Natural Science Foundation(No.8122005)of Chinathe Beijing Municipal EducationCommission General Program(No.KM2012-10005028)
文摘The objective of this study was to investigate the nitritation performance in a biofilm reactor for treating domestic wastewater.The reactor was operated in continuous feed mode from phases 1 to 3.The dissolved oxygen（DO）was controlled at 3.5–7 mg/L throughout the experiment.The biofilm reactor showed excellent nitritation performance after the inoculation of nitrifying sludge,with the hydraulic retention time being reduced from 24 to 7 hr.Above 90%nitrite accumulation ratio（NAR）was maintained in phase 1.Afterwards,nitratation occurred with the low NH4^＋–N concentration in the reactor.The improvement of NH4^＋–N concentration to 20–35 mg/L had a limited effect on the recovery of nitritation.However,nitritation recovered rapidly when sequencing batch feed mode was adopted in phase 4,with the effluent NH4^＋-N concentration above 7 mg/L.The improvement of ammonia oxidizing bacteria（AOB）activity and the combined inhibition effect of free ammonia（FA）and free nitrous acid（FNA）on the nitrite oxidizing bacteria（NOB）were two key factors for the rapid recovery of nitritation.Sludge activity was obtained in batch tests.The results of batch tests had a good relationship with the long term operation performance of the biofilm reactor.
文摘Binary composites(ZIF-67/rGO)were synthesized by one-step precipitation method using cobalt nitrate hexahydrate as metal source,2-methylimidazole as organic ligand,and reduced graphene oxide(rGO)as carbon carrier.Then Ru3+was introduced for ion exchange,and the porous Ru-doped Co_(3)O_(4)/rGO(Ru-Co_(3)O_(4)/rGO)composite electrocatalyst was prepared by annealing.The phase structure,morphology,and valence state of the catalyst were analyzed by X-ray powder diffraction(XRD),scanning electron microscope(SEM),transmission electron microscopy(TEM),and X-ray photoelectron spectroscopy(XPS).In 1 mol·L^(-1)KOH,the oxygen evolution reaction(OER)performance of the catalyst was measured by linear sweep voltammetry,cyclic voltammetry,and chronoamperometry.The results show that the combination of Ru doping and rGO provides a fast channel for collaborative electron transfer.At the same time,rGO as a carbon carrier can improve the electrical conductivity of Ru-Co_(3)O_(4)particles,and the uniformly dispersed nanoparticles enable the reactants to diffuse freely on the catalyst.The results showed that the electrochemical performance of Ru-Co_(3)O_(4)/rGO was much better than that of Co_(3)O_(4)/rGO,and the overpotential of Ru-Co_(3)O_(4)/rGO was 363.5 mV at the current density of 50 mA·cm^(-2).
文摘Sulfur-doped iron-cobalt tannate nanorods(S-FeCoTA)derived from metal-organic frameworks(MOFs)as electrocatalysts were synthesized via a one-step hydrothermal method.The optimized S-FeCoTA was interlaced by loose nanorods,which had many voids.The S-FeCoTA catalysts exhibited excellent electrochemical oxygen evolution reaction(OER)performance with a low overpotential of 273 mV at 10 mA·cm^(-2)and a small Tafel slope of 36 mV·dec^(-1)in 1 mol·L^(-1)KOH.The potential remained at 1.48 V(vs RHE)at 10 mA·cm^(-2)under continuous testing for 15 h,implying that S-FeCoTA had good stability.The Faraday efficiency of S-FeCoTA was 94%.The outstanding OER activity of S-FeCoTA is attributed to the synergistic effects among S,Fe,and Co,thus promoting electron transfer,reducing the reaction kinetic barrier,and enhancing the OER performance.
