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
Chemical looping methane steam reforming(CL-MSR)has garnered significant attention owing to its ability to sequentially produce syngas with high selectivity and high-purity hydrogen through redox cycling.To overcome t...Chemical looping methane steam reforming(CL-MSR)has garnered significant attention owing to its ability to sequentially produce syngas with high selectivity and high-purity hydrogen through redox cycling.To overcome the limitations of single ironbased oxygen carriers,including poor cycling stability,low reactivity and susceptibility to sintering,this study employed a dipcoating method to modify Fe_(2)O_(3)/Al_(2)O_(3)oxygen carriers by incorporating three distinct metal additives:Cu,La and Ce.The composite oxygen carriers were systematically characterized and evaluated under redox conditions to investigate the structure-activity relationships between the physicochemical properties,reactivity,and hydrogen production performance.Results revealed that the spinel-phase CuFe_(2)O_(4)exhibited higher reactivity than the perovskite-phase LaFeO_(3)and CeO_(2),promoting the deeper reduction of Fe_(2)O_(3).Fe58Cu2Al exhibited an oxygen storage capacity as high as 6.5 mmol/g.During the CH4 reaction stage,Fe58Cu2Al achieved the highest oxygen loss of 12.1 g/100 g oxygen carrier,accompanied by a syngas yield of 5.15 mmol/g-1.33 times and 1.59 times greater than that of Fe60Al.In the hydrogen production stage,the 2%Cu-modified oxygen carrier demonstrated optimal performance,yielding 5.13 mmol/g of hydrogen,which was 1.51 times that of the pristine sample.Even after ten cycles,the H_(2)yield remained at 3.61 mmol/g,surpassing the single-cycle output of the pristine sample and the H2 purity consistently exceeded 98%.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
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
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
The primary challenge in rechargeable Zn-air batteries lies in developing a catalyst capable of simultaneously improving performance for oxygen reduction reaction(ORR)during discharge and oxygen evolution reaction(OER...The primary challenge in rechargeable Zn-air batteries lies in developing a catalyst capable of simultaneously improving performance for oxygen reduction reaction(ORR)during discharge and oxygen evolution reaction(OER)during charge.Engineering spin configuration is essential for enhancing the intrinsic bifunctional activity and stability of spinel Co_(3)O_(4).Herein,Cr^(3+)is doped into Co_(3)O_(4),inducing directional distortion of CoO_6 octahedron to modify crystal field splitting energy,pushing Co_(Oh)toward intermediate-spin(IS)configuration(t_(2g)^(5)e_(g^(1)))with optimized eg occupancy of 1.04.As a result,9%Cr-Co_(3)O_(4)demonstrates an excellent bifunctional activity and remarkable rechargeable Zn-air battery performance that even outperforms Pt/C+RuO_(2).Density functional theory(DFT)studies reveal that IS Co_(Oh)not only regulates the adsorption energy of ORR/OER species but also transform the O_(2)adsorption configuration from end-on to Griffith configuration,thus modifies the mechanisms of both ORR and OER process and optimize bifunctional activity and selectivity.This work provides mechanistic insight into the spin origin of ORR/OER catalysis and highlights a promising strategy for developing robust bifunctional electrocatalysts.展开更多
High-entropy oxides(HEOs)derive their exceptional properties from the atomic-level homogenization of multiple constituent elements within the crystal lattice,which induces a sophisticated local environment that fundam...High-entropy oxides(HEOs)derive their exceptional properties from the atomic-level homogenization of multiple constituent elements within the crystal lattice,which induces a sophisticated local environment that fundamentally reconfigures electron density distributions and coordination environment at active sites.However,the mechanisms by which multi-component systems in HEOs precisely regulate high-activity catalytic sites remain poorly understood.This work addresses this gap by designing medium-entropy perovskite oxides through the strategic incorporation of transition metals with distinct electronegativities and ionic radii,aiming to