BACKGROUND Hyperphosphatemia(HP)is a common complication in an advanced stage of chronic kidney disease(CKD)and is associated with cardiovascular issues,metabolic bone abnormalities and worsening of secondary hyperpar...BACKGROUND Hyperphosphatemia(HP)is a common complication in an advanced stage of chronic kidney disease(CKD)and is associated with cardiovascular issues,metabolic bone abnormalities and worsening of secondary hyperparathyroidism.Most patients on dialysis require phosphate binders to control HP.Sucroferric oxyhydroxide(SO)(Dynulta^(TM))is a calcium-free,polynuclear iron(III)based oral phosphate binder,for the treatment of HP.In this phase IV,open-label,singlearm,multi-center,12-week,SOLO CKD study evaluated efficacy and safety of Dynulta^(TM)in Indian CKD patients undergoing hemodialysis.AIM To investigate the efficacy,safety and tolerability of SO Chewable Tablet(Dynulta^(TM))in patients with CKD on hemodialysis.METHODS Hyperphosphatemic patients on hemodialysis and fulfilling eligibility criteria were included in the study for at least 12 weeks and received SO 1500 mg chewable tablet per day.The key endpoint was change in mean serum phosphorus levels after 12 weeks.Data were analysed using analysis of variance,Paired test,Wilcoxon test,and post-hoc comparisons,with P<0.05 considered statistically significant,using Graph Pad software.RESULTS A total of 114 patients were enrolled and 94 patients completed the study.The mean±SD serum phosphorous level was reduced from 7.62 mg/dL±2.02 mg/dL at baseline to 5.13 mg/dL±1.88 mg/dL after 12 weeks of treatment.At each follow-up visit,the reduction in mean serum phosphorous levels was statistically significant(P value<0.05)compared to baseline,confirming the efficacy of SO.A total of 33.33%of patients experienced adverse events(AEs).The most frequently reported AEs were pyrexia,nasopharyngitis and headache,which were considered unlikely to be related to the study drug treatment.No serious AEs was reported during the study period and no patients discontinued treatment due to AEs.CONCLUSION This first real-world study in Indian CKD patients on hemodialysis shows SO as a safe,and effective monotherapy for HP,though its small sample size limits generalizability.展开更多
Seawater electrolysis holds significant importance for advancing clean energy conversion.NiFe-based catalysts exhibit outstanding performance in the oxygen evolution reaction(OER)under alkaline conditions.However,the ...Seawater electrolysis holds significant importance for advancing clean energy conversion.NiFe-based catalysts exhibit outstanding performance in the oxygen evolution reaction(OER)under alkaline conditions.However,the instability of the Fe active center leads to leakage issues,hindering further development in the field of seawater electrolysis.Here,we adopt an element doping engineering strategy to enhance the OER activity of Ni-Fe oxyhydroxides and greatly stabilize the Fe sites by meticulously optimizing the d-band centers.Among the selected metals(Al,Ce,Co,Cr,Cu,Mn,Sn,Zn and Zr),Mn doping is the most effective as confirmed by both theoretical calculations and experimental verifications.The NiFeMn-OOH/NF formed in situ from the corresponding metal-organic framework requires only 217 mV to achieve a current density of 10 mA·cm^(–2) in alkaline seawater,and exhibits exceptional stability.Theoretical calculations uncover that the Fe sites exhibit better balance of adsorption-desorption kinetics for OER intermediates than Ni sites and Ni-Fe dual-sites,while Mn sites with the polyvalent nature modulate the d-band center closer to Fermi level,facilitate the transfer of electrons across the catalyst surface,thus accelerating the reaction kinetics.This work is of considerable significance for achieving efficient and sustainable seawater electrolysis.展开更多
Selective oxidation of amines to imines through electrocatalysis is an attractive and efficient way for the chemical industry to produce nitrile compounds,but it is limited by the difficulty of designing efficient cat...Selective oxidation of amines to imines through electrocatalysis is an attractive and efficient way for the chemical industry to produce nitrile compounds,but it is limited by the difficulty of designing efficient catalysts and lack of understanding the mechanism of catalysis.Herein,we demonstrate a novel strategy by generation of oxyhydroxide layers on two-dimensional iron-doped layered nickel phosphorus trisulfides(Ni1-xFexPS_(3))during the oxidation of benzylamine(BA).In-depth structural and surface chemical characterizations during the electrocatalytic process combined with theoretical calculations reveal that Ni(1-x)FexPS_(3) undergoes surface reconstruction under alkaline conditions to form the metal oxyhydroxide/phosphorus trichalcogenide(NiFeOOH/Ni1-xFexPS_(3))heterostructure.Interestingly,the generated heterointerface facilitates BA oxidation with a low onset potential of 1.39 V and Faradaic efficiency of 53%for benzonitrile(BN)synthesis.Theoretical calculations further indicate that the as-formed NiFeOOH/Ni1-xFexPS_(3) heterostructure could offer optimum free energy for BA adsorption and BN desorption,resulting in promising BN synthesis.展开更多
Nanostructured iron oxyhydroxide（Fe OOH） thin films have been synthesized using an electrodeposition method on a nickel foam（NF） substrate and effect of air annealing temperature on the catalytic performance is st...Nanostructured iron oxyhydroxide（Fe OOH） thin films have been synthesized using an electrodeposition method on a nickel foam（NF） substrate and effect of air annealing temperature on the catalytic performance is studied. The as-deposited and annealed thin films were characterized by X-ray diffraction（XRD）,X-ray photoelectron spectroscopy（XPS）, field emission scanning electron microscopy（FE-SEM） and linear sweep voltammetry（LSV） to determine their structural, morphological, compositional and electrochemical properties, respectively. The as-deposited nanostructured amorphous Fe OOH thin film is converted into a polycrystalline Fe;O;with hematite crystal structure at a high temperature. The Fe OOH thin film acts as an efficient electrocatalyst for the oxygen evolution reaction（OER） in an alkaline 1 M KOH electrolyte. The film annealed at 200 °C shows high catalytic activity with an onset overpotential of 240 m V with a smaller Tafel slope of 48 m V/dec. Additionally, it needs an overpotential of 290 mV to the drive the current density of 10 m A/cm;and shows good stability in the 1 M KOH electrolyte solution.展开更多
High-entropy oxides(HEOs)have emerged as a promising class of memristive materials,characterized by entropy-stabilized crystal structures,multivalent cation coordination,and tunable defect landscapes.These intrinsic f...High-entropy oxides(HEOs)have emerged as a promising class of memristive materials,characterized by entropy-stabilized crystal structures,multivalent cation coordination,and tunable defect landscapes.These intrinsic features enable forming-free resistive switching,multilevel conductance modulation,and synaptic plasticity,making HEOs attractive for neuromorphic computing.This review outlines recent progress in HEO-based memristors across materials engineering,switching mechanisms,and synaptic emulation.Particular attention is given to vacancy migration,phase transitions,and valence-state dynamics—mechanisms that underlie the switching behaviors observed in both amorphous and crystalline systems.Their relevance to neuromorphic functions such as short-term plasticity and spike-timing-dependent learning is also examined.While encouraging results have been achieved at the device level,challenges remain in conductance precision,variability control,and scalable integration.Addressing these demands a concerted effort across materials design,interface optimization,and task-aware modeling.With such integration,HEO memristors offer a compelling pathway toward energy-efficient and adaptable brain-inspired electronics.展开更多
