Lithium-oxygen(Li-O2)batteries are perceived as a promising breakthrough in sustainable electrochemical energy storage,utilizing ambient air as an energy source,eliminating the need for costly cathode materials,and of...Lithium-oxygen(Li-O2)batteries are perceived as a promising breakthrough in sustainable electrochemical energy storage,utilizing ambient air as an energy source,eliminating the need for costly cathode materials,and offering the highest theoretical energy density(~3.5 k Wh kg^(-1))among discussed candidates.Contributing to the poor cycle life of currently reported Li-O_(2)cells is singlet oxygen(1O_(2))formation,inducing parasitic reactions,degrading key components,and severely deteriorating cell performance.Here,we harness the chirality-induced spin selectivity effect of chiral cobalt oxide nanosheets(Co_(3)O_(4)NSs)as cathode materials to suppress 1O_(2)in Li-O_(2)batteries for the first time.Operando photoluminescence spectroscopy reveals a 3.7-fold and 3.23-fold reduction in 1O_(2)during discharge and charge,respectively,compared to conventional carbon paperbased cells,consistent with differential electrochemical mass spectrometry results,which indicate a near-theoretical charge-to-O_(2)ratio(2.04 e-/O_(2)).Density functional theory calculations demonstrate that chirality induces a peak shift near the Fermi level,enhancing Co 3d-O 2p hybridization,stabilizing reaction intermediates,and lowering activation barriers for Li_(2)O_(2)formation and decomposition.These findings establish a new strategy for improving the stability and energy efficiency of sustainable Li-O_(2)batteries,abridging the current gap to commercialization.展开更多
Developing efficient and durable electrocatalysts for acidic oxygen evolution reaction(OER)is pivotal for advancing proton exchange membrane water electrolysis(PEMWEs),yet balancing activity and stability remains a fo...Developing efficient and durable electrocatalysts for acidic oxygen evolution reaction(OER)is pivotal for advancing proton exchange membrane water electrolysis(PEMWEs),yet balancing activity and stability remains a formidable challenge.Herein,we propose a dual-engineering strategy to stabilize Ru-based catalysts by synergizing the oxygen vacancy site-synergized mechanism-lattice oxygen mechanism(OVSM-LOM)with Ru-N bond stabilization.The engineered RuO_(2)@NCC catalyst exhibits exceptional OER performance in 0.5 M H2SO4,achieving an ultralow overpotential of 215 mV at 10 mA cm^(-2) and prolonged stability for over 327 h.The catalyst delivers 300 h of continuous operation at 1 A cm^(-2),with a negligible degradation rate of only 0.067 mV h-1,further demonstrating its potential for practical application.Oxygen vacancies unlock the OVSM-LOM pathway,bypassing the sluggish adsorbate evolution mechanism(AEM)and accelerating reaction kinetics,while the Ru-N bonds suppress Ru dissolution by anchoring low-valent Ru centers.Quasi-in situ X-ray photoelectron spectroscopy(XPS),X-ray absorption spectroscopy(XAS),and isotopic labeling experiments confirm the lattice oxygen participation with *O formation as the rate-determining step.The Ru-N bonds reinforce the structural integrity by stabilizing low-valent Ru centers and inhibiting overoxidation.Theoretical calculations further verify that the synergistic interaction between OVs and Ru-O(N)active sites optimizes the Ru d-band center and stabilizes intermediates,while Ru-N coordination enhances structural integrity.This study establishes a novel paradigm for designing robust acidic OER catalysts through defect and coordination engineering,bridging the gap between activity and stability for sustainable energy technologies.展开更多
Magnetic field-driven spin polarization modulation has emerged as an effective way to boost the electrocatalytic oxygen evolution reaction(OER).However,the correlation among catalyst structure,magnetic property,and ma...Magnetic field-driven spin polarization modulation has emerged as an effective way to boost the electrocatalytic oxygen evolution reaction(OER).However,the correlation among catalyst structure,magnetic property,and magnetic field enhanced-electrochemical activity remains to be fully elucidated.Herein,single-domain CoFe_(2)O_(4) catalysts with tunable oxygen vacancies(CFO-V_(O)) were synthesized to probe how V_(O) mediates magnetism and OER activity under magnetic field.The introduction of V_(O) can simultaneously modulate saturation magnetization(M_(s)) and coercivity(H_(c)),where the increased M_(s) dominates the magnetic field-enhanced OER activity.Under a 14,000 G magnetic field,the optimized CFO-V_(O) exhibits up to 16.1 % reduction in overpotential and 365 % enhancement in magnetocurrent(MC).Electrochemical analyses and post-OER characterization reveal that the magnetic field synergistically improves OER kinetics through lattice distortion induction,magnetohydrodynamic effect,and spin charge transfer effect.Importantly,the magnetic field promotes additional Co^(3+) generation to compensate for charge imbalance caused by V_(O) filling,maintaining dynamic equilibrium of V_(O) and effective reactant adsorption-conversion processes.This work unveils the synergistic mechanism of V_(O) and magnetic parameters for enhancing OER performance under the magnetic field,providing new insights into the design of high-efficiency spinregulated OER catalysts.展开更多
Covalent organic framework ionomers enable synergistic efficient transport of protons and oxygen in medium-temperature proton exchange membrane fuel cells Proton exchange membrane fuel cells(PEMFCs),as clean and effic...Covalent organic framework ionomers enable synergistic efficient transport of protons and oxygen in medium-temperature proton exchange membrane fuel cells Proton exchange membrane fuel cells(PEMFCs),as clean and efficient energy technologies,are constrained in their performance enhancement by the sluggish oxygen reduction reaction(ORR)kinetics at the cathode,anode CO poisoning(e.g.,from methanol crossover)and intricate water management dilemmas[1].展开更多
A composite electrocatalyst,CoMoNiO-S/NF-110(NF is nickel foam),was synthesized through electrodeposition,followed by pyrolysis and then the vulcanization process.CoMoNiO-S/NF-110 exhibited a structure where Ni3S2 and...A composite electrocatalyst,CoMoNiO-S/NF-110(NF is nickel foam),was synthesized through electrodeposition,followed by pyrolysis and then the vulcanization process.CoMoNiO-S/NF-110 exhibited a structure where Ni3S2 and Mo2S3 nanoparticles were integrated at the edges of Co3O4 nanosheets,creating a rich,heterogeneous interface that enhances the synergistic effects of each component.In an alkaline electrolyte,the synthesized CoMoNiO-S/NF-110 exhibited superior electrocatalytic performance for oxygen evolution reaction(OER),achieving current densities of 100 and 200 mA·cm^(-2) with low overpotentials of 199.4 and 224.4 mV,respectively,outperforming RuO2 and several high-performance Mo and Ni-based catalysts.This excellent performance is attributed to the rich interface formed between the components and active sites exposed by the defect structure.展开更多
The poor electrical conductivity of metal-organic frameworks(MOFs)limits their electrocatalytic performance in the oxygen evolution reaction(OER).In this study,a Py@Co-MOF composite material based on pyrene(Py)molecul...The poor electrical conductivity of metal-organic frameworks(MOFs)limits their electrocatalytic performance in the oxygen evolution reaction(OER).In this study,a Py@Co-MOF composite material based on pyrene(Py)molecules and{[Co2(BINDI)(DMA)_(2)]·DMA}_(n)(Co-MOF,H4BINDI=N,N'-bis(5-isophthalic acid)naphthalenediimide,DMA=N,N-dimethylacetamide)was synthesized via a one-pot method,leveragingπ-πinteractions between pyrene and Co-MOF to modulate electrical conductivity.Results demonstrate that the Py@Co-MOF catalyst exhibited significantly enhanced OER performance compared to pure Co-MOF or pyrene-based electrodes,achieving an overpotential of 246 mV at a current density of 10 mA·cm^(-2) along with excellent stability.Density functional theory(DFT)calculations reveal that the formation of O*in the second step is the rate-determining step(RDS)during the OER process on Co-MOF,with an energy barrier of 0.85 eV due to the weak adsorption affinity of the OH*intermediate for Co sites.CCDC:2419276.展开更多
