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
Conversion of CO_(2)back to hydrocarbons is the most direct way of closing the“carbon cycle”,and its significance is further enlarged if this process is driven by renewable energies such as electricity.However,preci...Conversion of CO_(2)back to hydrocarbons is the most direct way of closing the“carbon cycle”,and its significance is further enlarged if this process is driven by renewable energies such as electricity.However,precisely controlling the product selectivity towards hydrocarbons against the competitive hydrogen evolution remains challenging,especially for Cu-based catalysts.Herein,we report a novel defect engineering strategy,by which Cu-doping-induced oxygen vacancies on CeO_(2)nanorods were effectively created,with adjustable vacancy/Cu ratio.The resulting optimum catalyst shows up to 79%catalytic current density to hydrocarbons(excluding CO),with 49%faradaic efficiency to CH4.Experiments and density functional theory unveil that the ratio between oxygen vacancy and Cu affects significantly the formation of*CHO and activation of H2O,which leads to the following deep hydrogenation to hydrocarbons.These findings may spur new insights for designing and developing more controllable chemical process relevant to CO_(2)utilization.展开更多
Dissolved oxygen(DO)usually refers to the amount of oxygen dissolved in water.In the environment,medicine,and fermentation industries,the DO level needs to be accurate and capable of online monitoring to guide the pre...Dissolved oxygen(DO)usually refers to the amount of oxygen dissolved in water.In the environment,medicine,and fermentation industries,the DO level needs to be accurate and capable of online monitoring to guide the precise control of water quality,clinical treatment,and microbial metabolism.Compared with other analytical methods,the electrochemical strategy is superior in its fast response,low cost,high sensitivity,and portable device.However,an electrochemical DO sensor faces a trade-off between sensitivity and long-term stability,which strongly limits its practical applications.To solve this problem,various advanced nanomaterials have been proposed to promote detection performance owing to their excellent electrocatalysis,conductivity,and chemical stability.Therefore,in this review,we focus on the recent progress of advanced nanomaterial-based electrochemical DO sensors.Through the comparison of the working principles on the main analysis techniques toward DO,the advantages of the electrochemical method are discussed.Emphasis is placed on recently developed nanomaterials that exhibit special characteristics,including nanostructures and preparation routes,to benefit DO determination.Specifically,we also introduce some interesting research on the configuration design of the electrode and device,which is rarely introduced.Then,the different requirements of the electrochemical DO sensors in different application fields are included to provide brief guidance on the selection of appropriate nanomaterials.Finally,the main challenges are evaluated to propose future development prospects and detection strategies for nanomaterial-based electrochemical sensors.展开更多
Hypoxia off the Changjiang River Estuary has been the subject of much attention,yet systematic observations have been lacking,resulting in a lack of knowledge regarding its long-term change and drivers.By revisiting t...Hypoxia off the Changjiang River Estuary has been the subject of much attention,yet systematic observations have been lacking,resulting in a lack of knowledge regarding its long-term change and drivers.By revisiting the repeated surveys of dissolved oxygen(DO) and other relevant hydrographic parameters along the section from the Changjiang River Estuary to the Jeju-do in the summer from 1997 to 2014,rather different trends were revealed for the dual low-DO cores.The nearshore low-DO core,located close to the river mouth and relatively stable,shows that hypoxia has become more severe with the lowest DO descen ding at a rate of -0.07 mg/(L·a) and the thickness of low-DO zone rising at a rate of 0.43 m/a.The offshore core,centered around 40-m isobath but moving back and forth between 123.5°-125°E,shows large fluctuations in the minimum DO concentration,with the thickness of low-DO zone falling at a rate of -1.55 m/a.The probable factors affecting the minimum DO concentration in the two regions also vary.In the nearshore region,the decreasing minimum DO is driven by the increase in both stratification and primary productivity,with the enhanced extension of the Changjiang River Diluted Water(CDW) strengthening stratification.In the offshore region,the fluctuating trend of the minimum DO concentration indicates that both DO loss and DO supplement are distinct.The DO loss is primarily attributed to bottom apparent oxygen utilization caused by the organic matter decay and is also relevant to the advection of low-DO water from the nearshore region.The DO supplement is primarily due to weakened stratification.Our analysis also shows that the minimum DO concentration in the nearshore region was extremely low in 1998,2003,2007 and 2010,related to El Ni?o signal in these summers.展开更多
Oxygen facilitates the breakdown of the organic material to provide energy for life.The concentration of dissolved oxygen(DO) in the water must exceed a certain threshold to support the normal metabolism of marine org...Oxygen facilitates the breakdown of the organic material to provide energy for life.The concentration of dissolved oxygen(DO) in the water must exceed a certain threshold to support the normal metabolism of marine organisms.Located in the northern B eibu Gulf,Qinzhou B ay receives abundant freshwater and nutrients from several rivers which significantly influence the level of the dissolved oxygen.However,the spatial-temporal variations of DO as well as the associated driving mechanisms have been rarely studied through field observations.In this study,a three-dimension al coupled physical-biogeochemical model is used to investigate the spatial and seasonal variations of the DO and the associated driving mechanisms in Qinzhou B ay.The validation against observations indicates that the model can capture the seasonal and inter-annual variability of the DO concentration with the range of 5-10 mg/L.Sensitivity experiments show that the river discharges,winds and tides play crucial roles in the seasonal variability of the DO by changing the vertical mixing and stratification of the water column and the circulation pattern.In winter,the tide and wind forces have strong effects on the DO distribution by enhancing the vertical mixing,especially near the bay mouth.In summer,the river discharges play a dominant role in the DO distribution by inhibiting the vertical water exchange and delivering more nutrients to the Bay,which increases the DO depletion and results in lower DO on the bottom of the estuary salt wedge.These findings can contribute to the preservation and management of the coastal environment in the northern Beibu Gulf.展开更多
The structure of liquid water is primarily composed of three-dimensional networks of water clusters formed by hydrogen bonds,and dis-solved oxygen is one of the most important indicators for assessing water qual-ity.I...The structure of liquid water is primarily composed of three-dimensional networks of water clusters formed by hydrogen bonds,and dis-solved oxygen is one of the most important indicators for assessing water qual-ity.In this work,distilled water with different concentration of dissolved oxygen were prepared,and a clear negative correlation between the size of water clus-ters and dissolved oxygen concentration was observed.Besides,a phenomenon of rapid absorption and release of oxygen at the water interfaces was unveiled,suggesting that oxygen molecules predominantly exist at the interfaces of water clusters.Oxygen molecules can move rapidly through the interfaces among water clusters,allowing dissolved oxygen to quickly reach a saturation level at certain partial pressure of oxygen and temperature.Further exploration into the mechanism by molecular dynamics simulations of oxygen and water clusters found that oxygen molecules can only exist stably at the interfaces among water clusters.A semi-empirical formula relating the average number of water molecules in a cluster(n)to ^(17)O NMR half-peak width(W)was summarized:n=0.1 W+0.85.These findings provide a foundation for exploring the structure and properties of water.展开更多
