The exploration of high-performance near-infrared phosphors has attracted widespread attention.In this work,a brand new Rb2LiAlF6:Cr^(3+)(denoted as RLAF:Cr)phosphor has been constructed by the substitution of Al^(3+)...The exploration of high-performance near-infrared phosphors has attracted widespread attention.In this work,a brand new Rb2LiAlF6:Cr^(3+)(denoted as RLAF:Cr)phosphor has been constructed by the substitution of Al^(3+)ions with Cr^(3+)ions.Evidence shows that two sets of near-infrared emission bands,which originated from two types of Cr^(3+)sites,were observed upon blue light excitation.These emission bands merged into a wide emission band locating in the region of 650 nm-1050 nm,with a full width at half maximum(FWHM)of 125 nm.In addition,a high quantum efficiency of 77.7%and an excellent thermal stability at 417 K,with a retention rate of 90.5% of that at room temperature(RT),were witnessed.Profiting from the luminescence properties of the NIR phosphor,clear images of biological tissues and human palm veins were obtained using a light-emitting diode(LED)as a lighting source,which was constructed using an RLAF:Cr phosphor and a blue InGaN chip.These images showed the large potential of the RLAF:Cr phosphor for night vision and bioimaging in LED devices.展开更多
The mounting challenges of global energy shortage and climate change call for the development of low-cost and high performance energy storage systems.Here,we propose the facile preparation of a 3D sponge electrode mat...The mounting challenges of global energy shortage and climate change call for the development of low-cost and high performance energy storage systems.Here,we propose the facile preparation of a 3D sponge electrode material by the uniform deposition of NiMoO_(4)nanorods on a carbonized melamine sponge(CMS)during a solvothermal reaction.Under the templating of a macroporous CMS backbone,the obtained 3D hierarchical NiMoO_(4)/CMS composite sponge can offer numerous electrochemical sites for faradaic redox reactions and also provide interconnected conducting carbon networks for direct and rapid charge transfer.展开更多
Structural collapse and aggregation during the annealing process are the key obstacles for MOF-derived electrocatalysts,which will lead to a decrease in the active site density and stability of the electrocatalyst.The...Structural collapse and aggregation during the annealing process are the key obstacles for MOF-derived electrocatalysts,which will lead to a decrease in the active site density and stability of the electrocatalyst.The atomic layer deposition(ALD)technique can form dense and uniform thin films wrapping any complex 3D structure due to the self-limiting surface chemistry reactions.Herein,we developed a confinement strategy based on the ALD technique to prepare a durable Fe2Ni MIL 88-derived electrocatalyst(NiFe/NC@Al_(2)O_(3)-2).Due to the protection of the Al_(2)O_(3) layer deposited by the ALD technique,the asprepared catalyst retained the original rod-like structure of MIL 88 after the annealing process.With the confinement effect of the Al_(2)O_(3) nanolayer,the optimized NiFe/NC@Al_(2)O_(3)-2 exhibited remarkable electrocatalytic properties in the oxygen evolution reaction(OER)with low overpotentials of 270 and 391 mV at 10 and 100 mA cm^(-2),respectively.Furthermore,the catalyst obtained an excellent durability over 100 hours at a high current density of 50 mA cm^(-2),which is superior to those of many previously reported NiFe-based electrocatalysts.The ALD-assisted confinement strategy highlights a novel method to synthesize structure-and morphology-retained MOF-derived catalysts with excellent activity and stability at high current densities.展开更多
Directional catalytic transformation of volatile organic compounds(VOCs)into value-added chemicals represents a more sustainable strategy than complete mineralization,as it simultaneously mitigates environmental pollu...Directional catalytic transformation of volatile organic compounds(VOCs)into value-added chemicals represents a more sustainable strategy than complete mineralization,as it simultaneously mitigates environmental pollution and reduces carbon emissions.The primary challenge in achieving multifunctional olefin production from alcohol-type VOCs is the lack of mechanistic clarity,which hinders the targeted synthesis of selective catalysts.Herein,we developed W-Ti hybrid metal oxide catalysts(WTiO_(x))with active Ti-O-W interfaces via a one-step hydrothermal synthesis and demonstrated their effectiveness for isopropanol conversion processes.Remarkably,WTiO_(x)-500 achieved 99.8%isopropanol conversion and 99.3% propylene yield at 140℃,significantly outperforming TiO_(2)(98.4% yield at 180℃)and WO_(3)(90.5% yield at 240℃).WTiO_(x)-500 also displayed higher thermal stability,with isopropanol conversion and propylene yield decreasing by 1.0%and 1.6% after 35 h on-stream reaction.Although impurities(e.g.,CO_(2),HCl,SO_(2))caused partial deactivation of WTiO_(x)-500,oxygen treatment regenerated the catalyst.A series of characterization techniques indicated that the controlled calcination temperature promoted the formation of an optimal Ti-O-Winterface in WTiO_(x)-500 through W substitution into the TiO_(2)lattice and WO_(3)-TiO_(2)surface interaction,where W species effectively tuned the electronic structure.This configuration endowed WTiO_(x)-500 with moderate acidity of BrФnsted(-OH)and Lewis(Ti^(4+)/W^(6+))acid sites,which synergistically facilitated charge transfer between isopropanol and catalyst,accelerated C-O bond cleavage during dehydration.This work provides mechanistic insights into isopropanol dehydration and demonstrates a potential approach for VOC valorization.展开更多
Investigating structural and hydroxyl group effects in electrooxidation of alcohols to value-added products by solid-acid electrocatalysts is essential for upgrading biomass alcohols.Herein,we report efficient electro...Investigating structural and hydroxyl group effects in electrooxidation of alcohols to value-added products by solid-acid electrocatalysts is essential for upgrading biomass alcohols.Herein,we report efficient electrocatalytic oxidations of saturated alcohols(C_(1)-C_(6))to selectively form formate using Ni Co hydroxide(Ni Co-OH)derived Ni Co_(2)O_(4)solid-acid electrocatalysts with balanced Lewis acid(LASs)and Brønsted acid sites(BASs).Thermal treatment transforms BASs-rich(89.6%)Ni Co-OH into Ni Co_(2)O_(4)with nearly equal distribution of LASs(53.1%)and BASs(46.9%)which synergistically promote adsorption and activation of OH-and alcohol molecules for enhanced oxidation activity.In contrast,BASs-enriched Ni Co-OH facilitates formation of higher valence metal sites,beneficial for water oxidation.The combined experimental studies and theoretical calculation imply the oxidation ability of C1-C6alcohols increases as increased number of hydroxyl groups and decreased HOMO-LUMO gaps:methanol(C_(1))<ethylene glycol(C_(2))<glycerol(C3)<meso-erythritol(C4)<xylitol(C5)<sorbitol(C6),while the formate selectivity shows the opposite trend from 100 to 80%.This study unveils synergistic roles of LASs and BASs,as well as hydroxyl group effect in electro-upgrading of alcohols using solid-acid electrocatalysts.展开更多
Tire-derived aggregate(TDA)is an engineered construction material produced from recycled scrap tires and is often used as a compressible layer overlying buried structures to reduce overburden loads.The potential ampli...Tire-derived aggregate(TDA)is an engineered construction material produced from recycled scrap tires and is often used as a compressible layer overlying buried structures to reduce overburden loads.The potential amplification of ground motion in a tunnel site is well understood,but the effect of the tunnel-TDA layer system on ground surface acceleration remains unclear.In this study,both linear and nonlinear dynamic analyses were performed to evaluate the contributions of a TDA layer to the acceleration amplification at the ground surface.The numerical model was calibrated using recorded data from a shaking table test and validated against the literature results,followed by extensive parametric studies.The mechanical and geometrical parameters investigated for the TDA layer included damping ratio,density,Young’s modulus,width,thickness,and depth.The predominant frequency and intensity level of input motions were also investigated.This study showed that the presence of the TDA layer provided an additional acceleration amplification effect.The amplification was more pronounced in areas above the tunnel,particularly for the wider and shallower TDA layer subjected to high frequency and low intensity input motions.展开更多