To realize the practical application of anion exchange membrane water electrolysis(AEMWE),it is essential to develop highly active,durable,and cost-effective electrocatalyst for oxygen evolution reaction(OER).Herein,w...To realize the practical application of anion exchange membrane water electrolysis(AEMWE),it is essential to develop highly active,durable,and cost-effective electrocatalyst for oxygen evolution reaction(OER).Herein,we report a hollow-structured Ni_(x)Co_(1−x)O/Ni_(3)S_(2)/Co_(9)S_(8)heterostructure synthesized via sequential template-assisted growth,thermal oxidation,and controlled sulfidation process.The abundant bimetallic heterointerfaces not only provide additional active sites but also promote electronic modulation via charge redistribution.Additionally,the porous and hollow architecture enhances active surface area and mass transfer ability,thereby increasing the number of accessible active sites for alkaline OER.As a result,the prepared electrocatalyst achieves low overpotential of 310 mV at 10 mA cm^(−2)and small Tafel slope of 55.94 mV dec^(−1),demonstrating the exceptional electrocatalytic performance for alkaline OER.When integrated as the anode in an AEMWE cell,it delivers outstanding performance with only 1.657 V at 1.0 A cm^(−2)and reaches high current density of 5.0 A cm^(−2)at 1.989 V,surpassing those of commercial RuO_(2).The cell also shows excellent long-term durability over 100 h with minimal degradation.This study highlights the strong potential of rationally engineered oxide/sulfide heterostructures for next-generation alkaline water electrolysis.展开更多
The development of Pt-free catalysts for the oxygen reduction reaction(ORR)is a great issue for meeting the cost challenges of proton exchange membrane fuel cells(PEMFCs)in commercial applications.In this work,a serie...The development of Pt-free catalysts for the oxygen reduction reaction(ORR)is a great issue for meeting the cost challenges of proton exchange membrane fuel cells(PEMFCs)in commercial applications.In this work,a series of RuCo/C catalysts were synthesized by NaBH4 reduction method under the premise that the total metal mass percentage was 20%.X-ray diffraction(XRD)patterns and scanning electron microscopy(SEM)confirmed the formation of single-phase nanoparticles with an average size of 33 nm.Cyclic voltammograms(CV)and linear sweep voltammograms(LSV)tests indicated that RuCo(2:1)/C catalyst had the optimal ORR properties.Additionally,the RuCo(2:1)/C catalyst remarkably sustained 98.1% of its activity even after 3000 cycles,surpassing the performance of Pt/C(84.8%).Analysis of the elemental state of the catalyst surface after cycling using X-ray photoelectron spectroscopy(XPS)revealed that the Ru^(0) percentage of RuCo(2:1)/C decreased by 2.2%(from 66.3% to 64.1%),while the Pt^(0) percentage of Pt/C decreased by 7.1%(from 53.3% to 46.2%).It is suggested that the synergy between Ru and Co holds the potential to pave the way for future low-cost and highly stable ORR catalysts,offering significant promise in the context of PEMFCs.展开更多
Developing catalysts with excellent stability while significantly reducing the overpotential of the oxygen evolution reaction(OER) is crucial for advancing overall water splitting(OWS) systems.In this study,we synthes...Developing catalysts with excellent stability while significantly reducing the overpotential of the oxygen evolution reaction(OER) is crucial for advancing overall water splitting(OWS) systems.In this study,we synthesized the electrode material Ce-NiCo-LDHs@SnO_(2)/NF through a two-step hydrothermal reaction,where Ce-doped NiCo-LDHs are grown on nickel foam modified by a SnO_(2) layer.Ce doping adjusts the internal electronic distribution of Ni Co-LDHs,while the introduction of the SnO_(2) layer enhances electron transfer capability.Together,these factors contribute to the reduction of the OER energy barrier and experimental evidence confirms that the reaction proceeds via the lattice oxygen evolution mechanism(LOM).Consequently,Ce-NiCo-LDHs@SnO_(2)/NF exhibits high level electrochemical performance in OER,requiring only 234 m V overpotential to achieve a current density of 10 m A/cm^(2),with a Tafel slope of just 27.39 m V/dec.When paired with Pt/C/NF,an external potential of only 1.54 V is needed to drive OWS to attain a current density amounting to 10 m A/cm^(2).Furthermore,the catalyst demonstrates stability for 100 h during the OWS stability test.This study underscores the feasibility of enhancing the OER performance through Ce doping and the introduction of a conductive SnO_(2) layer.展开更多
Conventional ultrasound(US)evaluation of enthesitis in psoriatic arthritis(PsA)is limited by its inability to quantify metabolic alterations such as hypoxia,a key driver of disease activity.We introduce an oxygenation...Conventional ultrasound(US)evaluation of enthesitis in psoriatic arthritis(PsA)is limited by its inability to quantify metabolic alterations such as hypoxia,a key driver of disease activity.We introduce an oxygenation-integrated multimodal photoacoustic/ultrasound(PA/US)imaging framework designed to quantify entheseal oxygen saturation(SO_(2))for assessing entheseal disease activity in PsA.In this cross-sectional study,25 PsA patients underwent bilateral PA/US imaging of 12 entheses,where ultrasound lesions were scored using the Outcome Measures in Rheumatology scoring system,and PA-derived SO_(2) levels,quantified via dual-wavelength PA imaging,were classified into hyperoxia or hypoxia groups using k-means clustering.This approach provides metabolic insights complementary to conventional ultrasonic assessment.A composite score integrating hypoxia with US parameters was validated against clinical disease activity indices(Disease Activity Score 28-C-reactive protein,DAS28-CRP;Disease Activity Index for Psoriatic Arthritis,DAPSA).Among 300 entheses,103(34.3%)exhibited PA positivity,with 40(38.8%)classified as hypoxia.Hypoxia scores independently predicted DAS28-CRP(β=0.618,p=0.001)and DAPSA(β=0.612,p<0:001).The hypoxia-optimized PAUS score demonstrated superior correlation with disease activity indices compared to conventional US(DAS28-CRP:r=0.615,p=0.001 versus r=0.474,p=0.017;DAPSA:r=0.743,p<0:001 versus r=0.567,p=0.003),alongside superior diagnostic accuracy for minimal disease activity(area under the curve,AUC 0.776 versus 0.614,p=0.008)and low disease activity(AUC 0.853 versus 0.772,p=0.009).This multimodal scoring system enhances the stratification of PsA disease activity by providing unique metabolic insights,offering a potential tool for therapeutic monitoring and guiding treat-to-target strategies.展开更多
Heteroatom-doped carbon is considered a promising alternative to commercial Pt/C as an efficient catalyst for the oxygen reduction reaction(ORR).This study presents the synthesis of iron-loaded,sulfur and nitrogen co-...Heteroatom-doped carbon is considered a promising alternative to commercial Pt/C as an efficient catalyst for the oxygen reduction reaction(ORR).This study presents the synthesis of iron-loaded,sulfur and nitrogen co-doped carbon(Fe/SNC)via in situ incorporation of 2-aminothiazole molecules into zeolitic imidazolate framework-8(ZIF-8)through coordination between metal ions and organic ligands.Sulfur and nitrogen doping in carbon supports effectively modulates the electronic structure of the catalyst,increases the Brunauer-Emmett-Teller surface area,and exposes more Fe-N_(x)active centers.Fe-loaded,S and N co-doped carbon with Fe/S molar ratio of 1:10(Fe/SNC-10)exhibits a half-wave potential of 0.902 V vs.RHE.After 5000 cycles of cyclic voltammetry,its half-wave potential decreases by only 20 mV vs.RHE,indicating excellent stability.Due to sulfur s lower electronegativity,the electronic structure of the Fe-N_(x)active center is modulated.Additionally,the larger atomic radius of sulfur introduces defects into the carbon support.As a result,Fe/SNC-10 demonstrates superior ORR activity and stability in alkaline solution compared with Fe-loaded N-doped carbon(Fe/NC).Furthermore,the zinc-air battery assembled with the Fe/SNC-10 catalyst shows enhanced performance relative to those assembled with Fe/NC and Pt/C catalysts.This work offers a novel design strategy for advanced energy storage and conversion applications.展开更多