The sluggish kinetics of the electrochemical oxygen reduction reaction(ORR)in intermediatetemperature solid oxide fuel cells(IT-SOFCs)greatly limits the overall cell performance.In this study,an efficient and durable ...The sluggish kinetics of the electrochemical oxygen reduction reaction(ORR)in intermediatetemperature solid oxide fuel cells(IT-SOFCs)greatly limits the overall cell performance.In this study,an efficient and durable cathode material for IT-SOFCs is designed based on density functional theory(DFT)calculations by co-doping with Nb and Ta the B-site of the SrFeO_(3-δ)perovskite oxide.The DFT calculations suggest that Nb/Ta co-doping can regulate the energy band of the parent SrFeO_(3-δ)and help electron transfer.In symmetrical cells,such cathode with a SrFe_(0.8)Nb_(0.1)Ta_(0.1)O_(3-δ)(SFNT)detailed formula achieves a low cathode polarization resistance of 0.147Ωcm^(2) at 650℃.Electron spin resonance(ESR)and X-ray photoelectron spectroscopy(XPS)analysis confirm that the co-doping of Nb/Ta in SrFeO_(3-δ)B-site increases the balanced concentration of oxygen vacancies,enhancing the electrochemical performance when compared to 20 mol%Nb single-doped perovskite oxide.The cathode button cell with NiSDC|SDC|SFNT configuration achieves an outstanding peak power density of 1.3 W cm^(-2)at 650℃.Moreover,the button cell shows durability for 110 h under 0.65 V at 600℃ using wet H_(2) as fuel.展开更多
Rational design and construction of oxygen reduction reaction(ORR)electrocatalysts with high activity,good stability,and low price are essential for the practical applications of renewable energy conversion devices,su...Rational design and construction of oxygen reduction reaction(ORR)electrocatalysts with high activity,good stability,and low price are essential for the practical applications of renewable energy conversion devices,such as metal-air batteries.Electronic modification through constructing metal/semiconductor Schottky heterointerface represents a powerful strategy to enhance the electrochemical performance.Herein,we demonstrate a concept of Schottky electrocatalyst composed of uniform Co nanoparticles in situ anchored on the carbon nanotubes aligned on the carbon nanosheets(denoted as Co@N-CNTs/NSs hereafter)toward ORR.Both experimental findings and theoretical simulation testify that the rectifying contact could impel the voluntary electron flow from Co to N-CNTs/NSs and create an internal electric field,thereby boosting the electron transfer rate and improving the intrinsic activity.As a consequence,the Co@N-CNTs/NSs deliver outstanding ORR activity,impressive long-term durability,excellent methanol tolerance,and good performance as the air-cathode in the Zn-air batteries.The design concept of Schottky contact may provide the innovational inspirations for the synthesis of advanced catalysts in sustainable energy conversion fields.展开更多
Dissolved oxygen(DO)and apparent oxygen utilization(AOU)are essential parameters for evaluating the impact of climate change on marine ecosystems.In this study,we utilized data on DO and AOU collected from the Amundse...Dissolved oxygen(DO)and apparent oxygen utilization(AOU)are essential parameters for evaluating the impact of climate change on marine ecosystems.In this study,we utilized data on DO and AOU collected from the Amundsen Sea(western Antarctic)and the Cosmonaut Sea(eastern Antarctic)during the 38th Chinese National Antarctic Research Expedition,along with chlorophyll a(Chl a)data,to analyze the impact of primary production and the spatial distribution and structural features of water masses in these regions.The findings show that the standard deviation range of parallel DO samples is between 0.1 and 3.9μmol·L^(-1),meeting the precision criteria of the survey method.AOU values lower than 0.0μmol·L^(-1) were commonly observed in the surface waters of both regions,with the highest incidence in the polynya of Amundsen Sea,indicating a strong influence of high primary production.The Cosmonaut Sea exhibited the highest AOU values(higher than 160.0μmol·L^(-1))in the 75-500 m layer,while AOU value in the Amundsen Sea did not exceed 160.0μmol·L^(-1),suggesting potential upwelling of Circumpolar Deep Water to 100 m in the Cosmonaut Sea with minimal changes in its properties,whereas significant changes were noted in the properties of upwelling modified Circumpolar Deep Water in the Amundsen Sea.AOU values lower than 125.0μmol·L^(-1)were detected in the near-bottom waters of the Cosmonaut Sea,indicating the presence of Antarctic Bottom Water.展开更多
Transition-metal oxyhydroxides are attractive catalysts for oxygen evolution reactions(OERs).Further studies for developing transition-metal oxyhydroxide catalysts and understanding their catalytic mechanisms will ben...Transition-metal oxyhydroxides are attractive catalysts for oxygen evolution reactions(OERs).Further studies for developing transition-metal oxyhydroxide catalysts and understanding their catalytic mechanisms will benefit their quick transition to the next catalysts.Herein,Mo-doped CoOOH was designed as a high-performance model electrocatalyst with durability for 20 h at 10 mAcm−2.Additionally,it had an overpotential of 260 mV(glassy carbon)or 215 mV(nickel foam),which was 78 mV lower than that of IrO_(2)(338 mV).In situ,Raman spectroscopy revealed the transformation process of CoOOH.Calculations using the density functional theory showed that during OER,doped Mo increased the spin-up density of states and shrank the spin-down bandgap of the 3d orbits in the reconstructed CoOOH under the electrochemical activation process,which simultaneously optimized the adsorption and electron conduction of oxygen-related intermediates on Co sites and lowered the OER overpotentials.Our research provides new insights into the methodical planning of the creation of transition-metal oxyhydroxide OER catalysts.展开更多
BACKGROUND Whether hyperbaric oxygen therapy(HBOT)can cause paradoxical herniation is still unclear.CASE SUMMARY A 65-year-old patient who was comatose due to brain trauma underwent decompressive craniotomy and gradua...BACKGROUND Whether hyperbaric oxygen therapy(HBOT)can cause paradoxical herniation is still unclear.CASE SUMMARY A 65-year-old patient who was comatose due to brain trauma underwent decompressive craniotomy and gradually regained consciousness after surgery.HBOT was administered 22 d after surgery due to speech impairment.Paradoxical herniation appeared on the second day after treatment,and the patient’s condition worsened after receiving mannitol treatment at the rehabilitation hospital.After timely skull repair,the paradoxical herniation was resolved,and the patient regained consciousness and had a good recovery as observed at the follow-up visit.CONCLUSION Paradoxical herniation is rare and may be caused by HBOT.However,the underlying mechanism is unknown,and the understanding of this phenomenon is insufficient.The use of mannitol may worsen this condition.Timely skull repair can treat paradoxical herniation and prevent serious complications.展开更多