Background Goat milk is increasingly recognized for high digestibility and a distinctive compositional profile.Protein acetylation,an important post-translational modification,regulates biosynthetic and metabolic path...Background Goat milk is increasingly recognized for high digestibility and a distinctive compositional profile.Protein acetylation,an important post-translational modification,regulates biosynthetic and metabolic pathways.This study aimed to identify critical acetylated proteins and specific modification sites involved in milk production and component synthesis in dairy goats,thereby elucidating the molecular mechanisms of lactation.We performed a comparative TMT-based acetylomic and proteomic analysis of mammary tissues from Saanen dairy goats during peak lactation and the dry period using LC–MS/MS.A candidate acetylation site was further investigated in goat mammary epithelial cells(GMECs)through site-directed mutagenesis and lipid metabolic assays,establishing functional links between acetylation and mammary lipid metabolism and providing a foundation for molecular strategies to improve milk quality and yield.Results We established a comprehensive mammary acetylome,identifying 862 significantly acetylated proteins and 2,028 modification sites across the two physiological phases.Differentially acetylated proteins were predominantly localized to the cytoplasm(39.98%).From these,54 key acetylated proteins,including MTOR,BCAT2,QARS1,GOT1,GOT2,BDH1,ACSS1,STAT5B,FABP5,and GPAM were prioritized as candidates involved in milk protein synthesis,milk fat synthesis,lactose synthesis,and other lactation-related processes.Among them,β-hydroxybutyrate dehydrogenase 1(BDH1)acetylation was characterized in detail.Members of the HDAC family were identified as primary regulators mediating BDH1 deacetylation.BDH1 acetylation promoted lipid droplet formation and triglyceride synthesis in GMECs.At the transcriptional level,BDH1 acetylation upregulated LXRα,ACSL1 and SCD1,whereas deacetylation downregulated SCD1,FASN,and ACSL1.Notably,BDH1 acetylation/deacetylation significantly reduced SREBP1 expression,linking this modification to coordinated control of lipogenic gene networks.Conclusions This study established,for the first time,the comprehensive acetylome of mammary gland tissues in dairy goats,revealing a substantial number of differentially acetylated proteins and modification sites.We demonstrate that acetylation of BDH1 regulated by HDACs promotes lipid droplet biogenesis and triglyceride synthesis in GMECs through transcriptional modulation of key lipogenic genes and suppression of SREBP1.These findings provide mechanistic insights into the post-translational regulation of mammary lipid metabolism and offer molecular targets for future genetic and nutritional strategies aimed at enhancing milk quality and yield in dairy goats.展开更多
Polyimide-linkage covalent organic frameworks(PI-COFs),as a subclass of the COFs material family,featuring the unique combination of excellent thermal stability of polyimide,tunable pore sizes,as well as high crystall...Polyimide-linkage covalent organic frameworks(PI-COFs),as a subclass of the COFs material family,featuring the unique combination of excellent thermal stability of polyimide,tunable pore sizes,as well as high crystallinity and surface area of COFs,are expected to be a novel type of promising crystalline porous material with potential applications in adsorption and separation,catalysis,chemical sensing,and energy storage.Therefore,it is increasingly important to summarize polyimide-linkage in COFs and related applications and provide in-depth insight to accelerate future development.In this review,we offer a comprehensive overview of recent advancements in PI-COFs,emphasizing their synthesis methods,design principles and applications.Finally,our brief outlooks on the current challenges and future developments of PI-COFs are provided.Overall,this review aims to guide the recent and future development of PI-COFs.展开更多
Peroxymonosulfate(PMS)-based advanced oxidation technology has been proven to be a viable option for the decontamination of organic pollutants from water bodies.Advanced catalyst design is essential to this technology...Peroxymonosulfate(PMS)-based advanced oxidation technology has been proven to be a viable option for the decontamination of organic pollutants from water bodies.Advanced catalyst design is essential to this technology.Herein,a vanadium-doped LaFeO_(3) perovskite(LFO-V)featuring asymmetric Fe-O-V sites was rationally designed.Thanks to orbital electron interaction between Fe and V atoms,the modified electronic structure elevated electron density near the Fermi energy level while reducing the energy barrier toward effective PMS activation.This facilitated concurrent PMS reduction at the Fe sites to generate SO_(4)^(·-)and·OH(57.7%),and PMS oxidation at V sites to produce ^(1)O_(2)(42.3%).The LFO-V/PMS system demonstrated excellent tetracycline(TC)degradation performance with a 2-fold enhancement in rate constant compared to that of pristine LFO.Further,the LFO-V maintained long-term stability,and the toxicity of degradation intermediates was evaluated through microbial metabolomics.This work establishes an effective route to regulate the PMS activation pathways through precise electronic structure modulation,advancing the rational design of advanced Fenton-like catalysts.展开更多
Methanol steam reforming(MSR)represents a promising route for hydrogen production,leveraging the high energy density and liquid-phase storage advantages of methanol.Copper-based catalysts have become indispensable for...Methanol steam reforming(MSR)represents a promising route for hydrogen production,leveraging the high energy density and liquid-phase storage advantages of methanol.Copper-based catalysts have become indispensable for MSR due to their cost-effectiveness,exceptional catalytic activity,and tunable selectivity.However,persistent challenges such as thermal sintering,undesirable CO byproduct formation,diminished low-temperature reactivity,and long-term catalyst deactivation limit their broad industrial deployment.This review comprehensively examines the mechanistic pathways of MSR over Cu-based catalysts,with particular focus on differentiating catalyst formulations optimized for high-temperature(>200°C)versus low-temperature(<200°C)operation.It highlights the decisive influence of Cu nanoparticle size,electronic structure,and crystal structure on catalytic performance.Cutting-edge design strategies,including multi-element engineering,innovative synthesis techniques,and deactivation mitigation,are critically evaluated to elucidate mechanistic connections between atomic-scale structure and catalytic performance enhancement.Finally,industrial applications of commercial Cu/ZnO/Al_(2)O_(3)variants and their scalability challenges are discussed,alongside prospective strategies for catalyst innovation and engineering to advance next-generation hydrogen production.展开更多
