The recycling of neptunium(Np)from nuclear wastes is crucial for the sustainable development of nuclear energy,yet it is still a challenging task owing to the complexity of Np chemistry.Precise control of oxidation st...The recycling of neptunium(Np)from nuclear wastes is crucial for the sustainable development of nuclear energy,yet it is still a challenging task owing to the complexity of Np chemistry.Precise control of oxidation state is highly desirable for the effective recovery of Np.In this study,we report an innovative strategy for Np recovery through in-situ coordination and reduction of Np(Ⅴ)in a biphasic extraction system.By leveraging the synergistic effects of coordination by a P=O donating ligand(trialkyl phosphine oxide,TRPO)and reduction by hydroquinone(HQ)in the organic phase,efficient Np(Ⅴ)-to-Np(Ⅳ)conversion and high distribution ratio(D)of Np were achieved in a single extraction contact.The reduction mechanism of Np was elucidated through spectroscopic and theoretical analyses.This work enriches the redox chemistry of Np and provides a novel pathway for Np recovery in advanced nuclear fuel cycles.展开更多
In order to avoid the waste of iron caused by the direct use of ferronickel slag(FNS)in building materials,the effects of reduction iron extraction on the physical and chemical properties,cementitious reactivity and h...In order to avoid the waste of iron caused by the direct use of ferronickel slag(FNS)in building materials,the effects of reduction iron extraction on the physical and chemical properties,cementitious reactivity and hydration reaction characteristics of FNS and ferrum extraction tailing of nickel slag(FETNS)were studied.The experimental results show that the reduction ferrum extraction method changes the mineral phase composition of the waste slag,breaks the Si-O-Si bond,forms the tetrahedral structure of Si-O-NBO or Si-O-2NBO,and increases the content of active components such as Ca,Si,Mg,and Al.Compared with FNS,the 28 d compressive strength of pastes prepared by FETNS increases by 16.12%,22.57%,33.13%,44.26%,and 57.65%,respectively.The degree of hydration reaction of the composite cementitious systems in the FETNS group is higher than that in the FNS group at different ages,and the content of hydration products such as C-S-H gel and ettringite(AFt)is also higher than that in the FNS group.More hydration products can improve the curing ability to Cr and Mn of the composite cementitious systems in the FETNS group,and reduce the leaching value of Cr and Mn.展开更多
The extraction of manganese from low-grade manganese oxide ores using Ca S derived from Ca SO4 as reductant was investigated. The effects of mass ratio of Ca S to ore, reduction temperature, reduction time, liquid to ...The extraction of manganese from low-grade manganese oxide ores using Ca S derived from Ca SO4 as reductant was investigated. The effects of mass ratio of Ca S to ore, reduction temperature, reduction time, liquid to solid ratio（L/S ratio）, stirring speed, leaching temperature, leaching time and H2SO4 concentration on the leaching rates of Mn and Fe during the reduction–acid leaching process were discussed. The leaching rates of 96.47% for Mn and 19.24% for Fe were obtained under the optimized conditions of mass ratio of Ca S to manganese oxide ore 1：6.7, L/S ratio 5：1, stirring speed 300 r/min, reduction temperature of 95 °C for 2.0 h in the reduction process and leaching stirring speed of 200 r/min, H2SO4 concentration of 1.5 mol/L, leaching temperature of 80 °C for 5 min in the leaching process. In addition, this process can be employed in the recovery of manganese from various manganese oxide ores, and Mn leaching rate above 95% is obtained.展开更多
In order to explore the reduction pathways of zinc oxide in LiCl molten salt and the optimal process,experiments were conducted in an alumina crucible using metallic lithium as the reducing agent and lithium chloride ...In order to explore the reduction pathways of zinc oxide in LiCl molten salt and the optimal process,experiments were conducted in an alumina crucible using metallic lithium as the reducing agent and lithium chloride molten salt as the reaction medium at 923 K.The study assessed the effects of lithium thermochemical reduction and electrolytic reduction of ZnO.The volatilization behavior of metal oxides in molten salts,the equivalent of a reducing agent,reduction time,amount of molten salt,stirring time,and the method of reduction feed were investigated for their impacts on the reduction yield and product composition.X-ray powder diffraction(XRD)analysis of the products showed that lithium reduction of ZnO not only produced metallic Zn but also formed a LiZn alloy.Electrolytic reduction can be used to obtain the metallic Zn product by controlling the potential below-2.2 V(vs Ag/Ag^(+)).Moreover,sintered oxides and higher electrode potentials could enhance the efficiency of electrolysis.Under the optimal reaction conditions determined experimentally,the lithium reduction experiment achieved a yield of 77.2%after a 12-h test,and the electrolytic reduction reached a yield of 85.4%after a 6-h test.展开更多