unravel how local environmental modifications impact the energy band location,coordination states,and adsorption behavior of the Co site.A family of A_(2)BO_(4)-type medium-entropy oxides PrSr(Fe_(0.2)Co_(0.2)Ni_(0.2)Cu_(0.2)M_(0.2))O_(4)(M=Sc,Cr,Mn)was successfully synthesized.Divergent atomic properties among Sc,Cr,and Mn(electronegativity,ionic size,and metal-oxygen bond strength)triggered pronounced electron redistribution,effectively tuning the d-band center of Co.Remarkably,Cr substitution significantly enhanced O_(2) adsorption at Co-active sites,as indicated by an elongated O-O bond length(1.234Å→1.279Å).Concurrently,Cr doping destabilized the M'-O-Cr bonds(M'=Fe,Co,Ni,Cu)and lowered the thermodynamic barrier for oxygen vacancy formation.Electrochemical tests revealed that PrSr(Fe_(0.2)Co_(0.2)Ni_(0.2)Cu_(0.2)Cr_(0.2))O_(4)(PSMO-Cr)exhibited the highest electrical conductivity and fastest oxygen surface exchange kinetics.At 700℃,the area-specific resistance(ASR)of the PSMO-Cr cathode was 0.07Ωcm^(2).Corresponding fuel cells achieved a maximum power density of 0.76 W cm^(-2).In electrolysis mode,the maximum current density reached 0.56 A cm^(-2) under 1.3 V at 700℃using PSMO-Cr as the anode.These results demonstrate that PSMO-Cr is a promising bifunctional catalyst for energy conversion applications.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
Achieving high selectivity to 2,5-furandicarboxylic acid(FDCA)in the photocatalytic oxidation of 5-hydroxymethylfurfural(HMF)in aqueous solution advocates the principle of green and sustainable chemistry,but still rem...Achieving high selectivity to 2,5-furandicarboxylic acid(FDCA)in the photocatalytic oxidation of 5-hydroxymethylfurfural(HMF)in aqueous solution advocates the principle of green and sustainable chemistry,but still remains a significant challenge.Herein,manipulating the reactive oxygen species(ROS)has been realized and dramatically promotes the selective photocatalytic oxidation of HMF in aqueous solution.A high FDCAyield of 98.6% has been achieved after 3 h of visible light irradiation over the as-prepared FeO_(x)-Au/TiO_(2) catalyst,being one of the leading photocatalytic performances.Furthermore,satisfactory FDCA yields of higher than 80%could be realized even in the outdoor environment under natural sunlight irradiation,regardless of sunny or cloudy weather.A combination study including physical characterization,kinetic analysis,radical trapping experiments and density functional theory calculations unveils the rate-determining step(oxidation of hydroxyl group)and respective contributions of the generated ROS(1O_(2) and·O_(2)-)in each step of the entire reaction network.The present work would push ahead the understanding of HMF photocatalytic oxidation and contribute to the rational design of high-performance photocatalysts.展开更多
Silica nanoparticles-stabilized cobalt and nitrogen-doped carbon materials were synthesized through pyrolysis of metal-organic-framework of ZIF-67 supported by silica nanoparticles.The experimental results reveal that...Silica nanoparticles-stabilized cobalt and nitrogen-doped carbon materials were synthesized through pyrolysis of metal-organic-framework of ZIF-67 supported by silica nanoparticles.The experimental results reveal that the introduction of the silica nanoparticles can stabilize the microstructure of the derived CoN-C materials,which in turn exhibits the promising electrocatalytic activity towards both oxygen reduction and oxygen evolution reactions.The optimized sample exhibits a better oxygen reduction activity than commercial Pt/C catalyst as confirmed by the positive shift of half-wave potential by 20 mV while it has a low overpotential of 273 mV for oxygen evolution reactions with the retained performance over 80%after 25,000 s of continuous operation.It is demonstrated that the introduction of support frame might be an effective way to improve the activity and stability of metal-organic-framework derived electrocatalyst with stabilized microstructure.展开更多