基金The National Natural Science Foundation of China under contract Nos T2421002, 623B2071,and 42125601the National Key R&D Program of China under contract No. 2023YFF0805300
文摘Oceanic dissolved oxygen(DO)in the ocean has an indispensable role on supporting biological respiration,maintaining ecological balance and promoting nutrient cycling.According to existing research,the total DO has declined by 2%of the total over the past 50 a,and the tropical Pacific Ocean occupied the largest oxygen minimum zone(OMZ)areas.However,the sparse observation data is limited to understanding the dynamic variation and trend of ocean using traditional interpolation methods.In this study,we applied different machine learning algorithms to fit regression models between measured DO,ocean reanalysis physical variables,and spatiotemporal variables.We demonstrate that extreme gradient boosting(XGBoost)model has the best performance,hereby reconstructing a four-dimensional DO dataset of the tropical Pacific Ocean from 1920 to 2023.The results reveal that XGBoost significantly improves the reconstruction performance in the tropical Pacific Ocean,with a 35.3%reduction in root mean-squared error and a 39.5%decrease in mean absolute error.Additionally,we compare the results with three Coupled Model Intercomparison Project Phase 6(CMIP6)models data to confirm the high accuracy of the 4-dimensional reconstruction.Overall,the OMZ mainly dominates the eastern tropical Pacific Ocean,with a slow expansion.This study used XGBoost to efficiently reconstructing 4-dimensional DO enhancing the understanding of the hypoxic expansion in the tropical Pacific Ocean and we foresee that this approach would be extended to reconstruct more ocean elements.
基金supported by the Central Guiding Local Science and Technology Development Fund of Shandong-Yellow River Basin(No.YDZX2023019)Shandong Natural Science Foundation of China(Nos.ZR2020QF067 and ZR2023QD073)+6 种基金the Discipline Cluster Research Project of Qingdao University“Deep mining and intelligent prediction of multimodal big data for marine ecological disasters”(No.20240604)sourced from the International Argo Program and the national programs that contribute to it(https://argo.ucsd.edu)the CMEMS(http://marine.copernicus.eu/)the CDS(https://cds.climate.copernicus.eu/)the EMODnet(https://www.emodnet-chemistry.eu/)obtained from the ERA5(https://www.ecmwf.int)derived from the Glob Colour Project(http://globcolour.info).
文摘Oceanic dissolved oxygen(DO)concentration is crucial for assessing the status of marine ecosystems.Against the backdrop of global warming,DO shows a general decrease,posing a threat to the health of marine ecosystems.Therefore,there is an urgent need to develop advanced tools to characterize the spatio-temporal variations of three-dimensional(3D)DO.To address this challenge,this study introduces the Light Gradient Boosting Machine(Light-GBM),combining satellite remote sensing and reanalysis data with Biogeochemical Argo data to accurately reconstruct the 3D DO structure in the Mediterranean Sea from 2010 to 2022.Various environmental parameters are incorporated as inputs,including spatiotemporal features,meteorological characteristics,and ocean color properties.The LightGBM model demonstrates excellent performance on the testing dataset with R^(2) of 0.958.The modeled DO agrees better with in-situ measurements than products from numerical models.Using the Shapley Additive exPlanations method,the contributions of input features are assessed.Sea surface temperatures provide a correlation with DO at the sea surface,while spatial coordinates supplement the view of the ocean interior.Based on the reconstructed 3D DO structure,we identify an oxygen minimum zone in the western Mediterranean that expands continuously,reaching depths of approximately 300–800 m.The western Mediterranean exhibits a significant declining trend.This study enhances marine environmental evidence by proposing a precise and cost-effective approach for reconstructing 3D DO,thereby offering insights into the dynamics of DO variations under changing climatic conditions.
基金Open Access funding provided by Kobe UniversityThis research was partially performed by the Environment Research and Technology Development Fund(2RL-2301)of the Environmental Restoration and Conservation Agency provided by Ministry of the Environment of Japan.
文摘This study examines the potential impacts o climate change on Lake Biwa,Japan’s largest freshwate lake,with a focus on temperature,wind speed,and pre cipitation variations.Leveraging data from the IPCC Sixth Assessment Report,including CCP scenarios,projecting a significant temperature rise of 3.3–5.7℃in the case o very high GHG emission power,the research investigates how these shifts may influence dissolved oxygen levels in Lake Biwa.Through a one-dimensional model incorporat ing sediment redox reactions,various scenarios where ai temperature and wind speed are changed are simulated.I is revealed that a 5℃increase in air temperature leads to decreasing 1-2 mg/L of dissolved oxygen concentrations from the surface layer to the bottom layer,while a decrease in air temperature tends to elevate 1–3 mg/L of oxygen lev els.Moreover,doubling wind speed enhances surface laye oxygen but diminishes it in deeper layers due to increased mixing.Seasonal variations in wind effects are noted with significant surface layer oxygen increases from 0.4to 0.8 mg/L during summer to autumn,increases from 0.4 to 0.8 mg/L in autumn to winter due to intensified vertica mixing.This phenomenon impacts the lake’s oxygen cycle year-round.In contrast,precipitation changes show limited impact on oxygen levels,suggesting minor influence com pared to other meteorological factors.The study suggests the necessity of comprehensive three-dimensional models that account for lake-specific and geographical factors fo accurate predictions of future water conditions.A holistic approach integrating nutrient levels,water temperature,and river inflow is deemed essential for sustainable management of Lake Biwa’s water resources,particularly in addressing precipitation variations.