Transition metal-nitrogen-carbon(M-N-C)as a promising substitute for the conventional noble metalbased catalyst still suffers from low activity and durability for oxygen reduction reaction(ORR)in proton exchange membr...Transition metal-nitrogen-carbon(M-N-C)as a promising substitute for the conventional noble metalbased catalyst still suffers from low activity and durability for oxygen reduction reaction(ORR)in proton exchange membrane fuel cells(PEMFCs).To tackle the issue,herein,a new type of sulfur-doped ironnitrogen-hard carbon(S-Fe-N-HC)nanosheets with high activity and durability in acid media were developed by using a newly synthesized precursor of amide-based polymer with Fe ions based on copolymerizing two monomers of 2,5-thiophene dicarboxylic acid(TDA)as S source and 1,8-diaminonaphthalene(DAN)as N source via an amination reaction.The as-synthesized S-Fe-N-HC features highly dispersed atomic Fe Nxmoieties embedded into rich thiophene-S doped hard carbon nanosheets filled with highly twisted graphite-like microcrystals,which is distinguished from the majority of M-N-C with soft or graphitic carbon structures.These unique characteristics endow S-Fe-N-HC with high ORR activity and outstanding durability in 0.5 M H_(2)SO_(4).Its initial half-wave potential is 0.80 V and the corresponding loss is only 21 m V after 30,000 cycles.Meanwhile,its practical PEMFC performance is a maximum power output of 628.0 mW cm^(-2)and a slight power density loss is 83.0 m W cm^(-2)after 200-cycle practical operation.Additionally,theoretical calculation shows that the activity of Fe Nxmoieties on ORR can be further enhanced by sulfur doping at meta-site near FeN_(4)C.These results evidently demonstrate that the dual effect of hard carbon substrate and S doping derived from the precursor platform of amid-polymers can effectively enhance the activity and durability of Fe-N-C catalysts,providing a new guidance for developing advanced M-N-C catalysts for ORR.展开更多
P2/O3-type Ni/Mn-based layered oxides are promising cathode materials for sodium-ion batteries(SIBs)owing to their high energy density.However,exploring effective ways to enhance the synergy between the P2 and 03 phas...P2/O3-type Ni/Mn-based layered oxides are promising cathode materials for sodium-ion batteries(SIBs)owing to their high energy density.However,exploring effective ways to enhance the synergy between the P2 and 03 phases remains a necessity.Herein,we design a P2/O3-type Na_(0.76)Ni_(0.31)Zn_(0.07)Mn_(0.50)Ti_(0.12)0_(2)(NNZMT)with high chemical/electrochemical stability by enhancing the coupling between the two phases.For the first time,a unique Na*extraction is observed from a Na-rich O3 phase by a Na-poor P2 phase and systematically investigated.This process is facilitated by Zn^(2+)/Ti^(4+)dual doping and calcination condition regulation,allowing a higher Na*content in the P2 phase with larger Na^(+)transport channels and enhancing Na transport kinetics.Because of reduced Na^(+)in the O3 phase,which increases the difficulty of H^(+)/Na^(+) exchange,the hydrostability of the O3 phase in NNZMT is considerably improved.Furthermore,Zn^(2+)/Ti^(4+)presence in NNZMT synergistically regulates oxygen redox chemistry,which effectively suppresses O_(2)/CO_(2) gas release and electrolyte decomposition,and completely inhibits phase transitions above 4.0 V.As a result,NNZMT achieves a high discharge capacity of 144.8 mA h g^(-1) with a median voltage of 3.42 V at 20 mA g^(-1) and exhibits excellent cycling performance with a capacity retention of 77.3% for 1000 cycles at 2000 mA g^(-1).This study provides an effective strategy and new insights into the design of high-performance layered-oxide cathode materials with enhanced structure/interface stability forSIBs.展开更多
The preparation of bifunctional catalysts for oxygen reduction(ORR)and oxygen evolution(OER)is crucial for Zn-air batteries.Here,we report a La doped CoFe_(2)O_(4) spinel catalyst supported on threedimensional graphen...The preparation of bifunctional catalysts for oxygen reduction(ORR)and oxygen evolution(OER)is crucial for Zn-air batteries.Here,we report a La doped CoFe_(2)O_(4) spinel catalyst supported on threedimensional graphene(3D-G),where La can facilitate electron transfer from Co to Fe,leading to increased electron cloud density in Fe and improved catalytic performance.The redshift of the G peak in the Raman spectra indicates the interaction between theπbond of 3D-G and d orbitals in La_(0.2)CoFe_(1.8)O_(4).La_(0.2)CoFe_(1.8)/3D-G exhibits superior ORR performance(E_(1/2)=0.86 V vs.RHE)and OER performance(E_(j=10)=1.55 V vs.RHE)to CoFe_(2)O_(4)/3D-G(E_(1/2)=0.831 V vs.RHE,E_(j=10)=1.603 V vs.RHE).Furthermore,it demonstrates excellent bifunctional oxygen catalytic performance while maintaining high power density and stability in liquid zinc-air batteries(ZABs)and flexible ZABs(F-ZABs).This work presents a viable strategy for utilizing rare earth element doped spinels to enhance oxygen catalyst and ZABs performance.展开更多
The interaction between metal and support is critical in oxygen catalysis as it governs the charge transfer between these two entities,influences the electronic structures of the supported metal,affects the adsorption...The interaction between metal and support is critical in oxygen catalysis as it governs the charge transfer between these two entities,influences the electronic structures of the supported metal,affects the adsorption energies of reaction intermediates,and ultimately impacts the catalytic performance.In this study,we discovered a unique charge transfer reversal phenomenon in a metal/carbon nanohybrid system.Specifically,electrons were transferred from the metal-based species to N-doped carbon,while the carbon support reciprocally donated electrons to the metal domain upon the introduction of nickel.This led to the exceptional electrocatalytic performances of the resulting Ni-Fe/Mo_(2)C@nitrogen-doped carbon catalyst,with a half-wave potential of 0.91 V towards oxygen reduction reaction(ORR)and a low overpotential of 290 m V at 10 mA cm^(-2)towards oxygen evolution reaction(OER)under alkaline conditions.Additionally,the Fe-Ni/Mo_(2)C@carbon heterojunction catalyst demonstrated high specific capacity(794 mA h g_(Zn)~(-1))and excellent cycling stability(200 h)in a Zn-air battery.Theoretical calculations revealed that Mo_(2)C effectively inhibited charge transfer from Fe to the support,while secondary doping of Ni induced a charge transfer reversal,resulting in electron accumulation in the Fe-Ni alloy region.This local electronic structure modulation significantly reduced energy barriers in the oxygen catalysis process,enhancing the catalytic efficiency of both ORR and OER.Consequently,our findings underscore the potential of manipulating charge transfer reversal between the metal and support as a promising strategy for developing highly-active and durable bi-functional oxygen electrodes.展开更多
Understanding the structural origin of the competition between oxygen 2p and transition-metal 3d orbitals in oxygen-redox(OR)layered oxides is eminently desirable for exploring reversible and high-energy-density Li/Na...Understanding the structural origin of the competition between oxygen 2p and transition-metal 3d orbitals in oxygen-redox(OR)layered oxides is eminently desirable for exploring reversible and high-energy-density Li/Na-ion cathodes.Here,we reveal the correlation between cationic ordering transition and OR degradation in ribbon-ordered P3-Na_(0.6)Li_(0.2)Mn_(0.8)O_(2) via in situ structural analysis.Comparing two different voltage windows,the OR capacity can be improved approximately twofold when suppressing the in-plane cationic ordering transition.We find that the intralayer cationic migration is promoted by electrochemical reduction from Mn^(4+)to Jahn–Teller Mn^(3+)and the concomitant NaO_(6) stacking transformation from triangular prisms to octahedra,resulting in the loss of ribbon ordering and electrochemical decay.First-principles calculations reveal that Mn^(4+)/Mn^(3+)charge ordering and alignment of the degenerate eg orbital induce lattice-level collective Jahn–Teller distortion,which favors intralayer Mn-ion migration and thereby accelerates OR degradation.These findings unravel the relationship between in-plane cationic ordering and OR reversibility and highlight the importance of superstructure protection for the rational design of reversible OR-active layered oxide cathodes.展开更多