Silver nanoparticles(Ag NPs)have attracted attention in the field of biomaterials due to their excellent antibacterial property.However,the reducing and stabilizing agents used for the chemical reduction of Ag NPs are...Silver nanoparticles(Ag NPs)have attracted attention in the field of biomaterials due to their excellent antibacterial property.However,the reducing and stabilizing agents used for the chemical reduction of Ag NPs are usually toxic and may cause water pollution.In this work,Ag NPs(31.2 nm in diameter)were prepared using the extract of straw,an agricultural waste,as the reducing and stabilizing agent.Experimental analysis revealed that the straw extract contained lignin,the structure of which possesses phenolic hydroxyl and methoxy groups that facilitate the reduction of silver salts into Ag NPs.The surfaces of Ag NPs were negatively charged due to the encapsulation of a thin layer of lignin molecules that prevented their aggregation.After the prepared Ag NPs were added to the precursor solution of acrylamide,free radical polymerization was triggered without the need for extra heating or light irradiation,resulting in the rapid formation of an Ag NP-polyacrylamide composite hydrogel.The inhibition zone test proved that the composite hydrogel possessed excellent antibacterial ability due to the presence of Ag NPs.The prepared hydrogel may have potential applications in the fabrication of biomedical materials,such as antibacterial dressings.展开更多
Standard bacterial suspensions play a crucial role in microbiological diagnosis.Traditional prepar-ation methods,which rely heavily on manual operations,face challenges such as poor reproducibility,low ef-ficiency,and...Standard bacterial suspensions play a crucial role in microbiological diagnosis.Traditional prepar-ation methods,which rely heavily on manual operations,face challenges such as poor reproducibility,low ef-ficiency,and biosafety concerns.In this study,we propose a high-precision automated colony extraction and separation system that combines large-field imaging and artificial intelligence(AI)to facilitate intelligent screening and localization of colonies.Firstly,a large-field imaging system was developed to capture high-resolution images of 90 mm Petri dishes,achieving a physical resolution of 13.2μm and an imaging speed of 13 frames per second.Subsequently,AI technology was employed for the automatic recognition and localiza-tion of colonies,enabling the selection of target colonies with diameters ranging from 1.9 to 2.3 mm.Next,a three-axis motion control platform was designed,accompanied by a path planning algorithm for the efficient extraction of colonies.An electronic pipette was employed for accurate colony collection.Additionally,a bacterial suspension concentration measurement module was developed,incorporating a 650 nm laser diode as the light source,achieving a measurement accuracy of 0.01 McFarland concentration(MCF).Finally,the system’s performance was validated through the preparation of an Esckerichia coli(E.coli)suspension.After 17 hours of cultivation,E.coli was extracted four times,achieving the target concentration set by the system.This work is expected to enable rapid and accurate microbial sample preparation,significantly reducing de-tection cycles and alleviating the workload of healthcare personnel.展开更多
This paper reports the preparation of three di‑iron complexes containing a thiazole moiety.Esterification of complex[Fe_(2)(CO)_(6)(μ‑SCH_(2)CH(CH_(2)OH)S)](1)with 4‑methylthiazole‑5‑carboxylic acid gave the correspo...This paper reports the preparation of three di‑iron complexes containing a thiazole moiety.Esterification of complex[Fe_(2)(CO)_(6)(μ‑SCH_(2)CH(CH_(2)OH)S)](1)with 4‑methylthiazole‑5‑carboxylic acid gave the corresponding ester[Fe_(2)(CO)_(6)(μ‑tedt)](2),where tedt=SCH_(2)CH(CH_(2)OOC(5‑C_(3)HNSCH_(3)))S.Further reactions of complex 2 with tri(ptolyl)phosphine(tp)or tris(4‑fluorophenyl)phosphine(fp)gave the phosphine‑substituted derivatives[Fe_(2)(CO)_(5)(tp)(μ‑tedt)](3)and[Fe_(2)(CO)_(5)(fp)(μ‑tedt)](4).The structures of the newly prepared complexes were elucidated by elemental analysis,NMR,IR,and X‑ray photoelectron spectroscopy.Moreover,single‑crystal X‑ray diffraction analysis confirmed their molecular structures,showing that they contain a di‑iron core ligated by a bridged dithiolate bearing a thiazole moiety and terminal carbonyls.The electrochemical and electrocatalytic proton reduction were probed by cyclic voltammetry,revealing that three complexes can catalyze the reduction of protons to H_(2) under the electrochemical conditions.For comparison,complex 4 possessed the best efficiency with a turnover frequency of 23.5 s^(-1)at 10 mmol·L^(-1)HOAc concentration.In addition,the fungicidal activity of these complexes was also investigated in this study.CCDC:2477511,2;2477512,3;2477513,4.展开更多
Experts and officials shared their insights on poverty reduction cooperation and sustainable development during the 2025 International Seminar on Global Poverty Reduction Partnerships.