基金supported by the National Natural Science Foundation of China(Nos.52171236,51971062,52231005)Open Research Fund of Jiangsu Key Laboratory for Advanced Metallic Materials,Southeast University,China(No.AMM2024A01)+3 种基金Suzhou Science and Technology Project,China(Nos.SJC2023005,SZS2023023)City University of Hong Kong Donation Research Grant,China(No.DON-RMG 9229021)City University of Hong Kong Strategic Research Grant,China(No.SRG 7005505)City University of Hong Kong Donation Grant,China(No.9220061)。
文摘To investigate the influence of oxygen content in a physiological liquid environment on the corrosion behavior of biomedical zinc-based alloys,a simulated bodily fluid environment with varying dissolved oxygen was established in vitro using external oxygen supply equipment.The influence of dissolved oxygen concentration on the corrosion behavior of pure Zn and Zn−Cu alloys was studied with scanning electron microscopy,energy dispersive spectroscopy,Fourier transform infrared spectrometry,and electrochemical analysis.Due to oxygen absorption corrosion,the increase in dissolved oxygen concentration increases the pH value of the solution and promotes the accumulation of corrosion product layer.Compared with the environment without additional oxygen supply,the corrosion rate of the sample under the continuous oxygen supply condition is increased by one order of magnitude.Because the Zn−Cu alloy has micro-galvanic corrosion,its corrosion rate is about 1.5 times that of pure zinc under different dissolved oxygen conditions.
基金supported by the National Key Research and Development Program of China(No.2022YFC3204000).
文摘Lake Baiyangdian is one of China’s largest macrophyte-derived lakes,facing severe challenges related to water quality maintenance and eutrophication prevention.Dissolved organic matter(DOM)was a huge carbon pool and its abundance,property,and transformation played important roles in the biogeochemical cycle and energy flow in lake ecosystems.In this study,Lake Baiyangdian was divided into four distinct areas:Unartificial Area(UA),Village Area(VA),Tourism Area(TA),and Breeding Area(BA).We examined the diversity of DOM properties and sources across these functional areas.Our findings reveal that DOM in this lake is predominantly composed of protein-like substances,as determined by excitation-emission matrix and parallel factor analysis(EEM-PARAFAC).Notably,the exogenous tyrosine-like component C1 showed a stronger presence in VA and BA compared to UA and TA.Ultrahigh-resolution mass spectrometry(FT-ICR MS)unveiled a similar DOM molecular composition pattern across different functional areas due to the high relative abundances of lignan compounds,suggesting that macrophytes significantly influence the material structure of DOM.DOM properties exhibited specific associations with water quality indicators in various functional areas,as indicated by the Mantel test.The connections between DOM properties and NO_(3)-N andNH3-Nwere more pronounced in VA and BA than in UA and TA.Our results underscore the viability of using DOM as an indicator for more precise and scientific water quality management.
基金Project supported by the National Natural Science Foundation of China(22062019)the Natural Science Foundation of Inner Mongolia of China(2022QN02002)Science and Technology Program of Inner Mongolia Autonomous Region,China(2020PT0003)。
文摘The development of an e fficacious and easily prepared no nprecious metal electrocatalyst is crucial for the oxygen reduction reaction(ORR).This work used a dual template method to prepare the amorphous rare earth-based catalyst PrO_(x)-NC,and optimized the calcination temperature and proportion.The PrO_(x)-NC-900 catalyst has high durability and activity and exhibits superior ORR performance in alkaline electrolytes with an onset potential(E_(0))of 0.96 V and a half-wave potential(E_(1/2))of 0.85 V.The research results indicate that the ORR performance of rare earth oxide composite carbon catalysts can be improved by adjusting oxygen vacancies(Ov).In addition,high specific surface area,N rich defect carbon.increased oxygen vacancies,and the synergistic effect of oxygen vacancies and N-doped carbon interfacial layer play a significant part in the enhancement of ORR.The performance of the zinc air battery assembled with PrO_(x)-NC-900 is significantly improved,and rare earth oxides and carbon frameworks originating from metal organic frameworks(MOFs)contribute to the oxygen electrocatalyst and electron transfer rate of the zinc air battery.This catalyst provides promising information for the development of rare earth metal oxide nanostructures as potential candidate materials for ORR in alkaline media.