The development of economical,highly efficient,and stable bifunctional electrocatalysts for both the oxygen evolution reaction(OER)and the oxygen reduction reaction(ORR)remains a critical focus in advancing rechargeab...The development of economical,highly efficient,and stable bifunctional electrocatalysts for both the oxygen evolution reaction(OER)and the oxygen reduction reaction(ORR)remains a critical focus in advancing rechargeable metal-air battery systems.Significant progress has been made in the design of high-performance bifunctional electrocatalysts,the development of novel oxygen electrode architectures,and the in-depth understanding of electrocatalytic mechanisms through combined experimental and computational studies.This work provides a comprehensive review of recent advancements in design strategies for oxygen catalysts,including homogeneous electrodes,asymmetric electrodes,and biomimetic electrodes,are thoroughly discussed and summarized.Then,the advanced catalyst modification strategies for ORR/OER are summarized,focusing on critical factors such as enhancement effect of metal/nonmental and synergistic enhancement effect in multiple catalyst.Subsequently,a representative performance evaluation is presented,based on the reported oxygen electrodes used in rechargeable metal-air battery applications.By focusing on these key areas,the review outlines the current challenges and future prospects for the development of bifunctional oxygen electrocatalysts,aiming to guide the design of high-performance bifunctional electrocatalysts and to elucidate the underlying mechanisms involved.展开更多
Photosynthesis of H_(2)O_(2)via sustainable biomass-derived carbon catalysts facilitate the conversion of renewable resources into valuable chemicals.However,the regulatory function of surface functional groups over r...Photosynthesis of H_(2)O_(2)via sustainable biomass-derived carbon catalysts facilitate the conversion of renewable resources into valuable chemicals.However,the regulatory function of surface functional groups over reaction kinetics has not been sufficiently investigated.Herein,hydrothermal carbon spheres(CS)rich in oxygencontaining functional groups demonstrated a remarkably high H_(2)O_(2)production rate(653μmol/(g·h))in both pure water and actual seawater,even in the absence of any sacrificial agent.Meanwhile,the catalyst demonstrates outstanding activity(92%conversion and>99%selectivity)in the visible-light-driven photocatalytic oxidation of benzylamine to imines.Comprehensive analysis reveals that CS was rich in surface oxygen-containing functional groups,a feature strongly associated with its high photocatalytic efficiency.The observed positive Zeta potential of CS in seawater likely diminished the electrostatic repulsion against the positively charged intermediates,thereby facilitating their accumulation at the liquid-solid interface.This work proposes a strategic framework for developing metal-free photocatalysts from biomass,offering a sustainable pathway for photocatalytic applications.展开更多
Naphthalene,anthracene and pyridone endoperoxides are known to thermally release singlet oxygen.However,in the cycloreversion reaction,singlet oxygen is produced stoichiometrically;therefore,multiple singlet oxygen re...Naphthalene,anthracene and pyridone endoperoxides are known to thermally release singlet oxygen.However,in the cycloreversion reaction,singlet oxygen is produced stoichiometrically;therefore,multiple singlet oxygen releasing modules are expected to be very useful in inducing apoptosis of cancer cells.Herein,we present a potential therapeutic agent presenting three-pyridone endoperoxide modules and a mitochondria targeting group.Compared to previously reported pyridone-based monofunctional endoperoxides,the triple endoperoxide is highly effective as evidenced by assays and fluorescence microscopy.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
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
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