This study focused on improving the cathode performance of Ba_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.15)O_(3-δ)(BSCN)-based perovskite materials through molybdenum(Mo)doping.Pure BSCN and Mo-modified-BSCN—Ea_(0.6)Sr_(0.4)Co_(0...This study focused on improving the cathode performance of Ba_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.15)O_(3-δ)(BSCN)-based perovskite materials through molybdenum(Mo)doping.Pure BSCN and Mo-modified-BSCN—Ea_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.1)Mo_(0.05)O_(3-δ)(B S CNM_(0.05)),Ba_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.05)Mo_(0.1)O_(3-δ)(BSCNM_(0.1)),and Ba_(0.6)Sr_(0.4)Co_(0.85)Mo_(0.15)O_(3-δ)(BSCM)—with Mo doping contents of 5mol%,10mol%,and15mol%,respectively,were successfully prepared using the sol-gel method.The effects of Mo doping on the crystal structure,conductivity,thermal expansion coefficient,oxygen reduction reaction(ORR)activity,and electrochemical performance were systematically evaluated using X-ray diffraction analysis,thermally induced characterization,electrochemical impedance spectroscopy,and single-cell performance tests.The results revealed that Mo doping could improve the conductivity of the materials,suppress their thermal expansion effects,and significantly improve the electrochemical performance.Surface chemical state analysis using X-ray photoelectron spectroscopy revealed that 5mol%Mo doping could facilitate a high adsorbed oxygen concentration leading to enhanced ORR activity in the materials.Density functional theory calculations confirmed that Mo doping promoted the ORR activity in the materials.At an operating temperature of 600℃,the BSCNM_(0.05)cathode material exhibited significantly enhanced electrochemical impedance characteristics,with a reduced area specific resistance of 0.048Ω·cm~2,which was lower than that of the undoped BSCN matrix material by 32.39%.At the same operating temperature,an anode-supported single cell using a BSCNM_(0.05)cathode achieved a peak power density of 1477 mW·cm^(-2),which was 30.71%,56.30%,and 171.50%higher than those of BSCN,BSCNM_(0.1),and B SCM,respectively.The improved ORR activity and electrochemical performance of BSCNM_(0.05)indicate that it can be used as a cathode material in low-temperature solid oxide fuel cells.展开更多
Oxide dispersion strengthened(ODS)alloys are extensively used owing to high thermostability and creep strength contributed from uniformly dispersed fine oxides particles.However,the existence of these strengthening pa...Oxide dispersion strengthened(ODS)alloys are extensively used owing to high thermostability and creep strength contributed from uniformly dispersed fine oxides particles.However,the existence of these strengthening particles also deteriorates the processability and it is of great importance to establish accurate processing maps to guide the thermomechanical processes to enhance the formability.In this study,we performed particle swarm optimization-based back propagation artificial neural network model to predict the high temperature flow behavior of 0.25wt%Al2O3 particle-reinforced Cu alloys,and compared the accuracy with that of derived by Arrhenius-type constitutive model and back propagation artificial neural network model.To train these models,we obtained the raw data by fabricating ODS Cu alloys using the internal oxidation and reduction method,and conducting systematic hot compression tests between 400 and800℃with strain rates of 10^(-2)-10 S^(-1).At last,processing maps for ODS Cu alloys were proposed by combining processing parameters,mechanical behavior,microstructure characterization,and the modeling results achieved a coefficient of determination higher than>99%.展开更多
Investigating structural and hydroxyl group effects in electrooxidation of alcohols to value-added products by solid-acid electrocatalysts is essential for upgrading biomass alcohols.Herein,we report efficient electro...Investigating structural and hydroxyl group effects in electrooxidation of alcohols to value-added products by solid-acid electrocatalysts is essential for upgrading biomass alcohols.Herein,we report efficient electrocatalytic oxidations of saturated alcohols(C_(1)-C_(6))to selectively form formate using Ni Co hydroxide(Ni Co-OH)derived Ni Co_(2)O_(4)solid-acid electrocatalysts with balanced Lewis acid(LASs)and Brønsted acid sites(BASs).Thermal treatment transforms BASs-rich(89.6%)Ni Co-OH into Ni Co_(2)O_(4)with nearly equal distribution of LASs(53.1%)and BASs(46.9%)which synergistically promote adsorption and activation of OH-and alcohol molecules for enhanced oxidation activity.In contrast,BASs-enriched Ni Co-OH facilitates formation of higher valence metal sites,beneficial for water oxidation.The combined experimental studies and theoretical calculation imply the oxidation ability of C1-C6alcohols increases as increased number of hydroxyl groups and decreased HOMO-LUMO gaps:methanol(C_(1))<ethylene glycol(C_(2))<glycerol(C3)<meso-erythritol(C4)<xylitol(C5)<sorbitol(C6),while the formate selectivity shows the opposite trend from 100 to 80%.This study unveils synergistic roles of LASs and BASs,as well as hydroxyl group effect in electro-upgrading of alcohols using solid-acid electrocatalysts.展开更多
The arsenic removal efficiency of iron-modified activated carbons depends greatly on the number of available iron oxide surface sites, which are given by the surface area of the anchored particles. In this sense, aimi...The arsenic removal efficiency of iron-modified activated carbons depends greatly on the number of available iron oxide surface sites, which are given by the surface area of the anchored particles. In this sense, aiming the generation of an adsorbent with superior arsenic adsorption capacity, we developed a protocol to anchor interconnected fibrils of iron oxyhydroxides, using Mn^(2+) as a morphology regulator. The protocol was based on a microwave-assisted hydrothermal method, using bituminous based activated carbon and both Fe^(2+) and Mn^(2+) ions in the hydrolysis solution. The elemental analysis of modified carbons revealed that Mn does not anchor to the carbon. However, when Mn is included in the hydrolysis solution, the iron content in the activated carbon increased up to 3.5 wt%,without considerable decreasing the adsorbent surface area. Under specific hydrothermal conditions, the Mn^(2+) promoted the formation of iron oxide nanoparticles shaped as interconnected fibrils. This material showed a superior arsenic adsorption capacity in comparison to similar iron modified activated carbons(5 mg As/g carbon, at 2 mg As/L),attributed to the increase in quantity and availability of active sites located on the novel interconnected fibrils of iron oxyhydroxides nanostructures.展开更多
Mesenchymal stromal cell transplantation is an effective and promising approach for treating various systemic and diffuse diseases.However,the biological characteristics of transplanted mesenchymal stromal cells in hu...Mesenchymal stromal cell transplantation is an effective and promising approach for treating various systemic and diffuse diseases.However,the biological characteristics of transplanted mesenchymal stromal cells in humans remain unclear,including cell viability,distribution,migration,and fate.Conventional cell tracing methods cannot be used in the clinic.The use of superparamagnetic iron oxide nanoparticles as contrast agents allows for the observation of transplanted cells using magnetic resonance imaging.In 2016,the National Medical Products Administration of China approved a new superparamagnetic iron oxide nanoparticle,Ruicun,for use as a contrast agent in clinical trials.In the present study,an acute hemi-transection spinal cord injury model was established in beagle dogs.The injury was then treated by transplantation of Ruicun-labeled mesenchymal stromal cells.The results indicated that Ruicunlabeled mesenchymal stromal cells repaired damaged spinal cord fibers and partially restored neurological function in animals with acute spinal cord injury.T2*-weighted imaging revealed low signal areas on both sides of the injured spinal cord.The results of quantitative susceptibility mapping with ultrashort echo time sequences indicated that Ruicun-labeled mesenchymal stromal cells persisted stably within the injured spinal cord for over 4 weeks.These findings suggest that magnetic resonance imaging has the potential to effectively track the migration of Ruicun-labeled mesenchymal stromal cells and assess their ability to repair spinal cord injury.展开更多