基金financially supported by the National Natural Science Foundation of China(No.12304077)the Natural Science Foundation of Science and Technology Department of Sichuan Province(No.23NSFSC6224)+3 种基金Sichuan Science and Technology Program(No.2024NSFSC0989)the Key Laboratory of Computational Physics of Sichuan Province(No.YBUJSWL-YB-2022-03)the Material Corrosion and Protection Key Laboratory of Sichuan Province(No.2023CL14 and No.2023CL01)the National Innovation Practice Project(No.202411079005S).
文摘Oxygen release and electrolyte decomposition under high voltage endlessly exacerbate interfacial ramifications and structu ral degradation of high energy-density Li-rich layered oxide(LLO),leading to voltage and capacity fading.Herein,the dual-strategy of Cr,B complex coating and local gradient doping is simultaneously achieved on LLO surface by a one-step wet chemical reaction at room temperature.Density functional theory(DFT)calculations prove that stable B-O and Cr-O bonds through the local gradient doping can significantly reduce the high-energy O 2p states of interfacial lattice O,which is also effective for the near-surface lattice O,thus greatly stabilizing the LLO surface,Besides,differential electrochemical mass spectrometry(DEMS)indicates that the Cr_(x)B complex coating can adequately inhibit oxygen release and prevents the migration or dissolution of transition metal ions,including allowing speedy Li^(+)migration,The voltage and capacity fading of the modified cathode(LLO-C_(r)B)are adequately suppressed,which are benefited from the uniformly dense cathode electrolyte interface(CEI)composed of balanced organic/inorganic composition.Therefore,the specific capacity of LLO-CrB after 200 cycles at 1C is 209.3 mA h g^(-1)(with a retention rate of 95.1%).This dual-strategy through a one-step wet chemical reaction is expected to be applied in the design and development of other anionic redox cathode materials.
基金funded by the National Science Centre,Poland,on the basis of the decision number UMO-2020/37/B/ST8/02097supported by the program“Excellence Initiative-Research University”for the AGH University of Krakow(IDUB AGH,No.501.696.7996,Action 4,ID 9880).
文摘Multicomponent Gd_(1−x)Sm_(x)Ba_(0.5)Sr_(0.5)CoCuO_(5+δ)double perovskites are optimized for application in terms of chemical composi-tion and morphology for the use as oxygen electrodes in solid oxide cells.Structural studies of other physicochemical properties are con-ducted on a series of materials obtained by the sol-gel method with different ratios of Gd and Sm cations.It is documented that changing the x value,and the resulting adjustment of the average ionic radius,have a significant impact on the crystal structure,stability,as well as on the total conductivity and thermomechanical properties of the materials,with the best results obtained for the Gd_(0.75)Sm_(0.2)5Ba_(0.5)Sr_(0.5)CoCuO_(5+δ)composition.Oxygen electrodes are prepared using the selected compound,allowing to obtain low polarization resistance values,such as 0.086Ω·cm^(2)at 800℃.Systematic studies of electrocatalytic activity are conducted using La_(0.8)Sr_(0.2)Ga_(0.8)Mg_(_(0.2))O_(3−δ)as the electrolyte for all electrodes,and Ce_(0.8)Gd_(0.2)O_(2−δ)electrolyte for the best performing Gd_(0.75)Sm_(0.2)5Ba_(0.5)Sr_(0.5)CoCuO_(5+δ)electrodes.The electrochemical data are analyzed using the distribution of relaxation times method.Also,the influence of the preparation method of the electrode material is in-ve`stigated using the electrospinning technique.Finally,the performance of the Gd_(0.75)Sm_(0.2)5Ba_(0.5)Sr_(0.5)CoCuO_(5+δ)electrodes is tested in a Ni-YSZ(yttria-stabilized zirconia)anode-supported cell with a Ce_(0.8)Gd_(0.2)O_(2−δ)buffer layer,in the fuel cell and electrolyzer operating modes.With the electrospun electrode,a power density of 462 mW·cm^(−2)is obtained at 700℃,with a current density of ca.0.2 A·cm^(−2)at 1.3 V for the electrolysis at the same temperature,indicating better performance compared to the sol-gel-based electrode.