Long-afterglow photocatalytic technology offers promising potential fo r all-weather pollutant treatment,yet its efficiency is often constrained by competition between afterglow emission and photocatalytic reactions.T...Long-afterglow photocatalytic technology offers promising potential fo r all-weather pollutant treatment,yet its efficiency is often constrained by competition between afterglow emission and photocatalytic reactions.To address this,we developed a Pr^(3+)-doped Ca_(2)Al_(2)SiO_(7)(CASO)photocatalyst enriched with oxygen vacancies(V_(O)).The introduction of oxygen vacancies significantly increases trap concentration,enhancing both the intensity and du ration of the afterglow emission.A persulfate-assisted photo-Fenton system was designed based on V_(O)-CASO:Pr^(3+)enabling the self-activated degradation of tetracycline hydrochloride(TC)under ultraviolet afterglow.The photo-Fenton reaction consumes excess holes accumulated during the afterglow process,improving carrier utilization efficiency and mitigating rapid recombination.Additionally,persulfate addition can enrich reactive species and facilitate the Fe^(2+)/Fe^(3+)cycle.Benefiting from these synergistic effects,V_(O)-CASO:Pr^(3+)has achieved 75%TC degradation within1 h,significantly outperforming traditional systems.This study provides a new strategy for enhancing long-afterglow photocatalytic performance,paving the way for sustainable pollutant degradation technologies.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
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
Lithium-rich manganese-based cathode materials,as promising candidates for next-generation highenergy–density lithium-ion batteries due to their high specific capacity(>250 mAh g^(-1))and costeffectiveness,are lim...Lithium-rich manganese-based cathode materials,as promising candidates for next-generation highenergy–density lithium-ion batteries due to their high specific capacity(>250 mAh g^(-1))and costeffectiveness,are limited by severe capacity decay and voltage fade driven by irreversible structural transitions and oxygen release during cycling.Here,we report a Ti/Si dual-element modification strategy for cobalt-free Li_(1.2)Ni_(0.2)Mn_(0.6)O_(2)(LNMO)cathodes.The Ti/Si co-modified TS-LNMO cathode demonstrates superior structural stability and electrochemical performance.Bulk Ti^(4+)doping stabilizes the oxygen framework via robust Ti–O bonds and enhances the lattice oxygen redox reversibility,while an in situ formed Li_(2) SiO_(3) layer suppresses interfacial side reactions,enhances lithium-ion diffusion,and prevents HF-induced erosion.As a result,the TS-LNMO cathode achieves 90%capacity retention after 200 cycles at 0.5 C and maintains -80%capacity in full cells cycled to 4.8 V.Additionally,the TS-LNMO cathode exhibits impressive rate performance even at a high rate of 5 C.This work offers an effective strategy for advancing cobalt-free,high-performance lithium-rich cathodes for sustainable energy applications.展开更多
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.
基金Supported by the National Natural Science Foundation of China(52266008,52464057)Applied Basic Research Program of Yunnan Province(202301AT070067)the Yunnan Revitalization Talent Support Program Young Talent Project(XDYC-QNRC-2022-0060)。
文摘Chemical looping methane steam reforming(CL-MSR)has garnered significant attention owing to its ability to sequentially produce syngas with high selectivity and high-purity hydrogen through redox cycling.To overcome the limitations of single ironbased oxygen carriers,including poor cycling stability,low reactivity and susceptibility to sintering,this study employed a dipcoating method to modify Fe_(2)O_(3)/Al_(2)O_(3)oxygen carriers by incorporating three distinct metal additives:Cu,La and Ce.The composite oxygen carriers were systematically characterized and evaluated under redox conditions to investigate the structure-activity relationships between the physicochemical properties,reactivity,and hydrogen production performance.Results revealed that the spinel-phase CuFe_(2)O_(4)exhibited higher reactivity than the perovskite-phase LaFeO_(3)and CeO_(2),promoting the deeper reduction of Fe_(2)O_(3).Fe58Cu2Al exhibited an oxygen storage capacity as high as 6.5 mmol/g.During the CH4 reaction stage,Fe58Cu2Al achieved the highest oxygen loss of 12.1 g/100 g oxygen carrier,accompanied by a syngas yield of 5.15 mmol/g-1.33 times and 1.59 times greater than that of Fe60Al.In the hydrogen production stage,the 2%Cu-modified oxygen carrier demonstrated optimal performance,yielding 5.13 mmol/g of hydrogen,which was 1.51 times that of the pristine sample.Even after ten cycles,the H_(2)yield remained at 3.61 mmol/g,surpassing the single-cycle output of the pristine sample and the H2 purity consistently exceeded 98%.