Petroleum leakage is a major groundwater contamination source,with chemical composition of water soluble fractions(WSFs)from diverse oil sources significantly impacting groundwater quality and source identification.Th...Petroleum leakage is a major groundwater contamination source,with chemical composition of water soluble fractions(WSFs)from diverse oil sources significantly impacting groundwater quality and source identification.The aim of this study was to assess impact of 15 diverse oils on groundwater quality and environmental forensics based on oil-water equilibrium experiments.Our results indicate that contamination of groundwater by gasoline and naphtha is primarily attributed to volatile hydrocarbons,while pollution from diesel,kerosene,and crude oil is predominantly from non-hydrocarbons.Rapid determination of the extent of non-hydrocarbon pollution in WSFs was achieved through a new quantitative index.Gasoline and naphtha exhibited the highest groundwater contamination potential while kerosene and light crude oils were also likely to cause groundwater contamina-tion.Although volatile hydrocarbons in the WSFs of diesel and jet fuel do not easily exceed current regulatory standards,unregulated non-hydrocarbons may pose a more severe contamination risk to groundwater.Notably,the presence of significant benzene and toluene,hydrogenation and alkylation products(e.g.,C4-C5 alkylben-zenes,alkylindenes,alkyltetralins,and dihydro-indenes),cycloalkanes in WSFs can effectively be utilized for preliminary source identification of light distillates,middle distillates,and crude oils,respectively.展开更多
Overcoming kinetic limitations in the acidic oxygen reduction reaction(ORR)demands Pt-based catalysts with optimized surface adsorption.Herein,we engineer hierarchical PtPd dendrite nanocrystals(PtPd NDs)featuring pre...Overcoming kinetic limitations in the acidic oxygen reduction reaction(ORR)demands Pt-based catalysts with optimized surface adsorption.Herein,we engineer hierarchical PtPd dendrite nanocrystals(PtPd NDs)featuring precisely tailored asymmetric sites and high-index facets(HIFs)to overcome the kinetic limitations in acidic media.Controlled Pd incorporation disrupts symmetry of the single-oriented crystal plane,generating inhomogeneous strain and promoting HIFs exposure.This synergistic structural engineering optimizes the adsorption/desorption of oxygen-containing intermediates,significantly accelerating ORR kinetics.Consequently,PtPd NDs deliver exceptional mass activity(MA=1.37 A mg_(Pt)^(-1),11.42 times higher than Pt/C)and remarkable stability(83.9%MA retention after durability testing).In H_(2)-Air fuel cells,PtPd NDs also achieve higher peak power density versus Pt/C cathodes.In situ synchrotron radiation infrared spectroscopy and theoretical studies reveal that the synergistic effect between asymmetric sites and HIFs stimulates the strain field and causes a downward shift in the d-band center,thereby lowering the*OOH formation barrier and weakening intermediate adsorption,directly boosting the ORR performance.This work underscores the critical role of facet and site engineering in designing high-performance fuel cell electrocatalysts.展开更多
If you're tired of megacities that feel like nothing but glass,steel,and constant rush,Guangzhou moves at its own pace.Here,a 19th-century ancestral hall stands next to a 600-meter tower,and the day begins with te...If you're tired of megacities that feel like nothing but glass,steel,and constant rush,Guangzhou moves at its own pace.Here,a 19th-century ancestral hall stands next to a 600-meter tower,and the day begins with tea and delicate steamed treats instead of coffee.展开更多
Endogenous hydrogen systems,consisting of metal–organic coordination catalysts and alcohols,have been widely applied for the transfer hydrogenation(TH)of biomass-derived carbonyl compounds in recent years.Metal-organ...Endogenous hydrogen systems,consisting of metal–organic coordination catalysts and alcohols,have been widely applied for the transfer hydrogenation(TH)of biomass-derived carbonyl compounds in recent years.Metal-organic coordination catalysts showed satisfactory ability of TH in the secondary alcohols,but most of them could not effectively employ the cheaper primary alcohols as hydrogen donors.Furthermore,they commonly contained high metal contents,which also led to low catalytic efficiency in significant measure.In this work,we constructed a novel magnesium single-atom catalyst(Mg-NC)with merely 0.37 wt%Mg by means of a combined self-assembly and pyrolysis strategy.The characterization results indicated that Mg was atomically dispersed and it was coordinated with four pyridinic-N in Mg-NC.Due to the obvious electron transfer from Mg to its coordinated pyridinic-N,Mg–N_(4)active centers displayed high Lewis acid-base strength with abundant content,which brought remarkable catalytic activity.When Mg-NC was used for the TH of 5-hydroxymethylfurfural(HMF)in ethanol(EtOH),2,5-bis(hydroxymethyl)furan(BHMF)yield was up to 96.3%with high productivity of 19.85 molBHMF mol_(Mg)^(−1)h^(−1)at 150°C for 5 h.More interestingly,the process of TH over Mg-NC in EtOH was proved to proceed via the hydrogen radical mechanism.Additionally,Mg-NC exhibited powerful catalytic universality;it could not only utilize other primary alcohols(such as n-propanol and n-butanol)as hydrogen donors,but also catalyze the TH of other carbonyl compounds(such as furfural,5-methylfurfural,benzaldehyde,cyclohexanone,and levulinic acid).Overall,this work offered some important clues and references to reinforce the hydrogen-supplying ability of primary alcohols in the TH of various biomass-derived carbonyl compounds to high-value fine chemicals.展开更多
Doping metal ions offer a promising strategy to tune the intrinsic and surface properties of BiVO_(4)for enhanced photoelectrochemical(PEC)activity.Given this,experimental and theoretical studies on cadmium(Cd)doping ...Doping metal ions offer a promising strategy to tune the intrinsic and surface properties of BiVO_(4)for enhanced photoelectrochemical(PEC)activity.Given this,experimental and theoretical studies on cadmium(Cd)doping to BiVO_(4)photoanode were studied for PEC water splitting applications.The spectroscopic and PEC results indicate that the substitution of Cd at Bi lattice sites causes the reduction in the valence state of V^(5+)to V4+that creates hole trap states below the Fermi level of BiVO_(4).The introduced hole trap states at the BiVO_(4)surface suppress the charge recombination and provide effective hole transfer sites for the facile water oxidation reactions.The CdBiVO_(4)exhibited significantly higher photocurrent compared to the pristine BiVO_(4)reaching 3.5 mA cm^(-2)(with a hole scavenger)at 1.23 V vs RHE.Furthermore,doping increases the carrier density in the bulk of BiVO_(4)leading to improved charge separation,and charge transfer while reducing the hole transfer resistance at the interface.The Cd-doped BiVO_(4)exhibited a charge separation efficiency of 80%and with a 90%of overall water splitting faradaic efficiency.Importantly,the results of this work propose the advantages of doping metal ions at Bi lattice sites in BiVO_(4)for improved PEC activity.展开更多
Aqueous zinc(Zn)metal batteries are restricted due to Zn anodes facing notorious Zn dendrites and water-induced side reactions,which impede cycle performance.Herein,a zincophilic-hydrophobic interface layer is fabrica...Aqueous zinc(Zn)metal batteries are restricted due to Zn anodes facing notorious Zn dendrites and water-induced side reactions,which impede cycle performance.Herein,a zincophilic-hydrophobic interface layer is fabricated via an electrospinning method,where zincophilic silver(Ag)nanoparticles are evenly anchored in the hydrophobic polyvinylidene fluoride fiber matrix(Ag@PVDF),aiming to stabilize the Zn anode.The zincophilic nanoparticles can act as Zn nucleation sites and balance the interfacial electric field,ensuring a homogenous Zn deposition.Meanwhile,the hydrophobic fiber framework can prevent water-induced side reactions and modulate the Zn ion flux distribution.Consequently,the Ag@PVDF-Zn//Ag@PVDF-Zn symmetric cell delivers a superior lifespan over 2600 h(1.0 mA cm^(-2),1.0 mAh cm^(-2)).In addition,based on the stable Ag@PVDF-Zn anode,the Ag@PVDF-Zn//I_(2) full cell delivers84.3%capacity retention after 800 cycles at 2.0 C,and the aqueous Zn ion hybrid supercapacitor maintains a stable cycling performance over 15,000 cycles.This work highlights zincophilic-hydrophobic interface engineering to enable robust Zn anodes.展开更多