基金Funded by the Open Project of State Key Laboratory Cultivation Base for Nonmetal Composites and Functional Materials of Sichuan Province (No.10zxfk23)Scientific Research Project of Sichuan Normal University (No.11KYL06)
文摘To establish a immobilization method of oxygen sensitive dye, a dissolved oxygen sensor based on a sol-gel matrix doped with ruthenium complex ([Ru(bpy)3]2+) as the oxygen-sensitive material is reported. The results indicate that the I0 /I100 value of the [Ru(bpy)3]2+-doped in tetraethylorthosilane (TEOS) composite films are estimated to be 10.6, where I0 and I100 correspond to the detected fluorescence intensities in pure nitrogen saturated water and pure oxygen saturated water, respectively. Also, the Stern-Volmer plot shows a very good linearity at low dissolved oxygen concentrations. The response time of the composite films is 5 s upon switching from nitrogen saturated water to oxygen saturated water and 10 s from oxygen saturated water to nitrogen saturated water. The dissolved oxygen sensors based on the ruthenium complex/TEOS composite films exhibit greater sensitivity, stability and faster response time as compared to the existing ones. Furthermore, the thin films possess greatly minimized dye leaching effect.
基金financial support from the Natural Science Foundation of Shandong Province of China(ZR2023ME051,ZR2019MEM020)。
文摘Facilitating anion redox chemistry is an effective strategy to increase the capacity of layered oxides for sodium-ion batteries.Nevertheless,there remains a paucity of literature pertaining to the oxygen redox chemistry of O3-type layered oxide cathode materials.This work systematically investigates the effect of Fe doping on the anionic oxygen redox chemistry and electrochemical reactions in O3-NaNi_(0.4)Cu_(0.1)Mn_(0.4)Ti_(0.1)O_(2).The results of the density functional theory(DFT)calculations indicate that the electrons of the O 2p occupy a higher energy level.In the ex-situ X-ray photoelectron spectrometer(XPS)of O 1s,the addition of Fe facilitates the lattice oxygen(O^(n-))to exhibit enhanced activity at 4.45 V.The in-situ X-ray diffraction(XRD)demonstrates that the doping of Fe effectively suppresses the Y phase transition at high voltages.Furthermore,the Galvanostatic Intermittent Titration Technique(GITT)data indicate that Fe doping significantly increases the Na~+migration rate at high voltages.Consequently,the substitution of Fe can elevate the cut-off voltage to 4.45 V,thereby facilitating electron migration from O^(2-).The redox of O^(2-)/O^(n-)(n<2)contributes to the overall capacity.O3-Na(Ni_(0.4)Cu_(0.1)Mn_(0.4)Ti_(0.1))_(0.92)Fe_(0.08)O_(2)provides an initial discharge specific capacity of 180.55 mA h g^(-1)and71.6%capacity retention at 0.5 C(1 C=240 mA g^(-1)).This work not only demonstrates the beneficial impact of Fe substitution for promoting the redox activity and reversibility of O^(2-)in 03-type layered oxides,but also guarantees the structural integrity of the cathode materials at high voltages(>4.2 V).It offers a novel avenue for investigating the anionic redox reaction in O3-type layered oxides to design advanced cathode materials.