The design of cost-effective electrocatalysts is an open challenging for oxygen evolution reaction(OER)due to the“stable-oractive”dilemma.Zirconium dioxide(ZrO_(2)),a versatile and low-cost material that can be stab...The design of cost-effective electrocatalysts is an open challenging for oxygen evolution reaction(OER)due to the“stable-oractive”dilemma.Zirconium dioxide(ZrO_(2)),a versatile and low-cost material that can be stable under OER operating conditions,exhibits inherently poor OER activity from experimental observations.Herein,we doped a series of metal elements to regulate the ZrO_(2)catalytic activity in OER via spin-polarized density functional theory calculations with van der Waals interactions.Microkinetic modeling as a function of the OER activity descriptor(G_(O*)-G_(HO*))displays that 16 metal dopants enable to enhance OER activities over a thermodynamically stable ZrO_(2)surface,among which Fe and Rh(in the form of single-atom dopant)reach the volcano peak(i.e.the optimal activity of OER under the potential of interest),indicating excellent OER performance.Free energy diagram calculations,density of states,and ab initio molecular dynamics simulations further showed that Fe and Rh are the effective dopants for ZrO_(2),leading to low OER overpotential,high conductivity,and good stability.Considering cost-effectiveness,single-atom Fe doped ZrO_(2)emerged as the most promising catalyst for OER.This finding offers a valuable perspective and reference for experimental researchers to design cost-effective catalysts for the industrial-scale OER production.展开更多
Controlling the local electronic structure of active ingredients to improve the adsorption desorption characteristics of oxygen-containing intermediates over the electrochemical liquid-solid interfaces is a critical c...Controlling the local electronic structure of active ingredients to improve the adsorption desorption characteristics of oxygen-containing intermediates over the electrochemical liquid-solid interfaces is a critical challenge in the field of oxygen reduction reaction(ORR)catalysis.Here,we offer a simple approach for modulating the electronic states of metal nanocrystals by bimetal co-doping into carbon-nitrogen substrate,allowing us to modulate the electronic structure of catalytic active centers.To test our strategy,we designed a typical bimetallic nanoparticle catalyst(Fe-Co NP/NC)to flexibly alter the reaction kinetics of ORR.Our results from synchrotron Xray absorption spectroscopy and X-ray photoelectron spectroscopy showed that the co-doping of iron and cobalt could optimize the intrinsic charge distribution of Fe-Co NP/NC catalyst,promoting the oxygen reduction kinetics and ultimately achieving remarkable ORR activity.Consequently,the carefully designed Fe-Co NP/NC exhibits an ultra-high kinetic current density at the operating voltage(71.94 mA/cm^(2)at 0.80 V),and the half-wave potential achieves 0.915 V,which is obviously better than that of the corresponding controls including Fe NP/NC,Co NP/NC.Our findings provide a unique perspective for optimizing the electronic structure of active centers to achieve higher ORR catalytic activity and faster kinetics.展开更多
Amultifunctional liposomal polydopamine nanoparticle(MPM@Lipo)was designed in this study,to combine chemotherapy,photothermal therapy(PTT)and oxygen enrichment to clear hyperproliferating inflammatory cells and improv...Amultifunctional liposomal polydopamine nanoparticle(MPM@Lipo)was designed in this study,to combine chemotherapy,photothermal therapy(PTT)and oxygen enrichment to clear hyperproliferating inflammatory cells and improve the hypoxic microenvironment for rheumatoid arthritis(RA)treatment.MPM@Lipo significantly scavenged intracellular reactive oxygen species and relieved joint hypoxia,thus contributing to the repolarization of M1 macrophages into M2 phenotype.Furthermore,MPM@Lipo could accumulate at inflammatory joints,inhibit the production of inflammatory factors,and protect cartilage in vivo,effectively alleviating RA progression in a rat adjuvant-induced arthritis model.Moreover,upon laser irradiation,MPM@Lipo can elevate the temperature to not only significantly obliterate excessively proliferating inflammatory cells but also accelerate the production of methotrexate and oxygen,resulting in excellent RA treatment effects.Overall,the use of synergistic chemotherapy/PTT/oxygen enrichment therapy to treat RA is a powerful potential strategy.展开更多
To replace precious metal oxygen reduction reaction(ORR)electrocatalysts,many transition metals and N-doped car-bon composites have been proposed in the last decade resulting in their rapid development as promising no...To replace precious metal oxygen reduction reaction(ORR)electrocatalysts,many transition metals and N-doped car-bon composites have been proposed in the last decade resulting in their rapid development as promising non-precious metal catalysts.We used Ketjenblack carbon as the precursor and mixed it with a polymeric ionic liquid(PIL)of[Hvim]NO_(3) and Fe(NO_(3))_(3),which was thermally calcined at 900℃ to produce a porous FeO_(x),N co-doped carbon material denoted FeO_(x)-N/C.Because the PIL of[Hvim]NO_(3) strongly combines with and disperses Fe^(3+)ions,and NO_(3)−is thermally pyrolyzed to form the porous structure,the FeO_(x)-N/C catalyst has a high electrocatalytic activity for the ORR in both 0.1 mol L^(−1) KOH and 0.5 mol L^(−1) H_(2)SO_(4) electrolytes.It was used as the catalyst to assemble a zinc-air battery,which had a peak power density of 185 mW·cm^(−2).Its superior electrocatalytic activity,wide pH range,and easy preparation make FeO_(x)-N/C a promising electrocatalyst for fuel cells and metal-air batteries.展开更多
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).
基金National Natural Science Foundation of China(21968020,22302222)Natural Science Foundation of Inner Mongolia(2022MS02011)+3 种基金China Postdoctoral Science Foundation under Grant Number(2024T170965,2023M743641)Science and Technology Projects of China Northern Rare Earth(BFXT-2022-D-0023)Science and Technology Department of Shanxi Province(202303021222409)Education Department of Inner Mongolia Autonomous Region(NJZZ23094,NJYT23039)。
文摘Conversion of CO_(2)back to hydrocarbons is the most direct way of closing the“carbon cycle”,and its significance is further enlarged if this process is driven by renewable energies such as electricity.However,precisely controlling the product selectivity towards hydrocarbons against the competitive hydrogen evolution remains challenging,especially for Cu-based catalysts.Herein,we report a novel defect engineering strategy,by which Cu-doping-induced oxygen vacancies on CeO_(2)nanorods were effectively created,with adjustable vacancy/Cu ratio.The resulting optimum catalyst shows up to 79%catalytic current density to hydrocarbons(excluding CO),with 49%faradaic efficiency to CH4.Experiments and density functional theory unveil that the ratio between oxygen vacancy and Cu affects significantly the formation of*CHO and activation of H2O,which leads to the following deep hydrogenation to hydrocarbons.These findings may spur new insights for designing and developing more controllable chemical process relevant to CO_(2)utilization.