Objectives:Phosphodiesterase 1A(PDE1A)regulates intracellular cyclic nucleotide signaling and has been implicated in tumor progression,but its clinical relevance and functional role in epithelial ovarian cancer(EOC),p...Objectives:Phosphodiesterase 1A(PDE1A)regulates intracellular cyclic nucleotide signaling and has been implicated in tumor progression,but its clinical relevance and functional role in epithelial ovarian cancer(EOC),particularly in relation to the response to platinum remain unclear.This study aimed to evaluate the clinical significance of PDE1A in EOG and to clarify its functional role in tumor progression and response to platinum-based chemotherapy.Methods:PDE1A mRNA and protein levels were analyzed using public databases,RNA sequencing,and immunohistochemistry.Correlations between PDE1A expression,clinicopathological features,and prognosis were assessed.Functional roles were investigated in ovarian cancer cell lines.Results:PDE1A was significantly overexpressed in EOC tissues compared with that in normal ovarian epithelial tissues.Overexpression correlated with advanced International Federation of Gynecology and Obstetrics(FIGO)stage,poor tumor grade,and reduced response to platinum-based chemotherapy.High PDE1A levels were linked to worse disease-free survival and overall survival,and multivariate analysis confirmed PDE1A as an independent prognostic factor.To elucidate its functional role,we performed in vitro experiments showing that PDE1A knockdown suppressed cell proliferation and colony formation,induced G1 arrest,and downregulatedβ-catenin signaling with reduced cyclin D1 and c-Myc expression.Notably,these inhibitory effects were partially rescued by lithium chloride(LiCl),a Wingless-related integration site(Wnt)/β-catenin activator.Conclusions:In conclusion,our findings identify PDE1A as a Wnt/β-catenin-linked biomarker of tumor progression and platinum resistance in EOC and provide a biological rationale for further investigation of PDE1A-targeted strategies in preclinical models.展开更多
Co-free Li-rich Li_(1.2)Ni_(0.2)Mn_(0.6)O_(2)(LR)cathode shows the highest working capacity that can be applied to high-energy density Li-ion batteries(LIBs).However,poor cycle stability and voltage decay caused by ph...Co-free Li-rich Li_(1.2)Ni_(0.2)Mn_(0.6)O_(2)(LR)cathode shows the highest working capacity that can be applied to high-energy density Li-ion batteries(LIBs).However,poor cycle stability and voltage decay caused by phase transition are always hindering its further development.Herein,a novel medium-entropy Li-rich Mn-based cathode material(LRMEF)was synthesized via a simple sol-gel method.The introduction of multivalent ions(Al^(3+)/Cu^(2+)doping at Mn sites and F−doping at O sites)effectively mitigates the Jahn-Teller distortion of Mn ions and suppresses oxygen release.High-angle annular dark-field scanning transmission electron microscopy(HAADF-STEM)images confirm that this synergistic doping strategy induces the in-situ formation of an approximately 3 nm-thick spinel surface layer,which significantly enhances structural stability and ion diffusion kinetics.Besides,a series of in-situ/ex-situ characterization methods and density functional theory(DFT)calculations have been carried out to fundamentally shed light on the optimized structure-activity relationship and reaction mechanism.As a result,the LR material with entropy regulation and anion doping exhibits excellent cycling stability(189.2 mAh g^(−1)at 1 C with 84%capacity retention after 300 cycles),rate performance(164.1 mAh g^(−1)at 5 C),and voltage retention(82.7%at 1 C after 300 cycles),demonstrating great application prospects in future high-energy-density LIBs.展开更多
Large-scale CO_(2)emissions have exacerbated the greenhouse effect,reinforcing the critical need for efficient CO_(2)mitigation methods.Plasma-catalytic technology enables CO_(2)conversion under mild conditions,especi...Large-scale CO_(2)emissions have exacerbated the greenhouse effect,reinforcing the critical need for efficient CO_(2)mitigation methods.Plasma-catalytic technology enables CO_(2)conversion under mild conditions,especially for CO_(2)methanation(the Sabatier reaction),which has attracted significant attention due to its economic benefits and the potential for safe energy transportation via existing natural gas pipelines.The development of high-performance CO_(2)methanation catalysts remains an ongoing and long-term objective,and there is a lack of adequate in-situ characterization techniques to investigate the mechanisms.This study focuses on the Ni/La_(2)O_(3)(LN)catalyst and introduces two CO_(2)activation strategies through F and Na modifications:the Ni-Ov-Ni site activation with electron transfer from Ni0 under low-power conditions and basic site activation under high-power conditions.The LN-NaF catalysts enhance CO_(2)methanation activity across the entire power range compared to LN,achieving a CO_(2)conversion of 86.3%and CH4 selectivity of 99.4%.Additionally,LN-F(h)reaches a CH4 yield 4.15 times higher than that of LN at low power.Furthermore,in-situ diffuse reflectance infrared Fourier transform(DRIFT)spectroscopy with a self-made reactor are performed under plasma-catalytic conditions to reveal the CO_(2)adsorption and conversion mechanisms,indicating that different dopants(F,Na,and NaF)exhibit promoting effects on different intermediates,resulting in variations in CO_(2)methanation activity.This study provides valuable insights for improving catalyst performance and a thorough comprehension of mechanisms in CO_(2)methanation.展开更多
The oxygen evolution reaction(OER)suffers from sluggish kinetics,necessitating efficient electrocatalysts to reduce overpotentials in water splitting.Currently recognized OER mechanisms primarily include the adsorbate...The oxygen evolution reaction(OER)suffers from sluggish kinetics,necessitating efficient electrocatalysts to reduce overpotentials in water splitting.Currently recognized OER mechanisms primarily include the adsorbate evolution mechanism(AEM),lattice oxygen mechanism(LOM),and oxide path mechanism(OPM).Compared to AEM,limited by scaling relationships,and LOM,constrained by stability issues,the OPM offers a promising alternative by enabling direct O-O bond formation via dual active sites,thus bypassing^(*)OOH intermediates and lattice O involvement and achieving a balance between activity and durability.However,activating the OPM process requires precise control over the spatial and electronic structure of active sites,making the design of OPM-based catalysts challenging.While previous reviews have focused on homo/heteronuclear diatomic perspectives of OPM-based catalysts,it is urgent to systematically summarize design strategies to provide a rational reference for their development.Herein,a review of design strategies for OPM-based OER catalysts across three scales is comprehensively presented,including in-situ engineering,doping-enabled sites reconstruction,and introducing new sites for nanoparticles,direct synthesis or post-treatments for molecular catalysts,and doping or template strategies for atom pairs or arrays.The unique advantage of atom arrays is also highlighted,and their future research directions and possible strategies are discussed.This review provides a systematic summary and forward-looking perspectives for rationally designing high-performance OPM-based OER catalysts.展开更多
基金supported by the National Natural Science Foundation of China(grant nos.22365034,22065039,52272174 and U22A20135)the Yunnan Fundamental Research Projects(202101AT070072).
文摘The exploration of high-performance near-infrared phosphors has attracted widespread attention.In this work,a brand new Rb2LiAlF6:Cr^(3+)(denoted as RLAF:Cr)phosphor has been constructed by the substitution of Al^(3+)ions with Cr^(3+)ions.Evidence shows that two sets of near-infrared emission bands,which originated from two types of Cr^(3+)sites,were observed upon blue light excitation.These emission bands merged into a wide emission band locating in the region of 650 nm-1050 nm,with a full width at half maximum(FWHM)of 125 nm.In addition,a high quantum efficiency of 77.7%and an excellent thermal stability at 417 K,with a retention rate of 90.5% of that at room temperature(RT),were witnessed.Profiting from the luminescence properties of the NIR phosphor,clear images of biological tissues and human palm veins were obtained using a light-emitting diode(LED)as a lighting source,which was constructed using an RLAF:Cr phosphor and a blue InGaN chip.These images showed the large potential of the RLAF:Cr phosphor for night vision and bioimaging in LED devices.