Seawater zinc-air batteries are promising energy storage devices due to their high energy density and utilization of seawater electrolytes.However,their efficiency is hindered by the sluggish oxygen reduction reaction...Seawater zinc-air batteries are promising energy storage devices due to their high energy density and utilization of seawater electrolytes.However,their efficiency is hindered by the sluggish oxygen reduction reaction(ORR)and chlorideinduced degradation over conventional catalysts.In this study,we proposed a universal synthetic strategy to construct heteroatom axially coordinated Fe–N_(4) single-atom seawater catalyst materials(Cl–Fe–N_(4) and S–Fe–N_(4)).X-ray absorption spectroscopy confirmed their five-coordinated square pyramidal structure.Systematic evaluation of catalytic activities revealed that compared with S–Fe–N_(4),Cl–Fe–N_(4) exhibits smaller electrochemical active surface area and specific surface area,yet demonstrates higher limiting current density(5.8 mA cm^(−2)).The assembled zinc-air batteries using Cl–Fe–N_(4) showed superior power density(187.7 mW cm^(−2) at 245.1 mA cm^(−2)),indicating that Cl axial coordination more effectively enhances the intrinsic ORR activity.Moreover,Cl–Fe–N_(4) demonstrates stronger Cl−poisoning resistance in seawater environments.Chronoamperometry tests and zinc-air battery cycling performance evaluations confirmed its enhanced stability.Density functional theory calculations revealed that the introduction of heteroatoms in the axial direction regulates the electron center of Fe single atom,leading to more active reaction intermediates and increased electron density of Fe single sites,thereby enhancing the reduction in adsorbed intermediates and hence the overall ORR catalytic activity.展开更多
Carbon-based air cathodes offer low cost,high electrical conductivity,and structural tunability.However,they suffer from limited catalytic activity and inefficient gas transport,and they typically rely on noble metal ...Carbon-based air cathodes offer low cost,high electrical conductivity,and structural tunability.However,they suffer from limited catalytic activity and inefficient gas transport,and they typically rely on noble metal additives or complex multilayer configurations.To tackle these issues,this study devised a self-activated integrated carbon-based air cathode.By integrating in situ catalytic site construction with structural optimization,the strategy not only induces the formation of oxygen functional groups(─C─OH,─C═O,─COOH),hierarchical pores,and uniformly distributed active sites,but also establishes a favorable electronic and mass-transport environment.Furthermore,the roll-pressing-based integrated design streamlines electrode construction,reinforces interfacial bonding,and significantly enhances mechanical stability.Density functional theory(DFT)calculations show that oxygen functional groups initiate hydrogen bonding interaction and promote charge enrichment,which improves the activity of the cathode and facilitates intermediate adsorption/desorption in oxygen reduction and evolution reactions processes.As a result,the integrated air cathode-based rechargeable zinc-air batteries(RZABs)achieve a high specific capacity of 811 mAh g^(-1).It also performs well in quasi-solid-state RZABs and silicon-air batteries systems across a wide temperature range,demonstrating strong adaptability and application potential.This study provides a scalable and cost-effective design strategy for high-performance carbon-based air cathodes,offering new insights into advancing durable and practical metal-air energy systems.展开更多
Designing a heterogeneous interface to improve the kinetics of electrocatalysts represents an effective yet challenging approach for enhancing the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).Herei...Designing a heterogeneous interface to improve the kinetics of electrocatalysts represents an effective yet challenging approach for enhancing the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).Herein,a simple MOF-assisted etching-pyrolysis strategy is proposed to fabricate an advanced Mott-Schottky(M–S)electrocatalyst composed of Co/CeO_(2)hetero-nanoparticles embedded within N-doped hollow carbon nanoboxes(H-Co/CeO_(2)@NCBs).Notably,the interfacial Co–O–Ce bond bridging productively facilitates the electron transfer and modulates the charge distribution of the active center,thereby contributing to the ORR/OER kinetics.As expected,the optimal M–S H-Co/CeO_(2)@NCBs catalyst exhibits promising bifunctional electrocatalytic activity with a small potential discrepancy of 0.65 V.Theoretical calculations reveal that the built-in electric field in the M–S heterojunction promotes electron transfer in oxygen electrocatalysis and the interfacial bridge-induced electron redistribution optimizes the adsorption/desorption of the oxygen intermediates,leading to reduced activation energy for the bifunctional ORR/OER reactions.Importantly,H-Co/CeO_(2)@NCBs-assembled Zn-air battery(ZAB)delivers high power density(179.8 mW cm^(−2))and long-term stability(400 h).Furthermore,the assembled flexible solid-state ZAB with H-Co/CeO_(2)@NCBs cathode also exhibits excellent charge–discharge reversibility and flexibility at various bending angles.This work provides a novel perspective on developing efficient and stable M–S bifunctional oxygen electrocatalysts.展开更多
This paper summarizes the nursing experience of a child with acute fulminant myocarditis.Key nursing measures include establishing a multidisciplinary team to jointly formulate diagnosis and treatment plans;implementi...This paper summarizes the nursing experience of a child with acute fulminant myocarditis.Key nursing measures include establishing a multidisciplinary team to jointly formulate diagnosis and treatment plans;implementing refined volume management,anticoagulation management,and ventilator management during extracorporeal membrane oxygenation;providing personalized nutritional support for the child;and strengthening the prevention and management of complications.After active treatment and nursing care,the child recovered well and was successfully transferred out of the intensive care unit.展开更多
During the oxygen evolution reaction(OER),reconstruction of transition metal sulfides(TMSs)is inevitable.However,the lack of a clear theoretical understanding of this process has impeded the development of effective r...During the oxygen evolution reaction(OER),reconstruction of transition metal sulfides(TMSs)is inevitable.However,the lack of a clear theoretical understanding of this process has impeded the development of effective reconstruction regulation strategies.In this study,we first explored the reconstruction mechanism of CoS_(2)during OER from the perspective of electronic structure and identified two possible pathways:the OH-assisted mechanism and the O-assisted mechanism.Further verification showed that these mechanisms are universally applicable to other TMSs(e.g.,FeS_(2)).Based on the reconstruction mechanism,we investigated the basic reasons for the influence of various regulation strategies,such as vacancy modification and facet engineering,on the reconstruction ability.This verified that the method of analyzing the change in the reconstruction ability of catalysts based on the reconstruction mechanism has a high degree of applicability.Importantly,we proposed a core regulation strategy:the coordination symmetry regulation strategy.Specifically,by breaking the symmetry of the surface coordination environment of TMSs(such as introducing heteroatom doping or strain),the reconstruction process will be facilitated.Our findings provide a comprehensive mechanistic explanation for the reconstruction of TMS catalysts and offer a new idea for the rational design of OER catalysts with controllable reconstruction capacity.展开更多