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 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supported by the National Natural Science Foundation of China(No.22179032,51871088,51771068,52171176)the Natural Science Foundation of Hebei Province(No.B2021202011)。
文摘The primary challenge in rechargeable Zn-air batteries lies in developing a catalyst capable of simultaneously improving performance for oxygen reduction reaction(ORR)during discharge and oxygen evolution reaction(OER)during charge.Engineering spin configuration is essential for enhancing the intrinsic bifunctional activity and stability of spinel Co_(3)O_(4).Herein,Cr^(3+)is doped into Co_(3)O_(4),inducing directional distortion of CoO_6 octahedron to modify crystal field splitting energy,pushing Co_(Oh)toward intermediate-spin(IS)configuration(t_(2g)^(5)e_(g^(1)))with optimized eg occupancy of 1.04.As a result,9%Cr-Co_(3)O_(4)demonstrates an excellent bifunctional activity and remarkable rechargeable Zn-air battery performance that even outperforms Pt/C+RuO_(2).Density functional theory(DFT)studies reveal that IS Co_(Oh)not only regulates the adsorption energy of ORR/OER species but also transform the O_(2)adsorption configuration from end-on to Griffith configuration,thus modifies the mechanisms of both ORR and OER process and optimize bifunctional activity and selectivity.This work provides mechanistic insight into the spin origin of ORR/OER catalysis and highlights a promising strategy for developing robust bifunctional electrocatalysts.
基金supported by the National Natural Science Foundation of China(51872078,52272197,52572219)Heilongjiang Provincial Natural Science Foundation of China(LH2024E106)。
文摘High-entropy oxides(HEOs)derive their exceptional properties from the atomic-level homogenization of multiple constituent elements within the crystal lattice,which induces a sophisticated local environment that fundamentally reconfigures electron density distributions and coordination environment at active sites.However,the mechanisms by which multi-component systems in HEOs precisely regulate high-activity catalytic sites remain poorly understood.This work addresses this gap by designing medium-entropy perovskite oxides through the strategic incorporation of transition metals with distinct electronegativities and ionic radii,aiming to unravel how local environmental modifications impact the energy band location,coordination states,and adsorption behavior of the Co site.A family of A_(2)BO_(4)-type medium-entropy oxides PrSr(Fe_(0.2)Co_(0.2)Ni_(0.2)Cu_(0.2)M_(0.2))O_(4)(M=Sc,Cr,Mn)was successfully synthesized.Divergent atomic properties among Sc,Cr,and Mn(electronegativity,ionic size,and metal-oxygen bond strength)triggered pronounced electron redistribution,effectively tuning the d-band center of Co.Remarkably,Cr substitution significantly enhanced O_(2) adsorption at Co-active sites,as indicated by an elongated O-O bond length(1.234Å→1.279Å).Concurrently,Cr doping destabilized the M'-O-Cr bonds(M'=Fe,Co,Ni,Cu)and lowered the thermodynamic barrier for oxygen vacancy formation.Electrochemical tests revealed that PrSr(Fe_(0.2)Co_(0.2)Ni_(0.2)Cu_(0.2)Cr_(0.2))O_(4)(PSMO-Cr)exhibited the highest electrical conductivity and fastest oxygen surface exchange kinetics.At 700℃,the area-specific resistance(ASR)of the PSMO-Cr cathode was 0.07Ωcm^(2).Corresponding fuel cells achieved a maximum power density of 0.76 W cm^(-2).In electrolysis mode,the maximum current density reached 0.56 A cm^(-2) under 1.3 V at 700℃using PSMO-Cr as the anode.These results demonstrate that PSMO-Cr is a promising bifunctional catalyst for energy conversion applications.
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.
基金supported by the National Natural Science Foundation of China(22278021)State Key Laboratory of Chemical Engineering(No.SKL-ChE-23A01).