Europium oxyhydroxide crystals were synthesized by the flux method. The as-grown crystals were transparent and had a plate-like shape with natural flat surfaces. The powder XRD data were refined by assuming a monoclin...Europium oxyhydroxide crystals were synthesized by the flux method. The as-grown crystals were transparent and had a plate-like shape with natural flat surfaces. The powder XRD data were refined by assuming a monoclinic structure of the space group P21/m and lattice parameters of a=0.4346 nm, b=0.3744 nm, c=0.6107 nm, and β=108.62°. The magnetic susceptibility of the EuOOH crystals exhibited typical Van Vleck temperature-independent paramagnetism below 120 K. The calculated susceptibility, based on Van Vleck＇s theory, agreed with the experimental data to some extent, with the coupling constant λ=458±10 K. The experimental results were in close agreement with the results calculated using a modified formula with λ=505±2 K and a constant term C=4.6×10^-4 emu/（mol·Oe）.展开更多
Rational design of low‐cost and efficient electrocatalysts for ethanol oxidation reaction(EOR)is imperative for electrocatalytic ethanol fuel cells.In this work,we developed a copper‐doped nickel oxyhydroxide(Cu‐do...Rational design of low‐cost and efficient electrocatalysts for ethanol oxidation reaction(EOR)is imperative for electrocatalytic ethanol fuel cells.In this work,we developed a copper‐doped nickel oxyhydroxide(Cu‐doped NiOOH)catalyst via in situ electrochemical reconstruction of a NiCu alloy.The introduction of Cu dopants increases the specific surface area and more defect sites,as well as forms high‐valence Ni sites.The Cu‐doped NiOOH electrocatalyst exhibited an excellent EOR performance with a peak current density of 227 mA·cm^(–2)at 1.72 V versus reversible hydrogen electrode,high Faradic efficiencies for acetate production(>98%),and excellent electrochemical stability.Our work suggests an attractive route of designing non‐noble metal based electrocatalysts for ethanol oxidation.展开更多
Crystals of co-doped gadolinium oxyhydroxide （GdOOH）, Gd0.98Eu0.02-xTbxOOH and Gd1-y-zDyyBizOOH, were synthesized by a flux method. The color coordinates in the Commission Internationale de I＇Eelairage （CIE） chro...Crystals of co-doped gadolinium oxyhydroxide （GdOOH）, Gd0.98Eu0.02-xTbxOOH and Gd1-y-zDyyBizOOH, were synthesized by a flux method. The color coordinates in the Commission Internationale de I＇Eelairage （CIE） chromaticity diagram of Gd0.98Eu0.02-xTbxOOH, obtained under 254 nm irradiation, shifted along a straight line with the changing values ofx to include the yellow region. The CIE coordinates of Dy^3＋ doped in GdOOH were located in the yellow region, while the emission intensity of Dy^3＋ under 286 nm irradiation increased by more than 40 times when co-doped with Bi^3＋.展开更多
During the chemical weathering of the uranium mill tailings,released uranium could be immobilized by the newly formed secondary minerals such as oxyhydroxides.A deeper understanding of the interaction between uranium ...During the chemical weathering of the uranium mill tailings,released uranium could be immobilized by the newly formed secondary minerals such as oxyhydroxides.A deeper understanding of the interaction between uranium and common oxyhydroxides under environmental conditions is necessary.In this work,uranium sorption behaviors on Al-,Mn-and Fe-oxyhydroxide minerals(boehmite,manganite,goethite,and lepidocrocite)were investigated by batch experiments.Results showed that the uranium sorption on Al-oxyhydroxide behaved significantly differently from the other three minerals.The sorption edge of the Mn-and Fe-oxyhydroxides located around pH 5,while the sorption edge of boehmite shifted about 1.5 pH unit to near neutral.The sorption isotherms of uranium on manganite,goethite and lepidocrocite at pH 5.0 could be well fitted by the Langmuir model.Instead of surface complexation,sorption on boehmite happened mainly by uranium-bearing carbonates and hydroxides precipitation as illustrated by the characterization results.Both carbonate and phosphate strongly affected the uranium sorption behavior.The removal efficiency of uranium by boehmite exceeded 98%after three sorption-desorption cycles,indicating it may be a potential material for uranium removal and recovery.展开更多
Developing high-performing oxygen evolution reaction(OER)electrocatalysts under high-current operation conditions is critical for future commercial applications of alkaline water electrolysis for clean energy generati...Developing high-performing oxygen evolution reaction(OER)electrocatalysts under high-current operation conditions is critical for future commercial applications of alkaline water electrolysis for clean energy generation.Herein,we prepared a three-dimensional(3D)bimetallic oxyhydroxide hybrid grown on a Ni foam(NiFeOOH/NF)prepared by immersing Ni foam(NF)into Fe(NO_(3))_(3) solution.In this unique 3D structure,the NiFeOOH/NF hybrid was composed of crystalline Ni(OH)_(2) and amorphous FeOOH evenly grown on the NF surface.As a bimetallic oxyhydroxide electrocatalyst,the NiFeOOH/NF hybrid exhibited excellent catalytic activity,surpassing not only the other reported Ni–Fe based electrocatalysts,but also the commercial Ir/C catalyst.In situ electrochemical Raman spectroscopy demonstrated the active FeOOH and NiOOH phases involved in the OER process.Profiting from the synergy of Fe and Ni catalytic sites,the NiFeOOH/NF hybrid delivered an outstanding OER performance under challenging industrial conditions in a 10.0 mol·L^(-1) KOH electrolyte at 80℃,requiring potentials as small as 1.47 and 1.51 V to achieve the super-high catalytic current densities of 100 and 500mA∙cm^(-2),respectively.展开更多
Metal oxyhydroxides(MOOH)generated from irreversible reconstructions of transition metal compounds are intrinsic active species for oxygen evolution reaction,whose activities are still constrained by sluggish deproton...Metal oxyhydroxides(MOOH)generated from irreversible reconstructions of transition metal compounds are intrinsic active species for oxygen evolution reaction,whose activities are still constrained by sluggish deprotonation kinetics and inherent adsorption energy scaling relations.Herein,we construct a tunable proton acceptor(TPA)on oxyhydroxides by in-situ reconstruction of metal oxoacids such as NiC2O4to accelerate deprotonation and break adsorption energy scaling relations during OER.The modified C_(2)O_(4)^(2-)as a TPA can easily extract H of*OH(forming*HC2O4intermediate)and then promote deprotonation by the transmitted hydrogen bond with*OOH along conjugated(H...)O=C-O(-H)chain.As a result,Ni OOH-C2O4shows non-concerted proton-electron transfer and improved deprotonation rate,and delivers a good OER activity(270 mV@10 mA cm-2).The conjugate acidity coefficient(pKa)of the modified oxoacid group can be a descriptor for TPA selection.This TPA strategy can be universally applied to Co-,Fe-,and Ni-based oxyhydroxides to facilitate OER efficiency.展开更多