Oxygen evolution reaction(OER)is a key step in hydrogen production by water electrolysis technology.How-ever,developing efficient,stable,and low-cost OER electrocatalysts is still challenging.This article presents the...Oxygen evolution reaction(OER)is a key step in hydrogen production by water electrolysis technology.How-ever,developing efficient,stable,and low-cost OER electrocatalysts is still challenging.This article presents the preparation of a series of novel copper iridium nanocatalysts with heterostructures and low iridium content for OER.The electrochemical tests revealed higher OER of Cu@Ir_(0.3) catalyst under acidic conditions with a generated current density of 10 mA/cm^(2) at only 284 mV overpotential.The corresponding OER mass activity was estimated to be 1.057 A/mgIr,a value 8.39-fold higher than that of the commercial IrO_(2).After 50 h of endurance testing,the Cu@Ir_(0.3) catalyst preserved excellent catalytic activity with a negligible rise in overpotential and maintained a good heterostructures.Cu@Ir_(0.3) The excellent OER activity can be attributed to its heterostructure,as con-firmed by density functional theory(DFT)calculations,indicating that Cu@Ir The coupling between isoquanta causes charge redistribution,optimizing the adsorption energy of unsaturated Ir sites for oxygen intermediates and reducing the energy barrier of OER free energy determining the rate step.In summary,this method provides a new approach for designing efficient,stable,and low iridium content OER catalysts.展开更多
High-entropy alloy(HEA)nanoparticles(NPs)have attracted great attention in electrocatalysis due to their tailorable complex compositions and unique properties.Herein,we introduce Fe,Co,Ni,Cr and Mn into the metal-poly...High-entropy alloy(HEA)nanoparticles(NPs)have attracted great attention in electrocatalysis due to their tailorable complex compositions and unique properties.Herein,we introduce Fe,Co,Ni,Cr and Mn into the metal-polyphenol coordination system to prepare HEA NPs enclosed in N-doped carbon(FeCoNiCrMn)with great potential for catalyzing oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).The unique high-entropy structural characteristics in FeCoNiCrMn facilitate effective interplay between metal species,leading to improved ORR(E_(1/2)=0.89 V)and OER(η=330 mV,j=10 mA·cm^(−2))activity.Additionally,FeCoNiCrMn exhibits excellent open-circuit voltage(1.523 V),power density(110 mW·cm^(−2))and long-term durability,outperforming Pt/C+IrO_(2) electrodes as a cathode catalyst in Zn-air batteries(ZABs).Such polyphenol-assisted alloying method broadens and simplifies the development of HEA electrocatalysts for high-performance ZABs.展开更多
Reactive oxygen species(ROS),including singlet oxygen(^(1)O_(2)),hydroxyl radicals(·OH),and superoxide anions(O_(2)^(·-)),are highly reactive molecules that play central roles in many chemical,biological,and...Reactive oxygen species(ROS),including singlet oxygen(^(1)O_(2)),hydroxyl radicals(·OH),and superoxide anions(O_(2)^(·-)),are highly reactive molecules that play central roles in many chemical,biological,and environmental processes due to their strong oxidative power[1].Generating ROS in a controlled manner under mild conditions is essential for achieving selective oxidation reactions.Light-driven methods are especially appealing for this purpose,as they offer precise control over where and when ROS are produced.展开更多
The oxygen evolution reaction(OER)serves as a fundamental half–reaction in the electrolysis of water for hydrogen production,which is restricted by the sluggish OER reaction kinetics and unable to be practically appl...The oxygen evolution reaction(OER)serves as a fundamental half–reaction in the electrolysis of water for hydrogen production,which is restricted by the sluggish OER reaction kinetics and unable to be practically applied.The traditional lattice oxygen oxidation mechanism(LOM)offers an advantageous route by circumventing the formation of M-OOH^(*)in the adsorption evolution mechanism(AEM),thus enhancing the reaction kinetics of the OER but resulting in possible structural destabilization due to the decreased M–O bond order.Fortunately,the asymmetry of tetrahedral and octahedral sites in transition metal spinel oxides permits the existence of non-bonding oxygen,which could be activated by rational band structure design for direct O-O coupling,where the M–O bond maintains its initial bond order.Here,non-bonding oxygen was introduced into NiFe_(2)O_(4)via annealing in an oxygen-deficient atmosphere.Then,in-situ grown sulfate species on octahedral nickel sites significantly improved the reactivity of the non-bonding oxygen electrons,thereby facilitating the transformation of the redox center from metal to oxygen.LOM based on non-bonding oxygen(LOMNB)was successfully activated within NiFe_(2)O_(4),exhibiting a low overpotential of 206 mV to achieve a current density of 10 mA cm^(-2)and excellent durability of stable operation for over 150 h.Additionally,catalysts featuring varying band structures were synthesized for comparative analysis,and it was found that the reversible redox processes of non-bonding oxygen and the accumulation of non-bonding oxygen species containing 2p holes are critical prerequisites for triggering and sustaining the LOMNB pathway in transition metal spinel oxides.These findings may provide valuable insights for the future development of spinel-oxide-based LOM catalysts.展开更多
基金supported by Basic Science Research Program(Priority Research Institute)through the NRF of Korea funded by the Ministry of Education(2021R1A6A1A10039823)by the Korea Basic Science Institute(National Research Facilities and Equipment Center)grant funded by the Ministry of Education(2020R1A6C101B194)。
文摘Lithium-oxygen(Li-O2)batteries are perceived as a promising breakthrough in sustainable electrochemical energy storage,utilizing ambient air as an energy source,eliminating the need for costly cathode materials,and offering the highest theoretical energy density(~3.5 k Wh kg^(-1))among discussed candidates.Contributing to the poor cycle life of currently reported Li-O_(2)cells is singlet oxygen(1O_(2))formation,inducing parasitic reactions,degrading key components,and severely deteriorating cell performance.Here,we harness the chirality-induced spin selectivity effect of chiral cobalt oxide nanosheets(Co_(3)O_(4)NSs)as cathode materials to suppress 1O_(2)in Li-O_(2)batteries for the first time.Operando photoluminescence spectroscopy reveals a 3.7-fold and 3.23-fold reduction in 1O_(2)during discharge and charge,respectively,compared to conventional carbon paperbased cells,consistent with differential electrochemical mass spectrometry results,which indicate a near-theoretical charge-to-O_(2)ratio(2.04 e-/O_(2)).Density functional theory calculations demonstrate that chirality induces a peak shift near the Fermi level,enhancing Co 3d-O 2p hybridization,stabilizing reaction intermediates,and lowering activation barriers for Li_(2)O_(2)formation and decomposition.These findings establish a new strategy for improving the stability and energy efficiency of sustainable Li-O_(2)batteries,abridging the current gap to commercialization.