基金supported by the National Key Research and Development Program of China(2021YFC2103300)the National Natural Science Foundation of China(22078148)the Natural Science Foundation of Jiangsu Province(BK20220002).
文摘Dissolved oxygen(DO)usually refers to the amount of oxygen dissolved in water.In the environment,medicine,and fermentation industries,the DO level needs to be accurate and capable of online monitoring to guide the precise control of water quality,clinical treatment,and microbial metabolism.Compared with other analytical methods,the electrochemical strategy is superior in its fast response,low cost,high sensitivity,and portable device.However,an electrochemical DO sensor faces a trade-off between sensitivity and long-term stability,which strongly limits its practical applications.To solve this problem,various advanced nanomaterials have been proposed to promote detection performance owing to their excellent electrocatalysis,conductivity,and chemical stability.Therefore,in this review,we focus on the recent progress of advanced nanomaterial-based electrochemical DO sensors.Through the comparison of the working principles on the main analysis techniques toward DO,the advantages of the electrochemical method are discussed.Emphasis is placed on recently developed nanomaterials that exhibit special characteristics,including nanostructures and preparation routes,to benefit DO determination.Specifically,we also introduce some interesting research on the configuration design of the electrode and device,which is rarely introduced.Then,the different requirements of the electrochemical DO sensors in different application fields are included to provide brief guidance on the selection of appropriate nanomaterials.Finally,the main challenges are evaluated to propose future development prospects and detection strategies for nanomaterial-based electrochemical sensors.
基金The National Key Research&Development Program of China under contract No.2023YFC3108003 in Project No.2023YFC3108000the National Natural Science Foundation of China under contract No.41876026+3 种基金the Scientific Research Fund of the Second Institute of Oceanography,Ministry of Natural Resources under contract No.YJJC2201the National Programme on Global Change and Air–Sea Interaction Phase Ⅱ under contract No.GASI-01-CJKthe Zhejiang Provincial Ten Thousand Talents Program under contract No.2020R52038the Project of State Key Laboratory of Satellite Ocean Environment Dynamics under contract No.SOEDZZ2105。
文摘Hypoxia off the Changjiang River Estuary has been the subject of much attention,yet systematic observations have been lacking,resulting in a lack of knowledge regarding its long-term change and drivers.By revisiting the repeated surveys of dissolved oxygen(DO) and other relevant hydrographic parameters along the section from the Changjiang River Estuary to the Jeju-do in the summer from 1997 to 2014,rather different trends were revealed for the dual low-DO cores.The nearshore low-DO core,located close to the river mouth and relatively stable,shows that hypoxia has become more severe with the lowest DO descen ding at a rate of -0.07 mg/(L·a) and the thickness of low-DO zone rising at a rate of 0.43 m/a.The offshore core,centered around 40-m isobath but moving back and forth between 123.5°-125°E,shows large fluctuations in the minimum DO concentration,with the thickness of low-DO zone falling at a rate of -1.55 m/a.The probable factors affecting the minimum DO concentration in the two regions also vary.In the nearshore region,the decreasing minimum DO is driven by the increase in both stratification and primary productivity,with the enhanced extension of the Changjiang River Diluted Water(CDW) strengthening stratification.In the offshore region,the fluctuating trend of the minimum DO concentration indicates that both DO loss and DO supplement are distinct.The DO loss is primarily attributed to bottom apparent oxygen utilization caused by the organic matter decay and is also relevant to the advection of low-DO water from the nearshore region.The DO supplement is primarily due to weakened stratification.Our analysis also shows that the minimum DO concentration in the nearshore region was extremely low in 1998,2003,2007 and 2010,related to El Ni?o signal in these summers.
基金The Major Projects of the National Natural Science Foundation of China under contract No.U20A20105the Guangdong Key Project under contract No.2019BT2H594+2 种基金the National Key Research and Development Program of China under contract No.2022YFC3105000the State Key Laboratory of Tropical Oceanography Independent Research Fund under contract No.LTOZZ2103the Guangxi Key Laboratory of Marine Environmental Change and Disaster in Beibu Gulf,Beibu Gulf University under contract No.2023KF01。
文摘Oxygen facilitates the breakdown of the organic material to provide energy for life.The concentration of dissolved oxygen(DO) in the water must exceed a certain threshold to support the normal metabolism of marine organisms.Located in the northern B eibu Gulf,Qinzhou B ay receives abundant freshwater and nutrients from several rivers which significantly influence the level of the dissolved oxygen.However,the spatial-temporal variations of DO as well as the associated driving mechanisms have been rarely studied through field observations.In this study,a three-dimension al coupled physical-biogeochemical model is used to investigate the spatial and seasonal variations of the DO and the associated driving mechanisms in Qinzhou B ay.The validation against observations indicates that the model can capture the seasonal and inter-annual variability of the DO concentration with the range of 5-10 mg/L.Sensitivity experiments show that the river discharges,winds and tides play crucial roles in the seasonal variability of the DO by changing the vertical mixing and stratification of the water column and the circulation pattern.In winter,the tide and wind forces have strong effects on the DO distribution by enhancing the vertical mixing,especially near the bay mouth.In summer,the river discharges play a dominant role in the DO distribution by inhibiting the vertical water exchange and delivering more nutrients to the Bay,which increases the DO depletion and results in lower DO on the bottom of the estuary salt wedge.These findings can contribute to the preservation and management of the coastal environment in the northern Beibu Gulf.
基金funding support from National Natural Science Foundation of China(Project No.61574091)Wuxi River and Lake Management and Water Resources Management Center(Project No.JSXXCG2022-004).
文摘The structure of liquid water is primarily composed of three-dimensional networks of water clusters formed by hydrogen bonds,and dis-solved oxygen is one of the most important indicators for assessing water qual-ity.In this work,distilled water with different concentration of dissolved oxygen were prepared,and a clear negative correlation between the size of water clus-ters and dissolved oxygen concentration was observed.Besides,a phenomenon of rapid absorption and release of oxygen at the water interfaces was unveiled,suggesting that oxygen molecules predominantly exist at the interfaces of water clusters.Oxygen molecules can move rapidly through the interfaces among water clusters,allowing dissolved oxygen to quickly reach a saturation level at certain partial pressure of oxygen and temperature.Further exploration into the mechanism by molecular dynamics simulations of oxygen and water clusters found that oxygen molecules can only exist stably at the interfaces among water clusters.A semi-empirical formula relating the average number of water molecules in a cluster(n)to ^(17)O NMR half-peak width(W)was summarized:n=0.1 W+0.85.These findings provide a foundation for exploring the structure and properties of water.