Equilibrium Si isotope fractionation factors among orthosilicic acid(i.e.,H4 Si O4(aq)), quartz and the adsorption complexes of H4 Si O4(aq)on Fe(III)-oxyhydroxide surface were calculated using the full-electron wave-...Equilibrium Si isotope fractionation factors among orthosilicic acid(i.e.,H4 Si O4(aq)), quartz and the adsorption complexes of H4 Si O4(aq)on Fe(III)-oxyhydroxide surface were calculated using the full-electron wave-function quantum chemistry methods [i.e., B3LYP/6-311G(2df,p)]with a new cluster-model-based treatment. Solvation effects were carefully included in our calculations via water-droplet method combined with implicit solvent models(e.g., PCM).The results revealed that, if it is under equilibrium conditions,heavy Si isotopes would be significantly enriched in quartz in comparison to H4 Si O4(aq). However, most of the field observations suggested that quartz would have identical or even depleted d30 Si values compared to that of H4 Si O4(aq). To explain this discrepancy between the equilibrium calculation results and the field observations, the kinetic isotope effect(KIE) associated with the formation of amorphous silica,which usually is the precursor of crystalline quartz, was investigated using quantum chemistry methods. The KIE results showed that amorphous silica would be significantly enriched in light Si isotopes during its formation. Our equilibrium fractionation results, however, matched a special type of quartz(i.e., Herkimer ‘‘diamond'') very well, due to its nearly equilibrated precipitation condition. Opposite to the case of precipitated quartz, a large equilibrium Si isotope fractionation(i.e.,-3.0 %) was found between the absorbed bidentate Si surface complexes(i.e.,2C [ Fe2O2Si(OH)2) and H4 Si O4(aq). This calculated equilibrium Si isotope fractionation factor largely differed from a previous experimental result(ca.-1.08 %). We found that the formation of transient or temporary surface complexes [e.g.,1V [ Fe2OSi(OH)3] may have accounted for the smaller net fractionation observed.With the equilibrium and kinetic Si isotope fractionation factors provided here, the distributions and changes of Si isotope compositions in the Earth's surface systems can be better understood.展开更多
Utilizing Si, Fe and Mn concentrations within the end-member PACMANUS hydrothermal fluid, Si-Fe-Mn-H2O Pourbaix diagrams were constructed at 300℃and 25℃. ThePourbaix diagrams show that the main Si, Fe and Mn oxides ...Utilizing Si, Fe and Mn concentrations within the end-member PACMANUS hydrothermal fluid, Si-Fe-Mn-H2O Pourbaix diagrams were constructed at 300℃and 25℃. ThePourbaix diagrams show that the main Si, Fe and Mn oxides species precipitating from the hydrothermal fluid were SiO2, Fe（OH）3, Fe3（OH）8, Mn3O4, and Mn2O3at 25℃. During mixing of hydrothermal fluid with seawater, SiO2 precipitated earlier than Fe-Mn-oxyhydroxides because of the lower stability boundary. Then Fe（OH）2 precipitated first, followed by Fe3（OH）8 and Fe（OH）3, and last, small amounts of Mn3O4 and Mn2O3 precipitated. Fe（OH）3was readily de-posited in alkaline solution with little influence by Eh. There were many Si-Fe-Mn-concentric particles in the polished sections of the massive precipitates collected from PACMANUS. In the concentric nucleus and ellipsoid, Si oxides precipitated first before the hydrothermal fluid had mixed with seawater. In the concen-tric nucleus, after the precipitation of Si oxides, the increase of pH and Eh promoted the precipitation of Mn oxides around the Si oxides. In the large ellipsoid, the precipitation of Fe was divided into two periods. In the early period, increase of pH value of hydrothermal fluid produced by low-temperature convection and an input of a small volume of seawater promoted a small amount of Fe（OH）3 to precipitate in the Si-rich core. In the late period, after complete mixing with seawater and the resultant fluid was close to neutral or slightly alkaline in pH, Fe（OH）3was easily precipitated from the solution and distributed around the Si-rich core.展开更多
Polypyrrole(PPy)@cellulose fiber-based composites have been widely investigated as electrode materials for use in flexible supercapacitors.However,they cannot readily provide high specific capacitance and cyclic stabi...Polypyrrole(PPy)@cellulose fiber-based composites have been widely investigated as electrode materials for use in flexible supercapacitors.However,they cannot readily provide high specific capacitance and cyclic stability owing to their inherent drawbacks,such as high resistance,Weber impedance,and volume expansion or collapse during charging/discharging.In this study,iron oxyhydroxide(FeOOH)is incorporated in the abovementioned composite to decrease the equivalent series resistance,charge transfer resistance,and Weber impedance,thereby enhancing electron transfer and ion diffusion,which results in superior electrochemical performance.The PPy-wrapped FeOOH@cellulose fiber-based composite electrode with the molar ratio of FeSO_(4) to NaBH4 of 1∶1 exhibits a high specific capacitance of 513.8 F/g at a current density of 0.2 A/g,as well as an excellent capacitance retention of 89.4% after 1000 cycles.展开更多
Si-Fe-Mn-oxyhydroxides dredged at the PACMANUS （Papua New Guinea-Australia-Canada-Manus） hydrothermal field, Eastern Manus Basin, have 87Sr/SSSr=0.708 079-0.708 581; eNd=5.149 833-6.534 826; 208pb/204pb=38.245-38.44...Si-Fe-Mn-oxyhydroxides dredged at the PACMANUS （Papua New Guinea-Australia-Canada-Manus） hydrothermal field, Eastern Manus Basin, have 87Sr/SSSr=0.708 079-0.708 581; eNd=5.149 833-6.534 826; 208pb/204pb=38.245-38.440; 207pb/204pb=lS.503-15.560; 206pb/204pb=lS.682-18.783. s7sr/sSSr isotope ratios are relatively homogeneous and close to the value of the surrounding seawater （0.709 16）. The content of Sr in the samples contributed by seawater was estimated to be 76.7%-83.1% of total amount. The mixing temperature of hydrothermal fluids and seawater were ranging from 53.2℃ to 72.2℃ and the hydrothermal activities were unstable when the samples precipitated. The eNd values of all the samples are positive, which differ from the values of ferromanganese nodules （crusts） with hydrogenic origin. Nd was mainly derived from substrate rocks leached by hydrothermal circulation and preserved the hydrothermal signature. Ph isotopic compositions of most samples show minor variability except Sample #9-2 that has relatively high values of Pb isotopes. The Pb may be derived from the Eastern Manus Basin rocks leached by the hydrothermal fluid. The slightly lower 28pb/204pb and 207pb/204pb values of the samples indicated that the hydrothermal circulation in PACMANUS was not entire and sufficient, or that hydrothermal circulation had transient changes in the past. Si-Fe-Mn-oxyhydroxides in the samples preserved the heterogeneities of local rocks.展开更多
文摘BACKGROUND Hyperphosphatemia(HP)is a common complication in an advanced stage of chronic kidney disease(CKD)and is associated with cardiovascular issues,metabolic bone abnormalities and worsening of secondary hyperparathyroidism.Most patients on dialysis require phosphate binders to control HP.Sucroferric oxyhydroxide(SO)(Dynulta^(TM))is a calcium-free,polynuclear iron(III)based oral phosphate binder,for the treatment of HP.In this phase IV,open-label,singlearm,multi-center,12-week,SOLO CKD study evaluated efficacy and safety of Dynulta^(TM)in Indian CKD patients undergoing hemodialysis.AIM To investigate the efficacy,safety and tolerability of SO Chewable Tablet(Dynulta^(TM))in patients with CKD on hemodialysis.METHODS Hyperphosphatemic patients on hemodialysis and fulfilling eligibility criteria were included in the study for at least 12 weeks and received SO 1500 mg chewable tablet per day.The key endpoint was change in mean serum phosphorus levels after 12 weeks.Data were analysed using analysis of variance,Paired test,Wilcoxon test,and post-hoc comparisons,with P<0.05 considered statistically significant,using Graph Pad software.RESULTS A total of 114 patients were enrolled and 94 patients completed the study.The mean±SD serum phosphorous level was reduced from 7.62 mg/dL±2.02 mg/dL at baseline to 5.13 mg/dL±1.88 mg/dL after 12 weeks of treatment.At each follow-up visit,the reduction in mean serum phosphorous levels was statistically significant(P value<0.05)compared to baseline,confirming the efficacy of SO.A total of 33.33%of patients experienced adverse events(AEs).The most frequently reported AEs were pyrexia,nasopharyngitis and headache,which were considered unlikely to be related to the study drug treatment.No serious AEs was reported during the study period and no patients discontinued treatment due to AEs.CONCLUSION This first real-world study in Indian CKD patients on hemodialysis shows SO as a safe,and effective monotherapy for HP,though its small sample size limits generalizability.