基金support from the National Natural Science Foundation of China(Nos.12305373 and 52276220)the Guangzhou Basic Research Program(No.SL2024A04J00234).
文摘Developing efficient and durable electrocatalysts for acidic oxygen evolution reaction(OER)is pivotal for advancing proton exchange membrane water electrolysis(PEMWEs),yet balancing activity and stability remains a formidable challenge.Herein,we propose a dual-engineering strategy to stabilize Ru-based catalysts by synergizing the oxygen vacancy site-synergized mechanism-lattice oxygen mechanism(OVSM-LOM)with Ru-N bond stabilization.The engineered RuO_(2)@NCC catalyst exhibits exceptional OER performance in 0.5 M H2SO4,achieving an ultralow overpotential of 215 mV at 10 mA cm^(-2) and prolonged stability for over 327 h.The catalyst delivers 300 h of continuous operation at 1 A cm^(-2),with a negligible degradation rate of only 0.067 mV h-1,further demonstrating its potential for practical application.Oxygen vacancies unlock the OVSM-LOM pathway,bypassing the sluggish adsorbate evolution mechanism(AEM)and accelerating reaction kinetics,while the Ru-N bonds suppress Ru dissolution by anchoring low-valent Ru centers.Quasi-in situ X-ray photoelectron spectroscopy(XPS),X-ray absorption spectroscopy(XAS),and isotopic labeling experiments confirm the lattice oxygen participation with *O formation as the rate-determining step.The Ru-N bonds reinforce the structural integrity by stabilizing low-valent Ru centers and inhibiting overoxidation.Theoretical calculations further verify that the synergistic interaction between OVs and Ru-O(N)active sites optimizes the Ru d-band center and stabilizes intermediates,while Ru-N coordination enhances structural integrity.This study establishes a novel paradigm for designing robust acidic OER catalysts through defect and coordination engineering,bridging the gap between activity and stability for sustainable energy technologies.
基金supported by the “Climbing Plan” of Harbin Normal University (No.XKB202301)National Natural Science Foundation of China (Nos.21871065 and 22071038)。
文摘Magnetic field-driven spin polarization modulation has emerged as an effective way to boost the electrocatalytic oxygen evolution reaction(OER).However,the correlation among catalyst structure,magnetic property,and magnetic field enhanced-electrochemical activity remains to be fully elucidated.Herein,single-domain CoFe_(2)O_(4) catalysts with tunable oxygen vacancies(CFO-V_(O)) were synthesized to probe how V_(O) mediates magnetism and OER activity under magnetic field.The introduction of V_(O) can simultaneously modulate saturation magnetization(M_(s)) and coercivity(H_(c)),where the increased M_(s) dominates the magnetic field-enhanced OER activity.Under a 14,000 G magnetic field,the optimized CFO-V_(O) exhibits up to 16.1 % reduction in overpotential and 365 % enhancement in magnetocurrent(MC).Electrochemical analyses and post-OER characterization reveal that the magnetic field synergistically improves OER kinetics through lattice distortion induction,magnetohydrodynamic effect,and spin charge transfer effect.Importantly,the magnetic field promotes additional Co^(3+) generation to compensate for charge imbalance caused by V_(O) filling,maintaining dynamic equilibrium of V_(O) and effective reactant adsorption-conversion processes.This work unveils the synergistic mechanism of V_(O) and magnetic parameters for enhancing OER performance under the magnetic field,providing new insights into the design of high-efficiency spinregulated OER catalysts.
文摘Covalent organic framework ionomers enable synergistic efficient transport of protons and oxygen in medium-temperature proton exchange membrane fuel cells Proton exchange membrane fuel cells(PEMFCs),as clean and efficient energy technologies,are constrained in their performance enhancement by the sluggish oxygen reduction reaction(ORR)kinetics at the cathode,anode CO poisoning(e.g.,from methanol crossover)and intricate water management dilemmas[1].
文摘A composite electrocatalyst,CoMoNiO-S/NF-110(NF is nickel foam),was synthesized through electrodeposition,followed by pyrolysis and then the vulcanization process.CoMoNiO-S/NF-110 exhibited a structure where Ni3S2 and Mo2S3 nanoparticles were integrated at the edges of Co3O4 nanosheets,creating a rich,heterogeneous interface that enhances the synergistic effects of each component.In an alkaline electrolyte,the synthesized CoMoNiO-S/NF-110 exhibited superior electrocatalytic performance for oxygen evolution reaction(OER),achieving current densities of 100 and 200 mA·cm^(-2) with low overpotentials of 199.4 and 224.4 mV,respectively,outperforming RuO2 and several high-performance Mo and Ni-based catalysts.This excellent performance is attributed to the rich interface formed between the components and active sites exposed by the defect structure.
文摘The poor electrical conductivity of metal-organic frameworks(MOFs)limits their electrocatalytic performance in the oxygen evolution reaction(OER).In this study,a Py@Co-MOF composite material based on pyrene(Py)molecules and{[Co2(BINDI)(DMA)_(2)]·DMA}_(n)(Co-MOF,H4BINDI=N,N'-bis(5-isophthalic acid)naphthalenediimide,DMA=N,N-dimethylacetamide)was synthesized via a one-pot method,leveragingπ-πinteractions between pyrene and Co-MOF to modulate electrical conductivity.Results demonstrate that the Py@Co-MOF catalyst exhibited significantly enhanced OER performance compared to pure Co-MOF or pyrene-based electrodes,achieving an overpotential of 246 mV at a current density of 10 mA·cm^(-2) along with excellent stability.Density functional theory(DFT)calculations reveal that the formation of O*in the second step is the rate-determining step(RDS)during the OER process on Co-MOF,with an energy barrier of 0.85 eV due to the weak adsorption affinity of the OH*intermediate for Co sites.CCDC:2419276.