基金financially supported by the National Natural Science Foundation of China for Youths(No.21704035)the China Postdoctoral Science Foundation(No.2017M610304)+3 种基金the Natural Science Foundation of Jiangsu Province for Youths(BK20170544)the University Natural Science Research of Jiangsu(No.17KJB430010)the Jiangsu Province Postdoctoral Science Foundation(1701065C)a project funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions.
文摘The mounting challenges of global energy shortage and climate change call for the development of low-cost and high performance energy storage systems.Here,we propose the facile preparation of a 3D sponge electrode material by the uniform deposition of NiMoO_(4)nanorods on a carbonized melamine sponge(CMS)during a solvothermal reaction.Under the templating of a macroporous CMS backbone,the obtained 3D hierarchical NiMoO_(4)/CMS composite sponge can offer numerous electrochemical sites for faradaic redox reactions and also provide interconnected conducting carbon networks for direct and rapid charge transfer.
基金supported by the National Natural Science Foundation of China(21706090,51772135 and 51872124)the Ministry of Education of China(6141A02022516)+4 种基金the Natural Science Foundation of Guangdong Province(2014A030306010)the Natural Science Foundation of Guangzhou(201904010049)Jinan University(88016105)the Open Experimental Project by GETRC of Graphene-like Materials and Products(202001)the Fundamental Research Foundation for the Central Universities(21617326 and 11619103).
文摘Structural collapse and aggregation during the annealing process are the key obstacles for MOF-derived electrocatalysts,which will lead to a decrease in the active site density and stability of the electrocatalyst.The atomic layer deposition(ALD)technique can form dense and uniform thin films wrapping any complex 3D structure due to the self-limiting surface chemistry reactions.Herein,we developed a confinement strategy based on the ALD technique to prepare a durable Fe2Ni MIL 88-derived electrocatalyst(NiFe/NC@Al_(2)O_(3)-2).Due to the protection of the Al_(2)O_(3) layer deposited by the ALD technique,the asprepared catalyst retained the original rod-like structure of MIL 88 after the annealing process.With the confinement effect of the Al_(2)O_(3) nanolayer,the optimized NiFe/NC@Al_(2)O_(3)-2 exhibited remarkable electrocatalytic properties in the oxygen evolution reaction(OER)with low overpotentials of 270 and 391 mV at 10 and 100 mA cm^(-2),respectively.Furthermore,the catalyst obtained an excellent durability over 100 hours at a high current density of 50 mA cm^(-2),which is superior to those of many previously reported NiFe-based electrocatalysts.The ALD-assisted confinement strategy highlights a novel method to synthesize structure-and morphology-retained MOF-derived catalysts with excellent activity and stability at high current densities.
基金supported by the National Natural Science Foundation of China(U23A20120 and 22425601)National Key R&D Program of China(2023YFB3810801)+2 种基金Natural Science Foundation of Hebei Province(B2021208033)Beijing Nova Program(20240484659)R&D Program of Beijing Municipal Education Commission(KZ202210005011).
文摘Directional catalytic transformation of volatile organic compounds(VOCs)into value-added chemicals represents a more sustainable strategy than complete mineralization,as it simultaneously mitigates environmental pollution and reduces carbon emissions.The primary challenge in achieving multifunctional olefin production from alcohol-type VOCs is the lack of mechanistic clarity,which hinders the targeted synthesis of selective catalysts.Herein,we developed W-Ti hybrid metal oxide catalysts(WTiO_(x))with active Ti-O-W interfaces via a one-step hydrothermal synthesis and demonstrated their effectiveness for isopropanol conversion processes.Remarkably,WTiO_(x)-500 achieved 99.8%isopropanol conversion and 99.3% propylene yield at 140℃,significantly outperforming TiO_(2)(98.4% yield at 180℃)and WO_(3)(90.5% yield at 240℃).WTiO_(x)-500 also displayed higher thermal stability,with isopropanol conversion and propylene yield decreasing by 1.0%and 1.6% after 35 h on-stream reaction.Although impurities(e.g.,CO_(2),HCl,SO_(2))caused partial deactivation of WTiO_(x)-500,oxygen treatment regenerated the catalyst.A series of characterization techniques indicated that the controlled calcination temperature promoted the formation of an optimal Ti-O-Winterface in WTiO_(x)-500 through W substitution into the TiO_(2)lattice and WO_(3)-TiO_(2)surface interaction,where W species effectively tuned the electronic structure.This configuration endowed WTiO_(x)-500 with moderate acidity of BrФnsted(-OH)and Lewis(Ti^(4+)/W^(6+))acid sites,which synergistically facilitated charge transfer between isopropanol and catalyst,accelerated C-O bond cleavage during dehydration.This work provides mechanistic insights into isopropanol dehydration and demonstrates a potential approach for VOC valorization.
基金the financial support from the National Natural Science Foundation of China(52172110,52472231,52311530113)Shanghai"Science and Technology Innovation Action Plan"intergovernmental international science and technology cooperation project(23520710600)+1 种基金Science and Technology Commission of Shanghai Municipality(22DZ1205600)the Central Guidance on Science and Technology Development Fund of Zhejiang Province(2024ZY01011)。
文摘Investigating structural and hydroxyl group effects in electrooxidation of alcohols to value-added products by solid-acid electrocatalysts is essential for upgrading biomass alcohols.Herein,we report efficient electrocatalytic oxidations of saturated alcohols(C_(1)-C_(6))to selectively form formate using Ni Co hydroxide(Ni Co-OH)derived Ni Co_(2)O_(4)solid-acid electrocatalysts with balanced Lewis acid(LASs)and Brønsted acid sites(BASs).Thermal treatment transforms BASs-rich(89.6%)Ni Co-OH into Ni Co_(2)O_(4)with nearly equal distribution of LASs(53.1%)and BASs(46.9%)which synergistically promote adsorption and activation of OH-and alcohol molecules for enhanced oxidation activity.In contrast,BASs-enriched Ni Co-OH facilitates formation of higher valence metal sites,beneficial for water oxidation.The combined experimental studies and theoretical calculation imply the oxidation ability of C1-C6alcohols increases as increased number of hydroxyl groups and decreased HOMO-LUMO gaps:methanol(C_(1))<ethylene glycol(C_(2))<glycerol(C3)<meso-erythritol(C4)<xylitol(C5)<sorbitol(C6),while the formate selectivity shows the opposite trend from 100 to 80%.This study unveils synergistic roles of LASs and BASs,as well as hydroxyl group effect in electro-upgrading of alcohols using solid-acid electrocatalysts.
基金Natural Science Foundation of Hebei Province under Grant No.E2025201025,the Science Research Project of Hebei Education Department under Grant No.BJK2024121the Open Fund of Hebei Cangzhou Groundwater and Land Subsidence National Observation and Research Station under Grant No.CGLOS-2025-04+1 种基金the HBU Innovation Team for Multi-Disaster Prevention in Transportation Geotechnics under Grant No.IT2023C04the Research Fund for Talented Scholars of HBU under Grant No.521100221063。
文摘Tire-derived aggregate(TDA)is an engineered construction material produced from recycled scrap tires and is often used as a compressible layer overlying buried structures to reduce overburden loads.The potential amplification of ground motion in a tunnel site is well understood,but the effect of the tunnel-TDA layer system on ground surface acceleration remains unclear.In this study,both linear and nonlinear dynamic analyses were performed to evaluate the contributions of a TDA layer to the acceleration amplification at the ground surface.The numerical model was calibrated using recorded data from a shaking table test and validated against the literature results,followed by extensive parametric studies.The mechanical and geometrical parameters investigated for the TDA layer included damping ratio,density,Young’s modulus,width,thickness,and depth.The predominant frequency and intensity level of input motions were also investigated.This study showed that the presence of the TDA layer provided an additional acceleration amplification effect.The amplification was more pronounced in areas above the tunnel,particularly for the wider and shallower TDA layer subjected to high frequency and low intensity input motions.