文摘Seawater electrolysis holds significant importance for advancing clean energy conversion.NiFe-based catalysts exhibit outstanding performance in the oxygen evolution reaction(OER)under alkaline conditions.However,the instability of the Fe active center leads to leakage issues,hindering further development in the field of seawater electrolysis.Here,we adopt an element doping engineering strategy to enhance the OER activity of Ni-Fe oxyhydroxides and greatly stabilize the Fe sites by meticulously optimizing the d-band centers.Among the selected metals(Al,Ce,Co,Cr,Cu,Mn,Sn,Zn and Zr),Mn doping is the most effective as confirmed by both theoretical calculations and experimental verifications.The NiFeMn-OOH/NF formed in situ from the corresponding metal-organic framework requires only 217 mV to achieve a current density of 10 mA·cm^(–2) in alkaline seawater,and exhibits exceptional stability.Theoretical calculations uncover that the Fe sites exhibit better balance of adsorption-desorption kinetics for OER intermediates than Ni sites and Ni-Fe dual-sites,while Mn sites with the polyvalent nature modulate the d-band center closer to Fermi level,facilitate the transfer of electrons across the catalyst surface,thus accelerating the reaction kinetics.This work is of considerable significance for achieving efficient and sustainable seawater electrolysis.
基金National Natural Science Foundation of China,Grant/Award Number:22179029Fundamental Research Funds for the Central Universities,Grant/Award Number:buctrc202324+2 种基金Young Elite Scientists Sponsorship Program by BAST,Grant/Award Number:BYESS2023093Ministero dell'Istruzione,dell'Universitàe della Ricerca,Grant/Award Number:2022FNL89YKempestiftelserna。
文摘Selective oxidation of amines to imines through electrocatalysis is an attractive and efficient way for the chemical industry to produce nitrile compounds,but it is limited by the difficulty of designing efficient catalysts and lack of understanding the mechanism of catalysis.Herein,we demonstrate a novel strategy by generation of oxyhydroxide layers on two-dimensional iron-doped layered nickel phosphorus trisulfides(Ni1-xFexPS_(3))during the oxidation of benzylamine(BA).In-depth structural and surface chemical characterizations during the electrocatalytic process combined with theoretical calculations reveal that Ni(1-x)FexPS_(3) undergoes surface reconstruction under alkaline conditions to form the metal oxyhydroxide/phosphorus trichalcogenide(NiFeOOH/Ni1-xFexPS_(3))heterostructure.Interestingly,the generated heterointerface facilitates BA oxidation with a low onset potential of 1.39 V and Faradaic efficiency of 53%for benzonitrile(BN)synthesis.Theoretical calculations further indicate that the as-formed NiFeOOH/Ni1-xFexPS_(3) heterostructure could offer optimum free energy for BA adsorption and BN desorption,resulting in promising BN synthesis.
基金supported by the Human Resources Development program(no.20124010203180) of the Korea Institute of Energy Technology Evaluation and Planning(KETEP)Grant funded by the Korea government Ministry of Trade,Industry and Energysupported by Basic Science Research Program through the National Research Foundation of Korea(NRF) funded by the Ministry of Science,ICT and Future Planning(NRF-2015R1A2A2A01006856)
文摘Nanostructured iron oxyhydroxide（Fe OOH） thin films have been synthesized using an electrodeposition method on a nickel foam（NF） substrate and effect of air annealing temperature on the catalytic performance is studied. The as-deposited and annealed thin films were characterized by X-ray diffraction（XRD）,X-ray photoelectron spectroscopy（XPS）, field emission scanning electron microscopy（FE-SEM） and linear sweep voltammetry（LSV） to determine their structural, morphological, compositional and electrochemical properties, respectively. The as-deposited nanostructured amorphous Fe OOH thin film is converted into a polycrystalline Fe;O;with hematite crystal structure at a high temperature. The Fe OOH thin film acts as an efficient electrocatalyst for the oxygen evolution reaction（OER） in an alkaline 1 M KOH electrolyte. The film annealed at 200 °C shows high catalytic activity with an onset overpotential of 240 m V with a smaller Tafel slope of 48 m V/dec. Additionally, it needs an overpotential of 290 mV to the drive the current density of 10 m A/cm;and shows good stability in the 1 M KOH electrolyte solution.
基金financially supported by the National Natural Science Foundation of China(Grant No.12172093)the Guangdong Basic and Applied Basic Research Foundation(Grant No.2021A1515012607)。
文摘High-entropy oxides(HEOs)have emerged as a promising class of memristive materials,characterized by entropy-stabilized crystal structures,multivalent cation coordination,and tunable defect landscapes.These intrinsic features enable forming-free resistive switching,multilevel conductance modulation,and synaptic plasticity,making HEOs attractive for neuromorphic computing.This review outlines recent progress in HEO-based memristors across materials engineering,switching mechanisms,and synaptic emulation.Particular attention is given to vacancy migration,phase transitions,and valence-state dynamics—mechanisms that underlie the switching behaviors observed in both amorphous and crystalline systems.Their relevance to neuromorphic functions such as short-term plasticity and spike-timing-dependent learning is also examined.While encouraging results have been achieved at the device level,challenges remain in conductance precision,variability control,and scalable integration.Addressing these demands a concerted effort across materials design,interface optimization,and task-aware modeling.With such integration,HEO memristors offer a compelling pathway toward energy-efficient and adaptable brain-inspired electronics.