文摘Achieving high selectivity to 2,5-furandicarboxylic acid(FDCA)in the photocatalytic oxidation of 5-hydroxymethylfurfural(HMF)in aqueous solution advocates the principle of green and sustainable chemistry,but still remains a significant challenge.Herein,manipulating the reactive oxygen species(ROS)has been realized and dramatically promotes the selective photocatalytic oxidation of HMF in aqueous solution.A high FDCAyield of 98.6% has been achieved after 3 h of visible light irradiation over the as-prepared FeO_(x)-Au/TiO_(2) catalyst,being one of the leading photocatalytic performances.Furthermore,satisfactory FDCA yields of higher than 80%could be realized even in the outdoor environment under natural sunlight irradiation,regardless of sunny or cloudy weather.A combination study including physical characterization,kinetic analysis,radical trapping experiments and density functional theory calculations unveils the rate-determining step(oxidation of hydroxyl group)and respective contributions of the generated ROS(1O_(2) and·O_(2)-)in each step of the entire reaction network.The present work would push ahead the understanding of HMF photocatalytic oxidation and contribute to the rational design of high-performance photocatalysts.
基金Funded by the National Natural Science Foundation of China Guangdong(No.22279096)。
文摘Silica nanoparticles-stabilized cobalt and nitrogen-doped carbon materials were synthesized through pyrolysis of metal-organic-framework of ZIF-67 supported by silica nanoparticles.The experimental results reveal that the introduction of the silica nanoparticles can stabilize the microstructure of the derived CoN-C materials,which in turn exhibits the promising electrocatalytic activity towards both oxygen reduction and oxygen evolution reactions.The optimized sample exhibits a better oxygen reduction activity than commercial Pt/C catalyst as confirmed by the positive shift of half-wave potential by 20 mV while it has a low overpotential of 273 mV for oxygen evolution reactions with the retained performance over 80%after 25,000 s of continuous operation.It is demonstrated that the introduction of support frame might be an effective way to improve the activity and stability of metal-organic-framework derived electrocatalyst with stabilized microstructure.
基金financially supported by the National Natural Science Foundation of China(52302084)the National Key Research and Development Program of China(2022YFE0138900)+1 种基金Fundamental Research Funds for the Central Universities(2232025D-24)the Qin Shen Scholar Program of Jiaxing University。
文摘The development of economical,highly efficient,and stable bifunctional electrocatalysts for both the oxygen evolution reaction(OER)and the oxygen reduction reaction(ORR)remains a critical focus in advancing rechargeable metal-air battery systems.Significant progress has been made in the design of high-performance bifunctional electrocatalysts,the development of novel oxygen electrode architectures,and the in-depth understanding of electrocatalytic mechanisms through combined experimental and computational studies.This work provides a comprehensive review of recent advancements in design strategies for oxygen catalysts,including homogeneous electrodes,asymmetric electrodes,and biomimetic electrodes,are thoroughly discussed and summarized.Then,the advanced catalyst modification strategies for ORR/OER are summarized,focusing on critical factors such as enhancement effect of metal/nonmental and synergistic enhancement effect in multiple catalyst.Subsequently,a representative performance evaluation is presented,based on the reported oxygen electrodes used in rechargeable metal-air battery applications.By focusing on these key areas,the review outlines the current challenges and future prospects for the development of bifunctional oxygen electrocatalysts,aiming to guide the design of high-performance bifunctional electrocatalysts and to elucidate the underlying mechanisms involved.
基金Supported by the Natural Science Foundation of Shanxi Province(202203021222233,202203021212398,202203021212403)。
文摘Photosynthesis of H_(2)O_(2)via sustainable biomass-derived carbon catalysts facilitate the conversion of renewable resources into valuable chemicals.However,the regulatory function of surface functional groups over reaction kinetics has not been sufficiently investigated.Herein,hydrothermal carbon spheres(CS)rich in oxygencontaining functional groups demonstrated a remarkably high H_(2)O_(2)production rate(653μmol/(g·h))in both pure water and actual seawater,even in the absence of any sacrificial agent.Meanwhile,the catalyst demonstrates outstanding activity(92%conversion and>99%selectivity)in the visible-light-driven photocatalytic oxidation of benzylamine to imines.Comprehensive analysis reveals that CS was rich in surface oxygen-containing functional groups,a feature strongly associated with its high photocatalytic efficiency.The observed positive Zeta potential of CS in seawater likely diminished the electrostatic repulsion against the positively charged intermediates,thereby facilitating their accumulation at the liquid-solid interface.This work proposes a strategic framework for developing metal-free photocatalysts from biomass,offering a sustainable pathway for photocatalytic applications.