基金supported by National Natural Science Foundation of China(22379059)Applied Basic Research Program Project of Liaoning Province(2023JH2/101300224)+4 种基金Service Local Project of the Education Department of Liaoning Province(Enlisting and Leading)(LJKFZ20220201)General Project of the Educational Department of Liaoning Province(LJKMZ20220728)supported by Talent Scientific Research Fund of Liaoning Petrochemical University(2019-XJJL-028)Collaborative Innovation Project of Beijing-Tianjin-Hebei(Tianjin)(22PTXTHZ00020)Basic scientific research project of Liaoning Provincial Department of Education(LJ212410148019)。
文摘The adsorption of CO on different lattice oxygen sites in Cu doped CeO_(2)(111)was studied by DFT method,and the geometrical structure and electronic properties of adsorption systems were analyzed.The results showed that CO interacted with lattice oxygen on the first layer formed CO_(2).However,when adsorbed on the second layer lattice oxygen,carbonate species were formed with the participation of first layer lattice oxygens,i.e.,CO co-adsorbed on first and second layer lattice oxygens.For the second layer adsorption,the absolute CO adsorption energy was big on the Oss nearby Cu.This kind of carbonates was thermodynamically stable,and it was attributed to the facilitation of Cu on CO adsorption,manifested by an electron migration behavior from the C 2p orbitals to the Cu 3d orbitals.However,the absolute CO adsorption energy on the Oss away from Cu was small.Compared to the formation of carbonates,the formation CO_(2)had very small absolute adsorption energy,suggesting the formed carbonates on second layer was stable.Further,when CO adsorbed on the systems with a carbonate,the absolute CO adsorption energy was significantly smaller than that of the non-carbonated system,indicating that the formation of carbonates inhibited CO oxidation on Cu/CeO_(2)(111).Therefore,the formation of carbonates was unfavorable for CO oxidation reaction on Cu/CeO_(2)(111).The results of this study provide theoretical support for the negative effect of CO_(2)on ceria-based catalysts.
基金the National Key Research and Development Program of China(2022YFB4004100)National Natural Science Foundation of China(22272161,22179126)+1 种基金the Jilin Province Science and Technology Development Program(YDZJ202202CXJD011,20240101019JC)Jilin Province major science and technology project(222648GX0105103875)for financial supports.
文摘The weak adsorption energy of oxygen-containing intermediates on Co center leads to a considerable performance dis-parity between Co-N-C and costly Pt benchmark in catalyzing oxygen reduction reaction(ORR).In this work,we strategi-cally engineer the active site structure of Co-N-C via B substitution,which is accomplished by the pyrolysis of ammonium borate.During this process,the in-situ generated NH_(3)gas plays a critical role in creating surface defects and boron atoms substituting nitrogen atoms in the carbon structure.The well-designed CoB_(1)N_(3)active site endows Co with higher charge density and stronger adsorption energy toward oxygen species,potentially accelerating ORR kinetics.As expected,the resulting Co-B/N-C catalyst exhibited superior ORR performance over Co-N-C counterpart,with 40 mV,and fivefold en-hancement in half-wave potential and turnover frequency(TOF).More importantly,the excellent ORR performance could be translated into membrane electrode assembly(MEA)in a fuel cell test,delivering an impressive peak power density of 824 mW·cm^(-2),which is currently the best among Co-based catalysts under the same conditions.This work not only demon-strates an effective method for designing advanced catalysts,but also affords a highly promising non-precious metal ORR electrocatalyst for fuel cell applications.
基金supported by the National Natural Science Foundation of China(Nos.42207450,42067056,and 21866017)the Yunnan Fundamental Research Projects(No.202101BE070001-013)the Foundation for Distinguished Young Talents of Yunnan Province(No.202101AV070006).
文摘Dissolved black carbon(DBC)plays a crucial role in the migration and bioavailability of iron in water.However,the properties of DBC releasing under diverse pyrolysis conditions and dissolving processes have not been systematically studied.Here,the compositions of DBC released from biochar through redox processes dominated by bacteria and light were thoroughly studied.It was found that the DBC released from straw biochar possess more oxygen-containing functional groups and aromatic substances.The content of phenolic and carboxylic groups in DBC was increased under influence of microorganisms and light,respectively.The concentration of phenolic hydroxyl groups increased from 10.0~57.5 mmol/gC to 6.6~65.2 mmol/gC,and the concentration of carboxyl groups increased from49.7~97.5 mmol/gC to 62.1~113.3 mmol/gC.Then the impacts of DBC on pyrite dissolution andmicroalgae growth were also investigated.The complexing Fe^(3+)was proved to play a predominant role in the dissolution of ferrous mineral in DBC solution.Due to complexing between iron ion and DBC,the amount of dissolved Fe in aquatic water may rise as a result of elevated number of aromatic components with oxygen containing groups and low molecular weight generated under light conditions.Fe-DBC complexations in solution significantly promoted microalga growth,which might be attributed to the stimulating effect of dissolved Fe on the chlorophyll synthesis.The results of study will deepen our understanding of the behavior and ultimate destiny of DBC released into an iron-rich environment under redox conditions.