基金financially supported by the National Natural Science Foundation of China(No.22309067)the Open Project Program of the State Key Laboratory of Materials-Oriented Chemical Engineering,China(No.KL21-05)the Marine Equipment and Technology Institute,Jiangsu University of Science and Technology,China(No.XTCX202404)。
文摘This study focused on improving the cathode performance of Ba_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.15)O_(3-δ)(BSCN)-based perovskite materials through molybdenum(Mo)doping.Pure BSCN and Mo-modified-BSCN—Ea_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.1)Mo_(0.05)O_(3-δ)(B S CNM_(0.05)),Ba_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.05)Mo_(0.1)O_(3-δ)(BSCNM_(0.1)),and Ba_(0.6)Sr_(0.4)Co_(0.85)Mo_(0.15)O_(3-δ)(BSCM)—with Mo doping contents of 5mol%,10mol%,and15mol%,respectively,were successfully prepared using the sol-gel method.The effects of Mo doping on the crystal structure,conductivity,thermal expansion coefficient,oxygen reduction reaction(ORR)activity,and electrochemical performance were systematically evaluated using X-ray diffraction analysis,thermally induced characterization,electrochemical impedance spectroscopy,and single-cell performance tests.The results revealed that Mo doping could improve the conductivity of the materials,suppress their thermal expansion effects,and significantly improve the electrochemical performance.Surface chemical state analysis using X-ray photoelectron spectroscopy revealed that 5mol%Mo doping could facilitate a high adsorbed oxygen concentration leading to enhanced ORR activity in the materials.Density functional theory calculations confirmed that Mo doping promoted the ORR activity in the materials.At an operating temperature of 600℃,the BSCNM_(0.05)cathode material exhibited significantly enhanced electrochemical impedance characteristics,with a reduced area specific resistance of 0.048Ω·cm~2,which was lower than that of the undoped BSCN matrix material by 32.39%.At the same operating temperature,an anode-supported single cell using a BSCNM_(0.05)cathode achieved a peak power density of 1477 mW·cm^(-2),which was 30.71%,56.30%,and 171.50%higher than those of BSCN,BSCNM_(0.1),and B SCM,respectively.The improved ORR activity and electrochemical performance of BSCNM_(0.05)indicate that it can be used as a cathode material in low-temperature solid oxide fuel cells.
基金financial support of the National Natural Science Foundation of China(No.52371103)the Fundamental Research Funds for the Central Universities,China(No.2242023K40028)+1 种基金the Open Research Fund of Jiangsu Key Laboratory for Advanced Metallic Materials,China(No.AMM2023B01).financial support of the Research Fund of Shihezi Key Laboratory of AluminumBased Advanced Materials,China(No.2023PT02)financial support of Guangdong Province Science and Technology Major Project,China(No.2021B0301030005)。
文摘Oxide dispersion strengthened(ODS)alloys are extensively used owing to high thermostability and creep strength contributed from uniformly dispersed fine oxides particles.However,the existence of these strengthening particles also deteriorates the processability and it is of great importance to establish accurate processing maps to guide the thermomechanical processes to enhance the formability.In this study,we performed particle swarm optimization-based back propagation artificial neural network model to predict the high temperature flow behavior of 0.25wt%Al2O3 particle-reinforced Cu alloys,and compared the accuracy with that of derived by Arrhenius-type constitutive model and back propagation artificial neural network model.To train these models,we obtained the raw data by fabricating ODS Cu alloys using the internal oxidation and reduction method,and conducting systematic hot compression tests between 400 and800℃with strain rates of 10^(-2)-10 S^(-1).At last,processing maps for ODS Cu alloys were proposed by combining processing parameters,mechanical behavior,microstructure characterization,and the modeling results achieved a coefficient of determination higher than>99%.
基金the financial support from the National Natural Science Foundation of China(52172110,52472231,52311530113)Shanghai"Science and Technology Innovation Action Plan"intergovernmental international science and technology cooperation project(23520710600)+1 种基金Science and Technology Commission of Shanghai Municipality(22DZ1205600)the Central Guidance on Science and Technology Development Fund of Zhejiang Province(2024ZY01011)。
文摘Investigating structural and hydroxyl group effects in electrooxidation of alcohols to value-added products by solid-acid electrocatalysts is essential for upgrading biomass alcohols.Herein,we report efficient electrocatalytic oxidations of saturated alcohols(C_(1)-C_(6))to selectively form formate using Ni Co hydroxide(Ni Co-OH)derived Ni Co_(2)O_(4)solid-acid electrocatalysts with balanced Lewis acid(LASs)and Brønsted acid sites(BASs).Thermal treatment transforms BASs-rich(89.6%)Ni Co-OH into Ni Co_(2)O_(4)with nearly equal distribution of LASs(53.1%)and BASs(46.9%)which synergistically promote adsorption and activation of OH-and alcohol molecules for enhanced oxidation activity.In contrast,BASs-enriched Ni Co-OH facilitates formation of higher valence metal sites,beneficial for water oxidation.The combined experimental studies and theoretical calculation imply the oxidation ability of C1-C6alcohols increases as increased number of hydroxyl groups and decreased HOMO-LUMO gaps:methanol(C_(1))<ethylene glycol(C_(2))<glycerol(C3)<meso-erythritol(C4)<xylitol(C5)<sorbitol(C6),while the formate selectivity shows the opposite trend from 100 to 80%.This study unveils synergistic roles of LASs and BASs,as well as hydroxyl group effect in electro-upgrading of alcohols using solid-acid electrocatalysts.
文摘The arsenic removal efficiency of iron-modified activated carbons depends greatly on the number of available iron oxide surface sites, which are given by the surface area of the anchored particles. In this sense, aiming the generation of an adsorbent with superior arsenic adsorption capacity, we developed a protocol to anchor interconnected fibrils of iron oxyhydroxides, using Mn^(2+) as a morphology regulator. The protocol was based on a microwave-assisted hydrothermal method, using bituminous based activated carbon and both Fe^(2+) and Mn^(2+) ions in the hydrolysis solution. The elemental analysis of modified carbons revealed that Mn does not anchor to the carbon. However, when Mn is included in the hydrolysis solution, the iron content in the activated carbon increased up to 3.5 wt%,without considerable decreasing the adsorbent surface area. Under specific hydrothermal conditions, the Mn^(2+) promoted the formation of iron oxide nanoparticles shaped as interconnected fibrils. This material showed a superior arsenic adsorption capacity in comparison to similar iron modified activated carbons(5 mg As/g carbon, at 2 mg As/L),attributed to the increase in quantity and availability of active sites located on the novel interconnected fibrils of iron oxyhydroxides nanostructures.