基金supported by the National Natural Science Foundation of China (51702039)。
文摘The sluggish kinetics of the electrochemical oxygen reduction reaction(ORR)in intermediatetemperature solid oxide fuel cells(IT-SOFCs)greatly limits the overall cell performance.In this study,an efficient and durable cathode material for IT-SOFCs is designed based on density functional theory(DFT)calculations by co-doping with Nb and Ta the B-site of the SrFeO_(3-δ)perovskite oxide.The DFT calculations suggest that Nb/Ta co-doping can regulate the energy band of the parent SrFeO_(3-δ)and help electron transfer.In symmetrical cells,such cathode with a SrFe_(0.8)Nb_(0.1)Ta_(0.1)O_(3-δ)(SFNT)detailed formula achieves a low cathode polarization resistance of 0.147Ωcm^(2) at 650℃.Electron spin resonance(ESR)and X-ray photoelectron spectroscopy(XPS)analysis confirm that the co-doping of Nb/Ta in SrFeO_(3-δ)B-site increases the balanced concentration of oxygen vacancies,enhancing the electrochemical performance when compared to 20 mol%Nb single-doped perovskite oxide.The cathode button cell with NiSDC|SDC|SFNT configuration achieves an outstanding peak power density of 1.3 W cm^(-2)at 650℃.Moreover,the button cell shows durability for 110 h under 0.65 V at 600℃ using wet H_(2) as fuel.
基金This study was financially supported by the National Natural Science Foundation of China(Grant/Award Number:22232004,22272179,21972068,and 22072067).
文摘Rational design and construction of oxygen reduction reaction(ORR)electrocatalysts with high activity,good stability,and low price are essential for the practical applications of renewable energy conversion devices,such as metal-air batteries.Electronic modification through constructing metal/semiconductor Schottky heterointerface represents a powerful strategy to enhance the electrochemical performance.Herein,we demonstrate a concept of Schottky electrocatalyst composed of uniform Co nanoparticles in situ anchored on the carbon nanotubes aligned on the carbon nanosheets(denoted as Co@N-CNTs/NSs hereafter)toward ORR.Both experimental findings and theoretical simulation testify that the rectifying contact could impel the voluntary electron flow from Co to N-CNTs/NSs and create an internal electric field,thereby boosting the electron transfer rate and improving the intrinsic activity.As a consequence,the Co@N-CNTs/NSs deliver outstanding ORR activity,impressive long-term durability,excellent methanol tolerance,and good performance as the air-cathode in the Zn-air batteries.The design concept of Schottky contact may provide the innovational inspirations for the synthesis of advanced catalysts in sustainable energy conversion fields.
基金supported by the Scientific Research Fund of the Second Institute of Oceanography,MNR(Grant nos.JG2211 and JG2212)the National Polar Special Program“Impact and Response of Antarctic Seas to Climate Change”(Grant nos.IRASCC 01-01-02A and IRASCC 02-02)+1 种基金the National Key Research and Development Program of China(Grant no.2022YFE0136500)the National Natural Science Foundation of China(Grant no.41976228)。
文摘Dissolved oxygen(DO)and apparent oxygen utilization(AOU)are essential parameters for evaluating the impact of climate change on marine ecosystems.In this study,we utilized data on DO and AOU collected from the Amundsen Sea(western Antarctic)and the Cosmonaut Sea(eastern Antarctic)during the 38th Chinese National Antarctic Research Expedition,along with chlorophyll a(Chl a)data,to analyze the impact of primary production and the spatial distribution and structural features of water masses in these regions.The findings show that the standard deviation range of parallel DO samples is between 0.1 and 3.9μmol·L^(-1),meeting the precision criteria of the survey method.AOU values lower than 0.0μmol·L^(-1) were commonly observed in the surface waters of both regions,with the highest incidence in the polynya of Amundsen Sea,indicating a strong influence of high primary production.The Cosmonaut Sea exhibited the highest AOU values(higher than 160.0μmol·L^(-1))in the 75-500 m layer,while AOU value in the Amundsen Sea did not exceed 160.0μmol·L^(-1),suggesting potential upwelling of Circumpolar Deep Water to 100 m in the Cosmonaut Sea with minimal changes in its properties,whereas significant changes were noted in the properties of upwelling modified Circumpolar Deep Water in the Amundsen Sea.AOU values lower than 125.0μmol·L^(-1)were detected in the near-bottom waters of the Cosmonaut Sea,indicating the presence of Antarctic Bottom Water.
基金The National Natural Science Foundation of China(Grant Nos.52072114 and 51922008)the 111 Project(Grant No.D17007),the Henan Center for Outstanding Overseas Scientists(Grant No.GZS2018003)+2 种基金Xinxiang Major Science and Technology Projects(Grant No.21ZD001)Guangdong Innovative and Entrepreneurial Research Team Program(2016ZT06N500)Guangdong Provincial Key Laboratory of Energy Materials for Electric Power(2018B030322001)all provided financial support for this work.
文摘Transition-metal oxyhydroxides are attractive catalysts for oxygen evolution reactions(OERs).Further studies for developing transition-metal oxyhydroxide catalysts and understanding their catalytic mechanisms will benefit their quick transition to the next catalysts.Herein,Mo-doped CoOOH was designed as a high-performance model electrocatalyst with durability for 20 h at 10 mAcm−2.Additionally,it had an overpotential of 260 mV(glassy carbon)or 215 mV(nickel foam),which was 78 mV lower than that of IrO_(2)(338 mV).In situ,Raman spectroscopy revealed the transformation process of CoOOH.Calculations using the density functional theory showed that during OER,doped Mo increased the spin-up density of states and shrank the spin-down bandgap of the 3d orbits in the reconstructed CoOOH under the electrochemical activation process,which simultaneously optimized the adsorption and electron conduction of oxygen-related intermediates on Co sites and lowered the OER overpotentials.Our research provides new insights into the methodical planning of the creation of transition-metal oxyhydroxide OER catalysts.
文摘BACKGROUND Whether hyperbaric oxygen therapy(HBOT)can cause paradoxical herniation is still unclear.CASE SUMMARY A 65-year-old patient who was comatose due to brain trauma underwent decompressive craniotomy and gradually regained consciousness after surgery.HBOT was administered 22 d after surgery due to speech impairment.Paradoxical herniation appeared on the second day after treatment,and the patient’s condition worsened after receiving mannitol treatment at the rehabilitation hospital.After timely skull repair,the paradoxical herniation was resolved,and the patient regained consciousness and had a good recovery as observed at the follow-up visit.CONCLUSION Paradoxical herniation is rare and may be caused by HBOT.However,the underlying mechanism is unknown,and the understanding of this phenomenon is insufficient.The use of mannitol may worsen this condition.Timely skull repair can treat paradoxical herniation and prevent serious complications.