基金supported by the National Key Research and Development Program of China(2022YFF1000102)Xi’an Agricultural Technology Research General Project(24NYGG0025)the National Natural Science Foundation of China(31702098)。
文摘Background Goat milk is increasingly recognized for high digestibility and a distinctive compositional profile.Protein acetylation,an important post-translational modification,regulates biosynthetic and metabolic pathways.This study aimed to identify critical acetylated proteins and specific modification sites involved in milk production and component synthesis in dairy goats,thereby elucidating the molecular mechanisms of lactation.We performed a comparative TMT-based acetylomic and proteomic analysis of mammary tissues from Saanen dairy goats during peak lactation and the dry period using LC–MS/MS.A candidate acetylation site was further investigated in goat mammary epithelial cells(GMECs)through site-directed mutagenesis and lipid metabolic assays,establishing functional links between acetylation and mammary lipid metabolism and providing a foundation for molecular strategies to improve milk quality and yield.Results We established a comprehensive mammary acetylome,identifying 862 significantly acetylated proteins and 2,028 modification sites across the two physiological phases.Differentially acetylated proteins were predominantly localized to the cytoplasm(39.98%).From these,54 key acetylated proteins,including MTOR,BCAT2,QARS1,GOT1,GOT2,BDH1,ACSS1,STAT5B,FABP5,and GPAM were prioritized as candidates involved in milk protein synthesis,milk fat synthesis,lactose synthesis,and other lactation-related processes.Among them,β-hydroxybutyrate dehydrogenase 1(BDH1)acetylation was characterized in detail.Members of the HDAC family were identified as primary regulators mediating BDH1 deacetylation.BDH1 acetylation promoted lipid droplet formation and triglyceride synthesis in GMECs.At the transcriptional level,BDH1 acetylation upregulated LXRα,ACSL1 and SCD1,whereas deacetylation downregulated SCD1,FASN,and ACSL1.Notably,BDH1 acetylation/deacetylation significantly reduced SREBP1 expression,linking this modification to coordinated control of lipogenic gene networks.Conclusions This study established,for the first time,the comprehensive acetylome of mammary gland tissues in dairy goats,revealing a substantial number of differentially acetylated proteins and modification sites.We demonstrate that acetylation of BDH1 regulated by HDACs promotes lipid droplet biogenesis and triglyceride synthesis in GMECs through transcriptional modulation of key lipogenic genes and suppression of SREBP1.These findings provide mechanistic insights into the post-translational regulation of mammary lipid metabolism and offer molecular targets for future genetic and nutritional strategies aimed at enhancing milk quality and yield in dairy goats.
基金supported by the National Key R&D Program of China(No.2023YFA1507204)National Natural Science Foundation ofChina(Nos.22475074,22171139,22225109,22302055)+4 种基金Natural Science Foundation of Guangdong Province(No.2023B1515020076)Key Scientific Research Project Plan of Colleges and Universities of Henan Province(No.24B150004)The Double Thousand Talents Plan of Jiangxi Province(No.jxsq2023102003)Project supported by the Guangdong Provincial Key Laboratory of Carbon Dioxide Resource Utilization(No.2024B121201001)Project supportedby the Major Research plan of the National Natural Science Foundation of China(No.92461310).
文摘Polyimide-linkage covalent organic frameworks(PI-COFs),as a subclass of the COFs material family,featuring the unique combination of excellent thermal stability of polyimide,tunable pore sizes,as well as high crystallinity and surface area of COFs,are expected to be a novel type of promising crystalline porous material with potential applications in adsorption and separation,catalysis,chemical sensing,and energy storage.Therefore,it is increasingly important to summarize polyimide-linkage in COFs and related applications and provide in-depth insight to accelerate future development.In this review,we offer a comprehensive overview of recent advancements in PI-COFs,emphasizing their synthesis methods,design principles and applications.Finally,our brief outlooks on the current challenges and future developments of PI-COFs are provided.Overall,this review aims to guide the recent and future development of PI-COFs.
基金supported by the National Natural Science Foundation of China(Nos.W2412093 and 52170068)the Fundamental Research Funds for the Central Universities(No.DUT24RC(3)079).
文摘Peroxymonosulfate(PMS)-based advanced oxidation technology has been proven to be a viable option for the decontamination of organic pollutants from water bodies.Advanced catalyst design is essential to this technology.Herein,a vanadium-doped LaFeO_(3) perovskite(LFO-V)featuring asymmetric Fe-O-V sites was rationally designed.Thanks to orbital electron interaction between Fe and V atoms,the modified electronic structure elevated electron density near the Fermi energy level while reducing the energy barrier toward effective PMS activation.This facilitated concurrent PMS reduction at the Fe sites to generate SO_(4)^(·-)and·OH(57.7%),and PMS oxidation at V sites to produce ^(1)O_(2)(42.3%).The LFO-V/PMS system demonstrated excellent tetracycline(TC)degradation performance with a 2-fold enhancement in rate constant compared to that of pristine LFO.Further,the LFO-V maintained long-term stability,and the toxicity of degradation intermediates was evaluated through microbial metabolomics.This work establishes an effective route to regulate the PMS activation pathways through precise electronic structure modulation,advancing the rational design of advanced Fenton-like catalysts.
基金supported by the National Natural Science Foundation of China(No.22208374)the Excellent Youth Scientist Award Foundation of Shandong Province(No.ZR2024YQ009)+2 种基金the Distinguished Young Scholars of the National Natural Science Foundation of China(No.22322814)CNPC Innovation Found(2022DQ02-0607)the Fundamental Research Funds for the Central Universities(No.24CX07006A).
文摘Methanol steam reforming(MSR)represents a promising route for hydrogen production,leveraging the high energy density and liquid-phase storage advantages of methanol.Copper-based catalysts have become indispensable for MSR due to their cost-effectiveness,exceptional catalytic activity,and tunable selectivity.However,persistent challenges such as thermal sintering,undesirable CO byproduct formation,diminished low-temperature reactivity,and long-term catalyst deactivation limit their broad industrial deployment.This review comprehensively examines the mechanistic pathways of MSR over Cu-based catalysts,with particular focus on differentiating catalyst formulations optimized for high-temperature(>200°C)versus low-temperature(<200°C)operation.It highlights the decisive influence of Cu nanoparticle size,electronic structure,and crystal structure on catalytic performance.Cutting-edge design strategies,including multi-element engineering,innovative synthesis techniques,and deactivation mitigation,are critically evaluated to elucidate mechanistic connections between atomic-scale structure and catalytic performance enhancement.Finally,industrial applications of commercial Cu/ZnO/Al_(2)O_(3)variants and their scalability challenges are discussed,alongside prospective strategies for catalyst innovation and engineering to advance next-generation hydrogen production.
基金supported by the National Science Foundation of China(Nos.42177042,and 42477051)the National Key R&D Program of China(No.2023YFC3708700)the Science Foundation of China University of Petroleum-Beijing(No.2462022QNXZ006).