基金supported by the Korea Institute for Advancement of Technology(KIAT)and the Ministry of Trade,Industry&Energy(MOTIE)of the Republic of Korea(No.P0022130)by the Institute of Information&Communications Technology Planning&Evaluation(IITP)-Innovative Human Resource Development for Local Intellectualization program grant funded by the Korea government(MSIT)(IITP-2025-RS-2023-00259678).
文摘To realize the practical application of anion exchange membrane water electrolysis(AEMWE),it is essential to develop highly active,durable,and cost-effective electrocatalyst for oxygen evolution reaction(OER).Herein,we report a hollow-structured Ni_(x)Co_(1−x)O/Ni_(3)S_(2)/Co_(9)S_(8)heterostructure synthesized via sequential template-assisted growth,thermal oxidation,and controlled sulfidation process.The abundant bimetallic heterointerfaces not only provide additional active sites but also promote electronic modulation via charge redistribution.Additionally,the porous and hollow architecture enhances active surface area and mass transfer ability,thereby increasing the number of accessible active sites for alkaline OER.As a result,the prepared electrocatalyst achieves low overpotential of 310 mV at 10 mA cm^(−2)and small Tafel slope of 55.94 mV dec^(−1),demonstrating the exceptional electrocatalytic performance for alkaline OER.When integrated as the anode in an AEMWE cell,it delivers outstanding performance with only 1.657 V at 1.0 A cm^(−2)and reaches high current density of 5.0 A cm^(−2)at 1.989 V,surpassing those of commercial RuO_(2).The cell also shows excellent long-term durability over 100 h with minimal degradation.This study highlights the strong potential of rationally engineered oxide/sulfide heterostructures for next-generation alkaline water electrolysis.
基金Funded by the 111 Project(No.B17034)Open Project of Hubei Key Laboratory of Power System Design and Test for Electrical Vehicle(No.ZDSYS202212)+1 种基金Innovative Research Team Development Program of Ministry of Education of China(No.IRT_17R83)the Science and Technology Project of China Southern Power Grid Co.,Ltd.(No.GDKJXM20222546)。
文摘The development of Pt-free catalysts for the oxygen reduction reaction(ORR)is a great issue for meeting the cost challenges of proton exchange membrane fuel cells(PEMFCs)in commercial applications.In this work,a series of RuCo/C catalysts were synthesized by NaBH4 reduction method under the premise that the total metal mass percentage was 20%.X-ray diffraction(XRD)patterns and scanning electron microscopy(SEM)confirmed the formation of single-phase nanoparticles with an average size of 33 nm.Cyclic voltammograms(CV)and linear sweep voltammograms(LSV)tests indicated that RuCo(2:1)/C catalyst had the optimal ORR properties.Additionally,the RuCo(2:1)/C catalyst remarkably sustained 98.1% of its activity even after 3000 cycles,surpassing the performance of Pt/C(84.8%).Analysis of the elemental state of the catalyst surface after cycling using X-ray photoelectron spectroscopy(XPS)revealed that the Ru^(0) percentage of RuCo(2:1)/C decreased by 2.2%(from 66.3% to 64.1%),while the Pt^(0) percentage of Pt/C decreased by 7.1%(from 53.3% to 46.2%).It is suggested that the synergy between Ru and Co holds the potential to pave the way for future low-cost and highly stable ORR catalysts,offering significant promise in the context of PEMFCs.
基金supported by the National Natural Science Foundation of China (No.52274304)。
文摘Developing catalysts with excellent stability while significantly reducing the overpotential of the oxygen evolution reaction(OER) is crucial for advancing overall water splitting(OWS) systems.In this study,we synthesized the electrode material Ce-NiCo-LDHs@SnO_(2)/NF through a two-step hydrothermal reaction,where Ce-doped NiCo-LDHs are grown on nickel foam modified by a SnO_(2) layer.Ce doping adjusts the internal electronic distribution of Ni Co-LDHs,while the introduction of the SnO_(2) layer enhances electron transfer capability.Together,these factors contribute to the reduction of the OER energy barrier and experimental evidence confirms that the reaction proceeds via the lattice oxygen evolution mechanism(LOM).Consequently,Ce-NiCo-LDHs@SnO_(2)/NF exhibits high level electrochemical performance in OER,requiring only 234 m V overpotential to achieve a current density of 10 m A/cm^(2),with a Tafel slope of just 27.39 m V/dec.When paired with Pt/C/NF,an external potential of only 1.54 V is needed to drive OWS to attain a current density amounting to 10 m A/cm^(2).Furthermore,the catalyst demonstrates stability for 100 h during the OWS stability test.This study underscores the feasibility of enhancing the OER performance through Ce doping and the introduction of a conductive SnO_(2) layer.
基金supported by the National Natural Science Foundation of China(62325112)the National Key Research and Development Program of China(2023YFC2411700,2023YFC2411705)+2 种基金the National Natural Science Foundation of China(U22A2023)the National High-Level Hospital Clinical Research Funding(2022-PUMCH-C-009,2022-PUMCH-B-064,2022-PUMCH-D-002)the National Basic Research Program of China(973 Program,2014CB541801).
文摘Conventional ultrasound(US)evaluation of enthesitis in psoriatic arthritis(PsA)is limited by its inability to quantify metabolic alterations such as hypoxia,a key driver of disease activity.We introduce an oxygenation-integrated multimodal photoacoustic/ultrasound(PA/US)imaging framework designed to quantify entheseal oxygen saturation(SO_(2))for assessing entheseal disease activity in PsA.In this cross-sectional study,25 PsA patients underwent bilateral PA/US imaging of 12 entheses,where ultrasound lesions were scored using the Outcome Measures in Rheumatology scoring system,and PA-derived SO_(2) levels,quantified via dual-wavelength PA imaging,were classified into hyperoxia or hypoxia groups using k-means clustering.This approach provides metabolic insights complementary to conventional ultrasonic assessment.A composite score integrating hypoxia with US parameters was validated against clinical disease activity indices(Disease Activity Score 28-C-reactive protein,DAS28-CRP;Disease Activity Index for Psoriatic Arthritis,DAPSA).Among 300 entheses,103(34.3%)exhibited PA positivity,with 40(38.8%)classified as hypoxia.Hypoxia scores independently predicted DAS28-CRP(β=0.618,p=0.001)and DAPSA(β=0.612,p<0:001).The hypoxia-optimized PAUS score demonstrated superior correlation with disease activity indices compared to conventional US(DAS28-CRP:r=0.615,p=0.001 versus r=0.474,p=0.017;DAPSA:r=0.743,p<0:001 versus r=0.567,p=0.003),alongside superior diagnostic accuracy for minimal disease activity(area under the curve,AUC 0.776 versus 0.614,p=0.008)and low disease activity(AUC 0.853 versus 0.772,p=0.009).This multimodal scoring system enhances the stratification of PsA disease activity by providing unique metabolic insights,offering a potential tool for therapeutic monitoring and guiding treat-to-target strategies.