基金finically supported by the National Natural Science Foundation of China(22075055)the Guangxi Science and Technology Project(AB16380030)。
文摘Transition metal-nitrogen-carbon(M-N-C)as a promising substitute for the conventional noble metalbased catalyst still suffers from low activity and durability for oxygen reduction reaction(ORR)in proton exchange membrane fuel cells(PEMFCs).To tackle the issue,herein,a new type of sulfur-doped ironnitrogen-hard carbon(S-Fe-N-HC)nanosheets with high activity and durability in acid media were developed by using a newly synthesized precursor of amide-based polymer with Fe ions based on copolymerizing two monomers of 2,5-thiophene dicarboxylic acid(TDA)as S source and 1,8-diaminonaphthalene(DAN)as N source via an amination reaction.The as-synthesized S-Fe-N-HC features highly dispersed atomic Fe Nxmoieties embedded into rich thiophene-S doped hard carbon nanosheets filled with highly twisted graphite-like microcrystals,which is distinguished from the majority of M-N-C with soft or graphitic carbon structures.These unique characteristics endow S-Fe-N-HC with high ORR activity and outstanding durability in 0.5 M H_(2)SO_(4).Its initial half-wave potential is 0.80 V and the corresponding loss is only 21 m V after 30,000 cycles.Meanwhile,its practical PEMFC performance is a maximum power output of 628.0 mW cm^(-2)and a slight power density loss is 83.0 m W cm^(-2)after 200-cycle practical operation.Additionally,theoretical calculation shows that the activity of Fe Nxmoieties on ORR can be further enhanced by sulfur doping at meta-site near FeN_(4)C.These results evidently demonstrate that the dual effect of hard carbon substrate and S doping derived from the precursor platform of amid-polymers can effectively enhance the activity and durability of Fe-N-C catalysts,providing a new guidance for developing advanced M-N-C catalysts for ORR.
基金supported by the National Natural Science Foundation of China (22169002)the Chongzuo Key Research and Development Program of China (20220603)the Counterpart Aid Project for Discipline Construction from Guangxi University(2023M02)
文摘P2/O3-type Ni/Mn-based layered oxides are promising cathode materials for sodium-ion batteries(SIBs)owing to their high energy density.However,exploring effective ways to enhance the synergy between the P2 and 03 phases remains a necessity.Herein,we design a P2/O3-type Na_(0.76)Ni_(0.31)Zn_(0.07)Mn_(0.50)Ti_(0.12)0_(2)(NNZMT)with high chemical/electrochemical stability by enhancing the coupling between the two phases.For the first time,a unique Na*extraction is observed from a Na-rich O3 phase by a Na-poor P2 phase and systematically investigated.This process is facilitated by Zn^(2+)/Ti^(4+)dual doping and calcination condition regulation,allowing a higher Na*content in the P2 phase with larger Na^(+)transport channels and enhancing Na transport kinetics.Because of reduced Na^(+)in the O3 phase,which increases the difficulty of H^(+)/Na^(+) exchange,the hydrostability of the O3 phase in NNZMT is considerably improved.Furthermore,Zn^(2+)/Ti^(4+)presence in NNZMT synergistically regulates oxygen redox chemistry,which effectively suppresses O_(2)/CO_(2) gas release and electrolyte decomposition,and completely inhibits phase transitions above 4.0 V.As a result,NNZMT achieves a high discharge capacity of 144.8 mA h g^(-1) with a median voltage of 3.42 V at 20 mA g^(-1) and exhibits excellent cycling performance with a capacity retention of 77.3% for 1000 cycles at 2000 mA g^(-1).This study provides an effective strategy and new insights into the design of high-performance layered-oxide cathode materials with enhanced structure/interface stability forSIBs.
基金financially supported by the National Natural Science Foundation of China(22172093 and 21776167)the Natural Science Foundation of Shandong Province,China(ZR2023MB061).
文摘The preparation of bifunctional catalysts for oxygen reduction(ORR)and oxygen evolution(OER)is crucial for Zn-air batteries.Here,we report a La doped CoFe_(2)O_(4) spinel catalyst supported on threedimensional graphene(3D-G),where La can facilitate electron transfer from Co to Fe,leading to increased electron cloud density in Fe and improved catalytic performance.The redshift of the G peak in the Raman spectra indicates the interaction between theπbond of 3D-G and d orbitals in La_(0.2)CoFe_(1.8)O_(4).La_(0.2)CoFe_(1.8)/3D-G exhibits superior ORR performance(E_(1/2)=0.86 V vs.RHE)and OER performance(E_(j=10)=1.55 V vs.RHE)to CoFe_(2)O_(4)/3D-G(E_(1/2)=0.831 V vs.RHE,E_(j=10)=1.603 V vs.RHE).Furthermore,it demonstrates excellent bifunctional oxygen catalytic performance while maintaining high power density and stability in liquid zinc-air batteries(ZABs)and flexible ZABs(F-ZABs).This work presents a viable strategy for utilizing rare earth element doped spinels to enhance oxygen catalyst and ZABs performance.
基金financially supported by the Outstanding Youth Scientific Research Project for Colleges and Universities of Anhui Province of China (2022AH020054)the Anhui Provincial Natural Science Foundation (2208085Y06)+2 种基金the National Natural Science Foundation of China (Nos.21975001 and U2002213)the Support Program of Excellent Young Talents in Anhui Provincial Colleges and Universities (gxyq ZD2022034)the Double Tops Joint Fund of the Yunnan Science and Technology Bureau and Yunnan University (2019FY003025)。
文摘The interaction between metal and support is critical in oxygen catalysis as it governs the charge transfer between these two entities,influences the electronic structures of the supported metal,affects the adsorption energies of reaction intermediates,and ultimately impacts the catalytic performance.In this study,we discovered a unique charge transfer reversal phenomenon in a metal/carbon nanohybrid system.Specifically,electrons were transferred from the metal-based species to N-doped carbon,while the carbon support reciprocally donated electrons to the metal domain upon the introduction of nickel.This led to the exceptional electrocatalytic performances of the resulting Ni-Fe/Mo_(2)C@nitrogen-doped carbon catalyst,with a half-wave potential of 0.91 V towards oxygen reduction reaction(ORR)and a low overpotential of 290 m V at 10 mA cm^(-2)towards oxygen evolution reaction(OER)under alkaline conditions.Additionally,the Fe-Ni/Mo_(2)C@carbon heterojunction catalyst demonstrated high specific capacity(794 mA h g_(Zn)~(-1))and excellent cycling stability(200 h)in a Zn-air battery.Theoretical calculations revealed that Mo_(2)C effectively inhibited charge transfer from Fe to the support,while secondary doping of Ni induced a charge transfer reversal,resulting in electron accumulation in the Fe-Ni alloy region.This local electronic structure modulation significantly reduced energy barriers in the oxygen catalysis process,enhancing the catalytic efficiency of both ORR and OER.Consequently,our findings underscore the potential of manipulating charge transfer reversal between the metal and support as a promising strategy for developing highly-active and durable bi-functional oxygen electrodes.