The lack of macro-continuity and mechanical strength of covalent organic frameworks(COFs)has significantly limited their practical applications.Here,we propose an“alcohol-triggered defect cleavage”strategy to precis...The lack of macro-continuity and mechanical strength of covalent organic frameworks(COFs)has significantly limited their practical applications.Here,we propose an“alcohol-triggered defect cleavage”strategy to precisely regulate the growth and stacking of COF grains through a moderate reversed Schiff base reaction,realizing the direct synthesis of COF nanofibers(CNFs)with high aspect ratio(L/D=103.05)and long length(>20μm).An individual CNF exhibits a biomimetic scale-like architecture,achieving superior flexibility and fatigue resistance under dynamic bending via a multiscale stress dissipation mechanism.Taking advantages of these structural features,we engineer CNF aerogels(CNF-As)with programmable porous structures(e.g.,honeycomb,lamellar,isotropic)via directional ice-template methodology.CNF-As demonstrate 100%COF content,high specific surface area(396.15 m^(2)g^(-1))and superelasticity(~0%elastic deformation after 500 compression cycles at 50%strain),outperforming most COF-based counterparts.Compared with the conventional COF aerogels,the unique structural features of CNF-A enable it to perform outstandingly in uranium extraction,with an 11.72-fold increment in adsorption capacity(920.12 mg g^(-1))and adsorption rate(89.9%),and a 2.48-fold improvement in selectivity(U/V=2.31).This study provides a direct strategy for the development of next-generation COF materials with outstanding functionality and structural robustness.展开更多
The demand for ^(238)Pu(nuclear battery heat source)drives the separation of its precursor,^(237)Np,from spent nuclear fuel(SNF).However,the co-existence of multi-valence states(IV/V/VI)of Np and similar redox behavio...The demand for ^(238)Pu(nuclear battery heat source)drives the separation of its precursor,^(237)Np,from spent nuclear fuel(SNF).However,the co-existence of multi-valence states(IV/V/VI)of Np and similar redox behavior with Pu(IV)hinder the effective separation of Np.N-Butyraldehyde(n-C_(3)H_(7)CHO)selectively reduces Np(VI)to Np(V)without reducing Pu(IV).Herein,we examined the reduction mechanisms of Np(VI)and Pu(IV)by n-C_(3)H_(7)CHO using relativistic density functional theory.Based on the results of the potential energy profiles,the reductions of both Np(VI)and Pu(IV)by n-C_(3)H_(7)CHO are thermodynamically feasible,whereas only the former is kinetically achievable.It uncovers that n-C_(3)H_(7)CHO can only reduce Np(VI)to Np(V)owing to kinetically controlled selective reduction.The analyses of spin density and bond distance indicate that the reduction nature for the first Np(VI)/Pu(IV)belongs to hydrogen atom transfer,whereas that for the second one involves outer-sphere electron transfer.Localized molecular orbitals(LMOs)analysis discloses the bonding evolution during the reduction process of Np(VI)/Pu(IV).This study elucidates the reason behind the kinetically controlled selective reduction of Np(VI)/Pu(IV)by n-C_(3)H_(7)CHO at the molecular level and offers in-depth perspectives on the isolation of specific metal ions from the view of kinetic control.展开更多
In comparison with their 2D and 3D counterparts,1D covalent organic frameworks(COFs)have rarely been investigated due to the synthetic challenge arising from the strict necessary matching in the molecular symmetry bet...In comparison with their 2D and 3D counterparts,1D covalent organic frameworks(COFs)have rarely been investigated due to the synthetic challenge arising from the strict necessary matching in the molecular symmetry between corresponding building blocks and linking units in addition to the unmanageable packing of 1D organic chains once formed.Herein,two novel imide-linked 1D COFs with phthalocyanine building blocks,namely NiPc-CZDM-COF and