基金financial support of the National Natural Science Foundation of China(No.52472271)the National Key Research and Development Program of China(No.2023YFE0115800)。
文摘Heteroatom-doped carbon is considered a promising alternative to commercial Pt/C as an efficient catalyst for the oxygen reduction reaction(ORR).This study presents the synthesis of iron-loaded,sulfur and nitrogen co-doped carbon(Fe/SNC)via in situ incorporation of 2-aminothiazole molecules into zeolitic imidazolate framework-8(ZIF-8)through coordination between metal ions and organic ligands.Sulfur and nitrogen doping in carbon supports effectively modulates the electronic structure of the catalyst,increases the Brunauer-Emmett-Teller surface area,and exposes more Fe-N_(x)active centers.Fe-loaded,S and N co-doped carbon with Fe/S molar ratio of 1:10(Fe/SNC-10)exhibits a half-wave potential of 0.902 V vs.RHE.After 5000 cycles of cyclic voltammetry,its half-wave potential decreases by only 20 mV vs.RHE,indicating excellent stability.Due to sulfur s lower electronegativity,the electronic structure of the Fe-N_(x)active center is modulated.Additionally,the larger atomic radius of sulfur introduces defects into the carbon support.As a result,Fe/SNC-10 demonstrates superior ORR activity and stability in alkaline solution compared with Fe-loaded N-doped carbon(Fe/NC).Furthermore,the zinc-air battery assembled with the Fe/SNC-10 catalyst shows enhanced performance relative to those assembled with Fe/NC and Pt/C catalysts.This work offers a novel design strategy for advanced energy storage and conversion applications.
基金funded by the Innovative Research Group Project of the National Natural Science Foundation of China(52121004)the Research Development Fund(No.RDF-21-02-060)by Xi’an Jiaotong-Liverpool University+1 种基金support received from the Suzhou Industrial Park High Quality Innovation Platform of Functional Molecular Materials and Devices(YZCXPT2023105)the XJTLU Advanced Materials Research Center(AMRC).
文摘Seawater zinc-air batteries are promising energy storage devices due to their high energy density and utilization of seawater electrolytes.However,their efficiency is hindered by the sluggish oxygen reduction reaction(ORR)and chlorideinduced degradation over conventional catalysts.In this study,we proposed a universal synthetic strategy to construct heteroatom axially coordinated Fe–N_(4) single-atom seawater catalyst materials(Cl–Fe–N_(4) and S–Fe–N_(4)).X-ray absorption spectroscopy confirmed their five-coordinated square pyramidal structure.Systematic evaluation of catalytic activities revealed that compared with S–Fe–N_(4),Cl–Fe–N_(4) exhibits smaller electrochemical active surface area and specific surface area,yet demonstrates higher limiting current density(5.8 mA cm^(−2)).The assembled zinc-air batteries using Cl–Fe–N_(4) showed superior power density(187.7 mW cm^(−2) at 245.1 mA cm^(−2)),indicating that Cl axial coordination more effectively enhances the intrinsic ORR activity.Moreover,Cl–Fe–N_(4) demonstrates stronger Cl−poisoning resistance in seawater environments.Chronoamperometry tests and zinc-air battery cycling performance evaluations confirmed its enhanced stability.Density functional theory calculations revealed that the introduction of heteroatoms in the axial direction regulates the electron center of Fe single atom,leading to more active reaction intermediates and increased electron density of Fe single sites,thereby enhancing the reduction in adsorbed intermediates and hence the overall ORR catalytic activity.
基金funded by the National Nature Science Foundation of China(62264006,62574102)“Thousand Talents Program”of Yunnan Province for Young Talents,Innovative Research Teams(in Science and Technology)in the University of Yunnan Province(IRTSTYN),XingDian Talent Support Program for Young Talents,and Frontier Research Team of Kunming University 2023,The Basic Research Project of Yunnan Province(Nos.202201AU070022)+2 种基金Kunming University Talent Introduction Fund(Nos.YJL20024)Yunnan Province Education Department Scientific Research Fund Project(Nos.2024Y759)Undergraduate Innovation and Entrepreneurship Training Program Project of Yunnan Provincial(202411393005)。
文摘Carbon-based air cathodes offer low cost,high electrical conductivity,and structural tunability.However,they suffer from limited catalytic activity and inefficient gas transport,and they typically rely on noble metal additives or complex multilayer configurations.To tackle these issues,this study devised a self-activated integrated carbon-based air cathode.By integrating in situ catalytic site construction with structural optimization,the strategy not only induces the formation of oxygen functional groups(─C─OH,─C═O,─COOH),hierarchical pores,and uniformly distributed active sites,but also establishes a favorable electronic and mass-transport environment.Furthermore,the roll-pressing-based integrated design streamlines electrode construction,reinforces interfacial bonding,and significantly enhances mechanical stability.Density functional theory(DFT)calculations show that oxygen functional groups initiate hydrogen bonding interaction and promote charge enrichment,which improves the activity of the cathode and facilitates intermediate adsorption/desorption in oxygen reduction and evolution reactions processes.As a result,the integrated air cathode-based rechargeable zinc-air batteries(RZABs)achieve a high specific capacity of 811 mAh g^(-1).It also performs well in quasi-solid-state RZABs and silicon-air batteries systems across a wide temperature range,demonstrating strong adaptability and application potential.This study provides a scalable and cost-effective design strategy for high-performance carbon-based air cathodes,offering new insights into advancing durable and practical metal-air energy systems.
基金supported by the National Natural Science Foundation of China(U24A20550,52273264 and 52470073)the Key Project of the Heilongjiang Provincial Natural Science Foundation(ZD2024B001)Outstanding Youth Fund of Heilongjiang Province(JQ2022E005).
文摘Designing a heterogeneous interface to improve the kinetics of electrocatalysts represents an effective yet challenging approach for enhancing the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).Herein,a simple MOF-assisted etching-pyrolysis strategy is proposed to fabricate an advanced Mott-Schottky(M–S)electrocatalyst composed of Co/CeO_(2)hetero-nanoparticles embedded within N-doped hollow carbon nanoboxes(H-Co/CeO_(2)@NCBs).Notably,the interfacial Co–O–Ce bond bridging productively facilitates the electron transfer and modulates the charge distribution of the active center,thereby contributing to the ORR/OER kinetics.As expected,the optimal M–S H-Co/CeO_(2)@NCBs catalyst exhibits promising bifunctional electrocatalytic activity with a small potential discrepancy of 0.65 V.Theoretical calculations reveal that the built-in electric field in the M–S heterojunction promotes electron transfer in oxygen electrocatalysis and the interfacial bridge-induced electron redistribution optimizes the adsorption/desorption of the oxygen intermediates,leading to reduced activation energy for the bifunctional ORR/OER reactions.Importantly,H-Co/CeO_(2)@NCBs-assembled Zn-air battery(ZAB)delivers high power density(179.8 mW cm^(−2))and long-term stability(400 h).Furthermore,the assembled flexible solid-state ZAB with H-Co/CeO_(2)@NCBs cathode also exhibits excellent charge–discharge reversibility and flexibility at various bending angles.This work provides a novel perspective on developing efficient and stable M–S bifunctional oxygen electrocatalysts.