基金supported by the National Key R&D Program of China,Nos.2017YFA0104302(to NG and XM)and 2017YFA0104304(to BW and ZZ)
文摘Mesenchymal stromal cell transplantation is an effective and promising approach for treating various systemic and diffuse diseases.However,the biological characteristics of transplanted mesenchymal stromal cells in humans remain unclear,including cell viability,distribution,migration,and fate.Conventional cell tracing methods cannot be used in the clinic.The use of superparamagnetic iron oxide nanoparticles as contrast agents allows for the observation of transplanted cells using magnetic resonance imaging.In 2016,the National Medical Products Administration of China approved a new superparamagnetic iron oxide nanoparticle,Ruicun,for use as a contrast agent in clinical trials.In the present study,an acute hemi-transection spinal cord injury model was established in beagle dogs.The injury was then treated by transplantation of Ruicun-labeled mesenchymal stromal cells.The results indicated that Ruicunlabeled mesenchymal stromal cells repaired damaged spinal cord fibers and partially restored neurological function in animals with acute spinal cord injury.T2*-weighted imaging revealed low signal areas on both sides of the injured spinal cord.The results of quantitative susceptibility mapping with ultrashort echo time sequences indicated that Ruicun-labeled mesenchymal stromal cells persisted stably within the injured spinal cord for over 4 weeks.These findings suggest that magnetic resonance imaging has the potential to effectively track the migration of Ruicun-labeled mesenchymal stromal cells and assess their ability to repair spinal cord injury.
基金Project supported by Japan Society for the Promotion of Science(JSPS)KAKENHI Grants(21560696,24560827)
文摘Europium oxyhydroxide crystals were synthesized by the flux method. The as-grown crystals were transparent and had a plate-like shape with natural flat surfaces. The powder XRD data were refined by assuming a monoclinic structure of the space group P21/m and lattice parameters of a=0.4346 nm, b=0.3744 nm, c=0.6107 nm, and β=108.62°. The magnetic susceptibility of the EuOOH crystals exhibited typical Van Vleck temperature-independent paramagnetism below 120 K. The calculated susceptibility, based on Van Vleck＇s theory, agreed with the experimental data to some extent, with the coupling constant λ=458±10 K. The experimental results were in close agreement with the results calculated using a modified formula with λ=505±2 K and a constant term C=4.6×10^-4 emu/（mol·Oe）.
文摘Rational design of low‐cost and efficient electrocatalysts for ethanol oxidation reaction(EOR)is imperative for electrocatalytic ethanol fuel cells.In this work,we developed a copper‐doped nickel oxyhydroxide(Cu‐doped NiOOH)catalyst via in situ electrochemical reconstruction of a NiCu alloy.The introduction of Cu dopants increases the specific surface area and more defect sites,as well as forms high‐valence Ni sites.The Cu‐doped NiOOH electrocatalyst exhibited an excellent EOR performance with a peak current density of 227 mA·cm^(–2)at 1.72 V versus reversible hydrogen electrode,high Faradic efficiencies for acetate production(>98%),and excellent electrochemical stability.Our work suggests an attractive route of designing non‐noble metal based electrocatalysts for ethanol oxidation.
基金Project supported by JSPS KAKENHI(21560696,24560827)
文摘Crystals of co-doped gadolinium oxyhydroxide （GdOOH）, Gd0.98Eu0.02-xTbxOOH and Gd1-y-zDyyBizOOH, were synthesized by a flux method. The color coordinates in the Commission Internationale de I＇Eelairage （CIE） chromaticity diagram of Gd0.98Eu0.02-xTbxOOH, obtained under 254 nm irradiation, shifted along a straight line with the changing values ofx to include the yellow region. The CIE coordinates of Dy^3＋ doped in GdOOH were located in the yellow region, while the emission intensity of Dy^3＋ under 286 nm irradiation increased by more than 40 times when co-doped with Bi^3＋.
基金National Natural Science Foundation of China(NSFC,No.11475008)。
文摘During the chemical weathering of the uranium mill tailings,released uranium could be immobilized by the newly formed secondary minerals such as oxyhydroxides.A deeper understanding of the interaction between uranium and common oxyhydroxides under environmental conditions is necessary.In this work,uranium sorption behaviors on Al-,Mn-and Fe-oxyhydroxide minerals(boehmite,manganite,goethite,and lepidocrocite)were investigated by batch experiments.Results showed that the uranium sorption on Al-oxyhydroxide behaved significantly differently from the other three minerals.The sorption edge of the Mn-and Fe-oxyhydroxides located around pH 5,while the sorption edge of boehmite shifted about 1.5 pH unit to near neutral.The sorption isotherms of uranium on manganite,goethite and lepidocrocite at pH 5.0 could be well fitted by the Langmuir model.Instead of surface complexation,sorption on boehmite happened mainly by uranium-bearing carbonates and hydroxides precipitation as illustrated by the characterization results.Both carbonate and phosphate strongly affected the uranium sorption behavior.The removal efficiency of uranium by boehmite exceeded 98%after three sorption-desorption cycles,indicating it may be a potential material for uranium removal and recovery.
基金Y.Hou expresses appreciation for the assistance of the National Natural Science Foundation of China(21922811,21878270,and 21961160742)the Zhejiang Provincial Natural Science Foundation of China(LR19B060002)+2 种基金the Fundamental Research Funds for the Central Universities(2020XZZX002-09)the Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang(2019R01006)the Startup Foundation for Hundred-Talent Program of Zhejiang University.K.Ostrikov acknowledges partial assistance from the Australian Research Council.
文摘Developing high-performing oxygen evolution reaction(OER)electrocatalysts under high-current operation conditions is critical for future commercial applications of alkaline water electrolysis for clean energy generation.Herein,we prepared a three-dimensional(3D)bimetallic oxyhydroxide hybrid grown on a Ni foam(NiFeOOH/NF)prepared by immersing Ni foam(NF)into Fe(NO_(3))_(3) solution.In this unique 3D structure,the NiFeOOH/NF hybrid was composed of crystalline Ni(OH)_(2) and amorphous FeOOH evenly grown on the NF surface.As a bimetallic oxyhydroxide electrocatalyst,the NiFeOOH/NF hybrid exhibited excellent catalytic activity,surpassing not only the other reported Ni–Fe based electrocatalysts,but also the commercial Ir/C catalyst.In situ electrochemical Raman spectroscopy demonstrated the active FeOOH and NiOOH phases involved in the OER process.Profiting from the synergy of Fe and Ni catalytic sites,the NiFeOOH/NF hybrid delivered an outstanding OER performance under challenging industrial conditions in a 10.0 mol·L^(-1) KOH electrolyte at 80℃,requiring potentials as small as 1.47 and 1.51 V to achieve the super-high catalytic current densities of 100 and 500mA∙cm^(-2),respectively.
基金the support from the National Key R&D Program of China(2020YFA0710000)the National Natural Science Foundation of China(22278307,22222808,21978200)the Haihe Laboratory of Sustainable Chemical Transformations。
文摘Metal oxyhydroxides(MOOH)generated from irreversible reconstructions of transition metal compounds are intrinsic active species for oxygen evolution reaction,whose activities are still constrained by sluggish deprotonation kinetics and inherent adsorption energy scaling relations.Herein,we construct a tunable proton acceptor(TPA)on oxyhydroxides by in-situ reconstruction of metal oxoacids such as NiC2O4to accelerate deprotonation and break adsorption energy scaling relations during OER.The modified C_(2)O_(4)^(2-)as a TPA can easily extract H of*OH(forming*HC2O4intermediate)and then promote deprotonation by the transmitted hydrogen bond with*OOH along conjugated(H...)O=C-O(-H)chain.As a result,Ni OOH-C2O4shows non-concerted proton-electron transfer and improved deprotonation rate,and delivers a good OER activity(270 mV@10 mA cm-2).The conjugate acidity coefficient(pKa)of the modified oxoacid group can be a descriptor for TPA selection.This TPA strategy can be universally applied to Co-,Fe-,and Ni-based oxyhydroxides to facilitate OER efficiency.