文摘Petroleum leakage is a major groundwater contamination source,with chemical composition of water soluble fractions(WSFs)from diverse oil sources significantly impacting groundwater quality and source identification.The aim of this study was to assess impact of 15 diverse oils on groundwater quality and environmental forensics based on oil-water equilibrium experiments.Our results indicate that contamination of groundwater by gasoline and naphtha is primarily attributed to volatile hydrocarbons,while pollution from diesel,kerosene,and crude oil is predominantly from non-hydrocarbons.Rapid determination of the extent of non-hydrocarbon pollution in WSFs was achieved through a new quantitative index.Gasoline and naphtha exhibited the highest groundwater contamination potential while kerosene and light crude oils were also likely to cause groundwater contamina-tion.Although volatile hydrocarbons in the WSFs of diesel and jet fuel do not easily exceed current regulatory standards,unregulated non-hydrocarbons may pose a more severe contamination risk to groundwater.Notably,the presence of significant benzene and toluene,hydrogenation and alkylation products(e.g.,C4-C5 alkylben-zenes,alkylindenes,alkyltetralins,and dihydro-indenes),cycloalkanes in WSFs can effectively be utilized for preliminary source identification of light distillates,middle distillates,and crude oils,respectively.
基金supported by Yunnan Province Key Research and Development Program(202503AA080007)the Open Project of Yunnan Precious Metals Laboratory Co.,Ltd.(YPML-20240502051and YPML-2023050204)+1 种基金the National Natural Science Foundation of China(12405377)the Science and Technology Planning Project of Yunnan Province(202302AH360001)。
文摘Overcoming kinetic limitations in the acidic oxygen reduction reaction(ORR)demands Pt-based catalysts with optimized surface adsorption.Herein,we engineer hierarchical PtPd dendrite nanocrystals(PtPd NDs)featuring precisely tailored asymmetric sites and high-index facets(HIFs)to overcome the kinetic limitations in acidic media.Controlled Pd incorporation disrupts symmetry of the single-oriented crystal plane,generating inhomogeneous strain and promoting HIFs exposure.This synergistic structural engineering optimizes the adsorption/desorption of oxygen-containing intermediates,significantly accelerating ORR kinetics.Consequently,PtPd NDs deliver exceptional mass activity(MA=1.37 A mg_(Pt)^(-1),11.42 times higher than Pt/C)and remarkable stability(83.9%MA retention after durability testing).In H_(2)-Air fuel cells,PtPd NDs also achieve higher peak power density versus Pt/C cathodes.In situ synchrotron radiation infrared spectroscopy and theoretical studies reveal that the synergistic effect between asymmetric sites and HIFs stimulates the strain field and causes a downward shift in the d-band center,thereby lowering the*OOH formation barrier and weakening intermediate adsorption,directly boosting the ORR performance.This work underscores the critical role of facet and site engineering in designing high-performance fuel cell electrocatalysts.
文摘If you're tired of megacities that feel like nothing but glass,steel,and constant rush,Guangzhou moves at its own pace.Here,a 19th-century ancestral hall stands next to a 600-meter tower,and the day begins with tea and delicate steamed treats instead of coffee.
基金financially supported by the National Natural Science Foundation of China(U22A20421)the Qinglan Project of Jiangsu Province,the 533 Talent Program of Huaian City,and the College Students’Innovative Entrepreneurial Training Plan Program of Jiangsu Province(X202510323027).
文摘Endogenous hydrogen systems,consisting of metal–organic coordination catalysts and alcohols,have been widely applied for the transfer hydrogenation(TH)of biomass-derived carbonyl compounds in recent years.Metal-organic coordination catalysts showed satisfactory ability of TH in the secondary alcohols,but most of them could not effectively employ the cheaper primary alcohols as hydrogen donors.Furthermore,they commonly contained high metal contents,which also led to low catalytic efficiency in significant measure.In this work,we constructed a novel magnesium single-atom catalyst(Mg-NC)with merely 0.37 wt%Mg by means of a combined self-assembly and pyrolysis strategy.The characterization results indicated that Mg was atomically dispersed and it was coordinated with four pyridinic-N in Mg-NC.Due to the obvious electron transfer from Mg to its coordinated pyridinic-N,Mg–N_(4)active centers displayed high Lewis acid-base strength with abundant content,which brought remarkable catalytic activity.When Mg-NC was used for the TH of 5-hydroxymethylfurfural(HMF)in ethanol(EtOH),2,5-bis(hydroxymethyl)furan(BHMF)yield was up to 96.3%with high productivity of 19.85 molBHMF mol_(Mg)^(−1)h^(−1)at 150°C for 5 h.More interestingly,the process of TH over Mg-NC in EtOH was proved to proceed via the hydrogen radical mechanism.Additionally,Mg-NC exhibited powerful catalytic universality;it could not only utilize other primary alcohols(such as n-propanol and n-butanol)as hydrogen donors,but also catalyze the TH of other carbonyl compounds(such as furfural,5-methylfurfural,benzaldehyde,cyclohexanone,and levulinic acid).Overall,this work offered some important clues and references to reinforce the hydrogen-supplying ability of primary alcohols in the TH of various biomass-derived carbonyl compounds to high-value fine chemicals.
基金the support of the Natural Sciences and Engineering Research Council of Canada(NSERC)Tier 1 Canada Research Chair in Green Hydrogen Production,the Québec Ministère de l'Économie,de l'Innovation et de l'Énergie(MEIE)[Développement de catalyseurs et d'électrodes innovants,àfaibles coûts,performants et durables pour la production d'hydrogène vert,funding reference number 00393501]。
文摘Doping metal ions offer a promising strategy to tune the intrinsic and surface properties of BiVO_(4)for enhanced photoelectrochemical(PEC)activity.Given this,experimental and theoretical studies on cadmium(Cd)doping to BiVO_(4)photoanode were studied for PEC water splitting applications.The spectroscopic and PEC results indicate that the substitution of Cd at Bi lattice sites causes the reduction in the valence state of V^(5+)to V4+that creates hole trap states below the Fermi level of BiVO_(4).The introduced hole trap states at the BiVO_(4)surface suppress the charge recombination and provide effective hole transfer sites for the facile water oxidation reactions.The CdBiVO_(4)exhibited significantly higher photocurrent compared to the pristine BiVO_(4)reaching 3.5 mA cm^(-2)(with a hole scavenger)at 1.23 V vs RHE.Furthermore,doping increases the carrier density in the bulk of BiVO_(4)leading to improved charge separation,and charge transfer while reducing the hole transfer resistance at the interface.The Cd-doped BiVO_(4)exhibited a charge separation efficiency of 80%and with a 90%of overall water splitting faradaic efficiency.Importantly,the results of this work propose the advantages of doping metal ions at Bi lattice sites in BiVO_(4)for improved PEC activity.
基金(partially)funded by the BK21 FOUR Program of Graduate School,Kyung Hee University(GS-1-JO-ON-info2120241890)。
文摘Aqueous zinc(Zn)metal batteries are restricted due to Zn anodes facing notorious Zn dendrites and water-induced side reactions,which impede cycle performance.Herein,a zincophilic-hydrophobic interface layer is fabricated via an electrospinning method,where zincophilic silver(Ag)nanoparticles are evenly anchored in the hydrophobic polyvinylidene fluoride fiber matrix(Ag@PVDF),aiming to stabilize the Zn anode.The zincophilic nanoparticles can act as Zn nucleation sites and balance the interfacial electric field,ensuring a homogenous Zn deposition.Meanwhile,the hydrophobic fiber framework can prevent water-induced side reactions and modulate the Zn ion flux distribution.Consequently,the Ag@PVDF-Zn//Ag@PVDF-Zn symmetric cell delivers a superior lifespan over 2600 h(1.0 mA cm^(-2),1.0 mAh cm^(-2)).In addition,based on the stable Ag@PVDF-Zn anode,the Ag@PVDF-Zn//I_(2) full cell delivers84.3%capacity retention after 800 cycles at 2.0 C,and the aqueous Zn ion hybrid supercapacitor maintains a stable cycling performance over 15,000 cycles.This work highlights zincophilic-hydrophobic interface engineering to enable robust Zn anodes.