基金supported by the National Natural Science Foundation of China(22007008,22178048).
文摘Naphthalene,anthracene and pyridone endoperoxides are known to thermally release singlet oxygen.However,in the cycloreversion reaction,singlet oxygen is produced stoichiometrically;therefore,multiple singlet oxygen releasing modules are expected to be very useful in inducing apoptosis of cancer cells.Herein,we present a potential therapeutic agent presenting three-pyridone endoperoxide modules and a mitochondria targeting group.Compared to previously reported pyridone-based monofunctional endoperoxides,the triple endoperoxide is highly effective as evidenced by assays and fluorescence microscopy.
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 Korea Institute for Advancement of Technology (KIAT)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Project supported by the National Natural Science Foundation of China(12374181)Fundamental Research Funds for Public Universities in Liaoning(LJ212410140035,LJ212410140037,LJ212410140048)+2 种基金Shenyang Science and Technology Bureau(22-315-6-06)General Project of the Department of Education of Liaoning Province(LJKZ0084)Liaoning Province Science and Technology Plan Joint Program(Natural Science Foundation General Project,2024-MSLH-188)。
文摘Long-afterglow photocatalytic technology offers promising potential fo r all-weather pollutant treatment,yet its efficiency is often constrained by competition between afterglow emission and photocatalytic reactions.To address this,we developed a Pr^(3+)-doped Ca_(2)Al_(2)SiO_(7)(CASO)photocatalyst enriched with oxygen vacancies(V_(O)).The introduction of oxygen vacancies significantly increases trap concentration,enhancing both the intensity and du ration of the afterglow emission.A persulfate-assisted photo-Fenton system was designed based on V_(O)-CASO:Pr^(3+)enabling the self-activated degradation of tetracycline hydrochloride(TC)under ultraviolet afterglow.The photo-Fenton reaction consumes excess holes accumulated during the afterglow process,improving carrier utilization efficiency and mitigating rapid recombination.Additionally,persulfate addition can enrich reactive species and facilitate the Fe^(2+)/Fe^(3+)cycle.Benefiting from these synergistic effects,V_(O)-CASO:Pr^(3+)has achieved 75%TC degradation within1 h,significantly outperforming traditional systems.This study provides a new strategy for enhancing long-afterglow photocatalytic performance,paving the way for sustainable pollutant degradation technologies.
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supported by the National Natural Science Foundation of China(22379084)Department of Science and Technology of Guangdong Province(211233812024)Shenzhen Science and Technology Program(JCYJ20220818101007016,KJZD20240903101303005)。
文摘Lithium-rich manganese-based cathode materials,as promising candidates for next-generation highenergy–density lithium-ion batteries due to their high specific capacity(>250 mAh g^(-1))and costeffectiveness,are limited by severe capacity decay and voltage fade driven by irreversible structural transitions and oxygen release during cycling.Here,we report a Ti/Si dual-element modification strategy for cobalt-free Li_(1.2)Ni_(0.2)Mn_(0.6)O_(2)(LNMO)cathodes.The Ti/Si co-modified TS-LNMO cathode demonstrates superior structural stability and electrochemical performance.Bulk Ti^(4+)doping stabilizes the oxygen framework via robust Ti–O bonds and enhances the lattice oxygen redox reversibility,while an in situ formed Li_(2) SiO_(3) layer suppresses interfacial side reactions,enhances lithium-ion diffusion,and prevents HF-induced erosion.As a result,the TS-LNMO cathode achieves 90%capacity retention after 200 cycles at 0.5 C and maintains -80%capacity in full cells cycled to 4.8 V.Additionally,the TS-LNMO cathode exhibits impressive rate performance even at a high rate of 5 C.This work offers an effective strategy for advancing cobalt-free,high-performance lithium-rich cathodes for sustainable energy applications.