基金funding support from the 973 Program (2014CB440904)the Chinese NSF projects (41490635, 41173023, 41225012)
文摘Equilibrium Si isotope fractionation factors among orthosilicic acid(i.e.,H4 Si O4(aq)), quartz and the adsorption complexes of H4 Si O4(aq)on Fe(III)-oxyhydroxide surface were calculated using the full-electron wave-function quantum chemistry methods [i.e., B3LYP/6-311G(2df,p)]with a new cluster-model-based treatment. Solvation effects were carefully included in our calculations via water-droplet method combined with implicit solvent models(e.g., PCM).The results revealed that, if it is under equilibrium conditions,heavy Si isotopes would be significantly enriched in quartz in comparison to H4 Si O4(aq). However, most of the field observations suggested that quartz would have identical or even depleted d30 Si values compared to that of H4 Si O4(aq). To explain this discrepancy between the equilibrium calculation results and the field observations, the kinetic isotope effect(KIE) associated with the formation of amorphous silica,which usually is the precursor of crystalline quartz, was investigated using quantum chemistry methods. The KIE results showed that amorphous silica would be significantly enriched in light Si isotopes during its formation. Our equilibrium fractionation results, however, matched a special type of quartz(i.e., Herkimer ‘‘diamond'') very well, due to its nearly equilibrated precipitation condition. Opposite to the case of precipitated quartz, a large equilibrium Si isotope fractionation(i.e.,-3.0 %) was found between the absorbed bidentate Si surface complexes(i.e.,2C [ Fe2O2Si(OH)2) and H4 Si O4(aq). This calculated equilibrium Si isotope fractionation factor largely differed from a previous experimental result(ca.-1.08 %). We found that the formation of transient or temporary surface complexes [e.g.,1V [ Fe2OSi(OH)3] may have accounted for the smaller net fractionation observed.With the equilibrium and kinetic Si isotope fractionation factors provided here, the distributions and changes of Si isotope compositions in the Earth's surface systems can be better understood.
基金The National Key Basic Research Program of China under contract Nos 2013CB429700the National Special Fund for the 12th Five Year Plan of COMRA under contract Nos DY125-12-R-02 and DY125-12-R-05+3 种基金the National Natural Science Foundation of China under contract Nos 41325021,40830849,40976027 and 41476044the Shandong Province Natural Science Foundation of China for Distinguished Young Scholars under contract Nos JQ200913the Strategic Priority Research Program of the Chinese Academy of Sciences under contract No.XDA11030302the CAS/SAFEA International Partnership Program for Creative Research Teams
文摘Utilizing Si, Fe and Mn concentrations within the end-member PACMANUS hydrothermal fluid, Si-Fe-Mn-H2O Pourbaix diagrams were constructed at 300℃and 25℃. ThePourbaix diagrams show that the main Si, Fe and Mn oxides species precipitating from the hydrothermal fluid were SiO2, Fe（OH）3, Fe3（OH）8, Mn3O4, and Mn2O3at 25℃. During mixing of hydrothermal fluid with seawater, SiO2 precipitated earlier than Fe-Mn-oxyhydroxides because of the lower stability boundary. Then Fe（OH）2 precipitated first, followed by Fe3（OH）8 and Fe（OH）3, and last, small amounts of Mn3O4 and Mn2O3 precipitated. Fe（OH）3was readily de-posited in alkaline solution with little influence by Eh. There were many Si-Fe-Mn-concentric particles in the polished sections of the massive precipitates collected from PACMANUS. In the concentric nucleus and ellipsoid, Si oxides precipitated first before the hydrothermal fluid had mixed with seawater. In the concen-tric nucleus, after the precipitation of Si oxides, the increase of pH and Eh promoted the precipitation of Mn oxides around the Si oxides. In the large ellipsoid, the precipitation of Fe was divided into two periods. In the early period, increase of pH value of hydrothermal fluid produced by low-temperature convection and an input of a small volume of seawater promoted a small amount of Fe（OH）3 to precipitate in the Si-rich core. In the late period, after complete mixing with seawater and the resultant fluid was close to neutral or slightly alkaline in pH, Fe（OH）3was easily precipitated from the solution and distributed around the Si-rich core.
基金This study was supported by the National Natural Science Foundation of China(grant no.31770620).
文摘Polypyrrole(PPy)@cellulose fiber-based composites have been widely investigated as electrode materials for use in flexible supercapacitors.However,they cannot readily provide high specific capacitance and cyclic stability owing to their inherent drawbacks,such as high resistance,Weber impedance,and volume expansion or collapse during charging/discharging.In this study,iron oxyhydroxide(FeOOH)is incorporated in the abovementioned composite to decrease the equivalent series resistance,charge transfer resistance,and Weber impedance,thereby enhancing electron transfer and ion diffusion,which results in superior electrochemical performance.The PPy-wrapped FeOOH@cellulose fiber-based composite electrode with the molar ratio of FeSO_(4) to NaBH4 of 1∶1 exhibits a high specific capacitance of 513.8 F/g at a current density of 0.2 A/g,as well as an excellent capacitance retention of 89.4% after 1000 cycles.
基金The National Key Basic Research Program of China under contract No.2013CB429700the National Special Fund for the 12th Five Year Plan of COMRA under contract No.DY125-12-R-05+3 种基金the National Special Fund for the 12th Five Year Plan of COMRA under contract Nos DY125-12-R-02 and DY125-11-R-05the Strategic Priority Research Program of the Chinese Academy of Sciences under contract No.XDA11030302the National Natural Science Foundation of China under contract Nos 41325021,40830849 and 40976027Shandong Province Natural Science Foundation of China for Distinguished Young Scholars under contract No.JQ200913
文摘Si-Fe-Mn-oxyhydroxides dredged at the PACMANUS （Papua New Guinea-Australia-Canada-Manus） hydrothermal field, Eastern Manus Basin, have 87Sr/SSSr=0.708 079-0.708 581; eNd=5.149 833-6.534 826; 208pb/204pb=38.245-38.440; 207pb/204pb=lS.503-15.560; 206pb/204pb=lS.682-18.783. s7sr/sSSr isotope ratios are relatively homogeneous and close to the value of the surrounding seawater （0.709 16）. The content of Sr in the samples contributed by seawater was estimated to be 76.7%-83.1% of total amount. The mixing temperature of hydrothermal fluids and seawater were ranging from 53.2℃ to 72.2℃ and the hydrothermal activities were unstable when the samples precipitated. The eNd values of all the samples are positive, which differ from the values of ferromanganese nodules （crusts） with hydrogenic origin. Nd was mainly derived from substrate rocks leached by hydrothermal circulation and preserved the hydrothermal signature. Ph isotopic compositions of most samples show minor variability except Sample #9-2 that has relatively high values of Pb isotopes. The Pb may be derived from the Eastern Manus Basin rocks leached by the hydrothermal fluid. The slightly lower 28pb/204pb and 207pb/204pb values of the samples indicated that the hydrothermal circulation in PACMANUS was not entire and sufficient, or that hydrothermal circulation had transient changes in the past. Si-Fe-Mn-oxyhydroxides in the samples preserved the heterogeneities of local rocks.