基金supported by the National Research Foundation of Korea(NRF)grant,funded by the Korean government(MIST),Jae-Hoon Kim(NRF-2020R1A2C2004782)Hanbyoul Cho(NRF-RS-2025-00522191)of Funderssupported by the Bio&Medical Technology Development Program of the National Research Foundation(NRF),funded by the Korean Government(MSIT),Jae-Hoon Kim of Funder(NRF-2017M3A9B 8069610).
文摘Objectives:Phosphodiesterase 1A(PDE1A)regulates intracellular cyclic nucleotide signaling and has been implicated in tumor progression,but its clinical relevance and functional role in epithelial ovarian cancer(EOC),particularly in relation to the response to platinum remain unclear.This study aimed to evaluate the clinical significance of PDE1A in EOG and to clarify its functional role in tumor progression and response to platinum-based chemotherapy.Methods:PDE1A mRNA and protein levels were analyzed using public databases,RNA sequencing,and immunohistochemistry.Correlations between PDE1A expression,clinicopathological features,and prognosis were assessed.Functional roles were investigated in ovarian cancer cell lines.Results:PDE1A was significantly overexpressed in EOC tissues compared with that in normal ovarian epithelial tissues.Overexpression correlated with advanced International Federation of Gynecology and Obstetrics(FIGO)stage,poor tumor grade,and reduced response to platinum-based chemotherapy.High PDE1A levels were linked to worse disease-free survival and overall survival,and multivariate analysis confirmed PDE1A as an independent prognostic factor.To elucidate its functional role,we performed in vitro experiments showing that PDE1A knockdown suppressed cell proliferation and colony formation,induced G1 arrest,and downregulatedβ-catenin signaling with reduced cyclin D1 and c-Myc expression.Notably,these inhibitory effects were partially rescued by lithium chloride(LiCl),a Wingless-related integration site(Wnt)/β-catenin activator.Conclusions:In conclusion,our findings identify PDE1A as a Wnt/β-catenin-linked biomarker of tumor progression and platinum resistance in EOC and provide a biological rationale for further investigation of PDE1A-targeted strategies in preclinical models.
基金financially supported by the Research and Development Program of China (2022YFA1505700)the National Natural Science Foundation of China (22475214, 22205232, 52102216)+6 种基金the Natural Science Foundation of Fujian Province (2023J06044,2022J01625, 2022-S-002)the Talent Plan of Shanghai BranchChinese Academy of Sciences (CASSHB-QNPD-2023-020)the Selfdeployment Project Research Program of Haixi Institutes,Chinese Academy of Sciences (CXZX-2022-JQ06 and CXZX-2022-GH03)the Anhui Key Laboratory of Nanomaterials and Nanotechnology,the Major Science and Technology Projects in Anhui Province(202305a12020006)the Open Project of State Key Laboratory of Inorganic Synthesis and Preparative Chemistry (2025-22)the Innovation Training Program for College Students(2025019300A, 20250193008)
文摘Co-free Li-rich Li_(1.2)Ni_(0.2)Mn_(0.6)O_(2)(LR)cathode shows the highest working capacity that can be applied to high-energy density Li-ion batteries(LIBs).However,poor cycle stability and voltage decay caused by phase transition are always hindering its further development.Herein,a novel medium-entropy Li-rich Mn-based cathode material(LRMEF)was synthesized via a simple sol-gel method.The introduction of multivalent ions(Al^(3+)/Cu^(2+)doping at Mn sites and F−doping at O sites)effectively mitigates the Jahn-Teller distortion of Mn ions and suppresses oxygen release.High-angle annular dark-field scanning transmission electron microscopy(HAADF-STEM)images confirm that this synergistic doping strategy induces the in-situ formation of an approximately 3 nm-thick spinel surface layer,which significantly enhances structural stability and ion diffusion kinetics.Besides,a series of in-situ/ex-situ characterization methods and density functional theory(DFT)calculations have been carried out to fundamentally shed light on the optimized structure-activity relationship and reaction mechanism.As a result,the LR material with entropy regulation and anion doping exhibits excellent cycling stability(189.2 mAh g^(−1)at 1 C with 84%capacity retention after 300 cycles),rate performance(164.1 mAh g^(−1)at 5 C),and voltage retention(82.7%at 1 C after 300 cycles),demonstrating great application prospects in future high-energy-density LIBs.
基金supported by the National Natural Science Foundation of China(No.51878292).
文摘Large-scale CO_(2)emissions have exacerbated the greenhouse effect,reinforcing the critical need for efficient CO_(2)mitigation methods.Plasma-catalytic technology enables CO_(2)conversion under mild conditions,especially for CO_(2)methanation(the Sabatier reaction),which has attracted significant attention due to its economic benefits and the potential for safe energy transportation via existing natural gas pipelines.The development of high-performance CO_(2)methanation catalysts remains an ongoing and long-term objective,and there is a lack of adequate in-situ characterization techniques to investigate the mechanisms.This study focuses on the Ni/La_(2)O_(3)(LN)catalyst and introduces two CO_(2)activation strategies through F and Na modifications:the Ni-Ov-Ni site activation with electron transfer from Ni0 under low-power conditions and basic site activation under high-power conditions.The LN-NaF catalysts enhance CO_(2)methanation activity across the entire power range compared to LN,achieving a CO_(2)conversion of 86.3%and CH4 selectivity of 99.4%.Additionally,LN-F(h)reaches a CH4 yield 4.15 times higher than that of LN at low power.Furthermore,in-situ diffuse reflectance infrared Fourier transform(DRIFT)spectroscopy with a self-made reactor are performed under plasma-catalytic conditions to reveal the CO_(2)adsorption and conversion mechanisms,indicating that different dopants(F,Na,and NaF)exhibit promoting effects on different intermediates,resulting in variations in CO_(2)methanation activity.This study provides valuable insights for improving catalyst performance and a thorough comprehension of mechanisms in CO_(2)methanation.
基金funding from the National Natural Science Foundation of China(22378289)the Key Central Government Guides Local Funds for Science and Technology Development(YDZJSX2022A021)the special fund for Science and Technology Innovation Teams of Shanxi Province(202304051001026)。
文摘The oxygen evolution reaction(OER)suffers from sluggish kinetics,necessitating efficient electrocatalysts to reduce overpotentials in water splitting.Currently recognized OER mechanisms primarily include the adsorbate evolution mechanism(AEM),lattice oxygen mechanism(LOM),and oxide path mechanism(OPM).Compared to AEM,limited by scaling relationships,and LOM,constrained by stability issues,the OPM offers a promising alternative by enabling direct O-O bond formation via dual active sites,thus bypassing^(*)OOH intermediates and lattice O involvement and achieving a balance between activity and durability.However,activating the OPM process requires precise control over the spatial and electronic structure of active sites,making the design of OPM-based catalysts challenging.While previous reviews have focused on homo/heteronuclear diatomic perspectives of OPM-based catalysts,it is urgent to systematically summarize design strategies to provide a rational reference for their development.Herein,a review of design strategies for OPM-based OER catalysts across three scales is comprehensively presented,including in-situ engineering,doping-enabled sites reconstruction,and introducing new sites for nanoparticles,direct synthesis or post-treatments for molecular catalysts,and doping or template strategies for atom pairs or arrays.The unique advantage of atom arrays is also highlighted,and their future research directions and possible strategies are discussed.This review provides a systematic summary and forward-looking perspectives for rationally designing high-performance OPM-based OER catalysts.