基金funding supports from the National Key R&D Program of China(Grant Nos.2022YFB2404400 and 2019YFA0308500)Beijing Natural Science Foundation(Z190010)National Natural Science Foundation of China(Grant Nos.51991344,52025025,52072400,and 52002394)。
文摘Understanding the structural origin of the competition between oxygen 2p and transition-metal 3d orbitals in oxygen-redox(OR)layered oxides is eminently desirable for exploring reversible and high-energy-density Li/Na-ion cathodes.Here,we reveal the correlation between cationic ordering transition and OR degradation in ribbon-ordered P3-Na_(0.6)Li_(0.2)Mn_(0.8)O_(2) via in situ structural analysis.Comparing two different voltage windows,the OR capacity can be improved approximately twofold when suppressing the in-plane cationic ordering transition.We find that the intralayer cationic migration is promoted by electrochemical reduction from Mn^(4+)to Jahn–Teller Mn^(3+)and the concomitant NaO_(6) stacking transformation from triangular prisms to octahedra,resulting in the loss of ribbon ordering and electrochemical decay.First-principles calculations reveal that Mn^(4+)/Mn^(3+)charge ordering and alignment of the degenerate eg orbital induce lattice-level collective Jahn–Teller distortion,which favors intralayer Mn-ion migration and thereby accelerates OR degradation.These findings unravel the relationship between in-plane cationic ordering and OR reversibility and highlight the importance of superstructure protection for the rational design of reversible OR-active layered oxide cathodes.
基金the funding support from the Research Grants Council of the Hong Kong Special Administrative Region,China[Project No.CityU11308923]the Basic Research Project from Shenzhen Science and Technology Innovation Committee in Shenzhen,China(No.JCYJ20210324134012034)+5 种基金the Applied Research Grant of City University of Hong Kong(project No.of 9667247)Chow Sang Sang Group Research Fund of City University of Hong Kong(project No.9229123)the funding supported by the Seed Collaborative Research Fund Scheme of State Key Laboratory of Marine Pollution which receives regular research funding from Innovation and Technology Commission(ITC)of the Hong Kong SAR Governmentthe JSPS KAKENHI(No.JP23K13703 and JP23KF0102)the high-level science and technology talents project of Lvliang City(No.2022RC07)foundation of Shanxi supercomputing center of China(No.11sxsc202301).
文摘The design of cost-effective electrocatalysts is an open challenging for oxygen evolution reaction(OER)due to the“stable-oractive”dilemma.Zirconium dioxide(ZrO_(2)),a versatile and low-cost material that can be stable under OER operating conditions,exhibits inherently poor OER activity from experimental observations.Herein,we doped a series of metal elements to regulate the ZrO_(2)catalytic activity in OER via spin-polarized density functional theory calculations with van der Waals interactions.Microkinetic modeling as a function of the OER activity descriptor(G_(O*)-G_(HO*))displays that 16 metal dopants enable to enhance OER activities over a thermodynamically stable ZrO_(2)surface,among which Fe and Rh(in the form of single-atom dopant)reach the volcano peak(i.e.the optimal activity of OER under the potential of interest),indicating excellent OER performance.Free energy diagram calculations,density of states,and ab initio molecular dynamics simulations further showed that Fe and Rh are the effective dopants for ZrO_(2),leading to low OER overpotential,high conductivity,and good stability.Considering cost-effectiveness,single-atom Fe doped ZrO_(2)emerged as the most promising catalyst for OER.This finding offers a valuable perspective and reference for experimental researchers to design cost-effective catalysts for the industrial-scale OER production.
基金supported by the Natural Science Foundation of Anhui Province(No.2208085J01 and No.2208085QA28).
文摘Controlling the local electronic structure of active ingredients to improve the adsorption desorption characteristics of oxygen-containing intermediates over the electrochemical liquid-solid interfaces is a critical challenge in the field of oxygen reduction reaction(ORR)catalysis.Here,we offer a simple approach for modulating the electronic states of metal nanocrystals by bimetal co-doping into carbon-nitrogen substrate,allowing us to modulate the electronic structure of catalytic active centers.To test our strategy,we designed a typical bimetallic nanoparticle catalyst(Fe-Co NP/NC)to flexibly alter the reaction kinetics of ORR.Our results from synchrotron Xray absorption spectroscopy and X-ray photoelectron spectroscopy showed that the co-doping of iron and cobalt could optimize the intrinsic charge distribution of Fe-Co NP/NC catalyst,promoting the oxygen reduction kinetics and ultimately achieving remarkable ORR activity.Consequently,the carefully designed Fe-Co NP/NC exhibits an ultra-high kinetic current density at the operating voltage(71.94 mA/cm^(2)at 0.80 V),and the half-wave potential achieves 0.915 V,which is obviously better than that of the corresponding controls including Fe NP/NC,Co NP/NC.Our findings provide a unique perspective for optimizing the electronic structure of active centers to achieve higher ORR catalytic activity and faster kinetics.
文摘Amultifunctional liposomal polydopamine nanoparticle(MPM@Lipo)was designed in this study,to combine chemotherapy,photothermal therapy(PTT)and oxygen enrichment to clear hyperproliferating inflammatory cells and improve the hypoxic microenvironment for rheumatoid arthritis(RA)treatment.MPM@Lipo significantly scavenged intracellular reactive oxygen species and relieved joint hypoxia,thus contributing to the repolarization of M1 macrophages into M2 phenotype.Furthermore,MPM@Lipo could accumulate at inflammatory joints,inhibit the production of inflammatory factors,and protect cartilage in vivo,effectively alleviating RA progression in a rat adjuvant-induced arthritis model.Moreover,upon laser irradiation,MPM@Lipo can elevate the temperature to not only significantly obliterate excessively proliferating inflammatory cells but also accelerate the production of methotrexate and oxygen,resulting in excellent RA treatment effects.Overall,the use of synergistic chemotherapy/PTT/oxygen enrichment therapy to treat RA is a powerful potential strategy.
文摘To replace precious metal oxygen reduction reaction(ORR)electrocatalysts,many transition metals and N-doped car-bon composites have been proposed in the last decade resulting in their rapid development as promising non-precious metal catalysts.We used Ketjenblack carbon as the precursor and mixed it with a polymeric ionic liquid(PIL)of[Hvim]NO_(3) and Fe(NO_(3))_(3),which was thermally calcined at 900℃ to produce a porous FeO_(x),N co-doped carbon material denoted FeO_(x)-N/C.Because the PIL of[Hvim]NO_(3) strongly combines with and disperses Fe^(3+)ions,and NO_(3)−is thermally pyrolyzed to form the porous structure,the FeO_(x)-N/C catalyst has a high electrocatalytic activity for the ORR in both 0.1 mol L^(−1) KOH and 0.5 mol L^(−1) H_(2)SO_(4) electrolytes.It was used as the catalyst to assemble a zinc-air battery,which had a peak power density of 185 mW·cm^(−2).Its superior electrocatalytic activity,wide pH range,and easy preparation make FeO_(x)-N/C a promising electrocatalyst for fuel cells and metal-air batteries.