文摘This paper summarizes the nursing experience of a child with acute fulminant myocarditis.Key nursing measures include establishing a multidisciplinary team to jointly formulate diagnosis and treatment plans;implementing refined volume management,anticoagulation management,and ventilator management during extracorporeal membrane oxygenation;providing personalized nutritional support for the child;and strengthening the prevention and management of complications.After active treatment and nursing care,the child recovered well and was successfully transferred out of the intensive care unit.
基金supported by the National Key Research and Development program(2022YFA1504000)the National Natural Science Foundation of China(22302101)+4 种基金the Fundamental Research Funds for the Central Universities(63185015)the Shenzhen Science and Technology Program(JCYJ20210324121002007,JCYJ20230807151503007)the Yunnan Provincial Science and Technology Project at Southwest United Graduate School(202402AO370001)the China Postdoctoral Science Foundation(2022M721699)the Guangdong Basic and Applied Basic Research Foundation(2024A1515010347).
文摘During the oxygen evolution reaction(OER),reconstruction of transition metal sulfides(TMSs)is inevitable.However,the lack of a clear theoretical understanding of this process has impeded the development of effective reconstruction regulation strategies.In this study,we first explored the reconstruction mechanism of CoS_(2)during OER from the perspective of electronic structure and identified two possible pathways:the OH-assisted mechanism and the O-assisted mechanism.Further verification showed that these mechanisms are universally applicable to other TMSs(e.g.,FeS_(2)).Based on the reconstruction mechanism,we investigated the basic reasons for the influence of various regulation strategies,such as vacancy modification and facet engineering,on the reconstruction ability.This verified that the method of analyzing the change in the reconstruction ability of catalysts based on the reconstruction mechanism has a high degree of applicability.Importantly,we proposed a core regulation strategy:the coordination symmetry regulation strategy.Specifically,by breaking the symmetry of the surface coordination environment of TMSs(such as introducing heteroatom doping or strain),the reconstruction process will be facilitated.Our findings provide a comprehensive mechanistic explanation for the reconstruction of TMS catalysts and offer a new idea for the rational design of OER catalysts with controllable reconstruction capacity.
基金supported by the Major Science and Technology Special Plan of Yunnan Province(Nos.202302AB080012 and 202402AB080004)the National Natural Science Foundation of China(No.22264025)+1 种基金the Basic Research Foundation of Yunnan Province(Nos.202401AS070033 and 202501AT070055)the Reserve talents for young and middleaged academic and technical leaders project of Yunnan Province(No.202405AC350071).
文摘Oxygen evolution reaction(OER)is a key step in hydrogen production by water electrolysis technology.How-ever,developing efficient,stable,and low-cost OER electrocatalysts is still challenging.This article presents the preparation of a series of novel copper iridium nanocatalysts with heterostructures and low iridium content for OER.The electrochemical tests revealed higher OER of Cu@Ir_(0.3) catalyst under acidic conditions with a generated current density of 10 mA/cm^(2) at only 284 mV overpotential.The corresponding OER mass activity was estimated to be 1.057 A/mgIr,a value 8.39-fold higher than that of the commercial IrO_(2).After 50 h of endurance testing,the Cu@Ir_(0.3) catalyst preserved excellent catalytic activity with a negligible rise in overpotential and maintained a good heterostructures.Cu@Ir_(0.3) The excellent OER activity can be attributed to its heterostructure,as con-firmed by density functional theory(DFT)calculations,indicating that Cu@Ir The coupling between isoquanta causes charge redistribution,optimizing the adsorption energy of unsaturated Ir sites for oxygen intermediates and reducing the energy barrier of OER free energy determining the rate step.In summary,this method provides a new approach for designing efficient,stable,and low iridium content OER catalysts.
基金supported by the Fundamental Research Funds for the Central Universities(No.22120230104).
文摘High-entropy alloy(HEA)nanoparticles(NPs)have attracted great attention in electrocatalysis due to their tailorable complex compositions and unique properties.Herein,we introduce Fe,Co,Ni,Cr and Mn into the metal-polyphenol coordination system to prepare HEA NPs enclosed in N-doped carbon(FeCoNiCrMn)with great potential for catalyzing oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).The unique high-entropy structural characteristics in FeCoNiCrMn facilitate effective interplay between metal species,leading to improved ORR(E_(1/2)=0.89 V)and OER(η=330 mV,j=10 mA·cm^(−2))activity.Additionally,FeCoNiCrMn exhibits excellent open-circuit voltage(1.523 V),power density(110 mW·cm^(−2))and long-term durability,outperforming Pt/C+IrO_(2) electrodes as a cathode catalyst in Zn-air batteries(ZABs).Such polyphenol-assisted alloying method broadens and simplifies the development of HEA electrocatalysts for high-performance ZABs.
文摘Reactive oxygen species(ROS),including singlet oxygen(^(1)O_(2)),hydroxyl radicals(·OH),and superoxide anions(O_(2)^(·-)),are highly reactive molecules that play central roles in many chemical,biological,and environmental processes due to their strong oxidative power[1].Generating ROS in a controlled manner under mild conditions is essential for achieving selective oxidation reactions.Light-driven methods are especially appealing for this purpose,as they offer precise control over where and when ROS are produced.
文摘The oxygen evolution reaction(OER)serves as a fundamental half–reaction in the electrolysis of water for hydrogen production,which is restricted by the sluggish OER reaction kinetics and unable to be practically applied.The traditional lattice oxygen oxidation mechanism(LOM)offers an advantageous route by circumventing the formation of M-OOH^(*)in the adsorption evolution mechanism(AEM),thus enhancing the reaction kinetics of the OER but resulting in possible structural destabilization due to the decreased M–O bond order.Fortunately,the asymmetry of tetrahedral and octahedral sites in transition metal spinel oxides permits the existence of non-bonding oxygen,which could be activated by rational band structure design for direct O-O coupling,where the M–O bond maintains its initial bond order.Here,non-bonding oxygen was introduced into NiFe_(2)O_(4)via annealing in an oxygen-deficient atmosphere.Then,in-situ grown sulfate species on octahedral nickel sites significantly improved the reactivity of the non-bonding oxygen electrons,thereby facilitating the transformation of the redox center from metal to oxygen.LOM based on non-bonding oxygen(LOMNB)was successfully activated within NiFe_(2)O_(4),exhibiting a low overpotential of 206 mV to achieve a current density of 10 mA cm^(-2)and excellent durability of stable operation for over 150 h.Additionally,catalysts featuring varying band structures were synthesized for comparative analysis,and it was found that the reversible redox processes of non-bonding oxygen and the accumulation of non-bonding oxygen species containing 2p holes are critical prerequisites for triggering and sustaining the LOMNB pathway in transition metal spinel oxides.These findings may provide valuable insights for the future development of spinel-oxide-based LOM catalysts.