NiPc-CZDL-COF,were fabricated from the hydrothermal synthesis reaction of 2,3,9,10,16,17,23,24-octacarboxyphthalocyaninato nickel(II)(NiPc(COOH)_(8))with 9H-carbazole-3,6-diamine(CZDM)and 4,4′-(9H-carbazole-3,6-diyl)dianiline(CZDL),respectively.Two COFs have high crystallinity on the basis of powder X-ray diffraction analysis and high-resolution transmission electron microscopy.Due to their high ratio of exposed active centers on the edge sites of porous ribbons,both NiPc-CZDM-COF and NiPc-CZDL-COF electrodes display high utilization efficiency of NiPc electroactive sites of 8.0%and 7.5% according to the electrochemical measurement,resulting in their excellent capacity toward electrocatalytic nitrate reduction with the nitrate-to-NH3 Faradaic efficiency of nearly 100%.In particular,NiPc-CZDM-COF electrode exhibits superior electrocatalytic performance with high NH3 partial current density of−246 mA/cm^(2),ammonia yield rate of 19.5 mg cm^(−2) h^(−1),and turnover frequency of 5.8 s^(−1) at−1.2 V in an H-type cell associated with its higher conductivity.This work reveals the good potential of 1D porous crystalline materials in electrocatalysis.展开更多
As an important class of phenanthroline derivatives containing soft N and hard O donor atoms,the laborious syntheses of unsymmetrical 1,10-phenanthroline-derived diamide ligands(DAPhen) have hindered its extensive stu...As an important class of phenanthroline derivatives containing soft N and hard O donor atoms,the laborious syntheses of unsymmetrical 1,10-phenanthroline-derived diamide ligands(DAPhen) have hindered its extensive study.In this work,we first report a convenient synthetic method for the construction of DAPhen using Friedländer reaction by two facile steps(vs.previous 12 steps).A variety of DAPhen ligands are readily available,especially unsymmetrical ones,which give us a platform to systematically study the substituent effect on f-block elements extraction performance.The performance of unsymmetrical extractants is experimentally confirmed to falls between that of their corresponding symmetrical extractants by extracting UO_(2)^(2+) as the representative f-block element.This work provides a direct and versatile method to synthesize symmetrical and unsymmetrical DAPhen,which paves way for the investigations on their coordination properties with metal ions and other applications.展开更多
The extraction of uranium from seawater via membrane adsorption is a promising strategy for ensuring a long-term supply of uranium and the sustainability of nuclear energy.However,this approach has been hindered by th...The extraction of uranium from seawater via membrane adsorption is a promising strategy for ensuring a long-term supply of uranium and the sustainability of nuclear energy.However,this approach has been hindered by the longstanding challenge of identifying sustainable membrane materials.In response,we propose a prototypal hybridization strategy to design a novel series of aminated conjugated microporous polymer(CMPN)@collagen fiber membrane(COLM).These sustainable and low-cost membrane materials allow a rapid and high-affinity kinetic to capture 90%of the uranium in just 30 min from 50 ppm with a high selectivity of Kd>105 mL·g^(−1).They also afford a robustly reusable adsorption capacity as high as 345 mg·g^(−1)that could harvest 1.61 mg·g^(−1)of uranium in a short 7-day real marine engineering in Fujian Province,even though suffered from very low uranium concentration of 3.29μg·L^(−1)and tough influence of salts such as 10.77 g·L^(−1)of Na^(+),1.75μg·L^(−1)of VO_(3)^(−)etc.in the rough seas.The structural evidence from both experimental and theoretical studies confirmed the formation of favorable chelating motifs from the amino group on CMPN-COLM,and the intensification by the synergistic effect from the size-sieving action of CMPN and the capillary inflow effect of COLM.展开更多
Deep learning has made significant progress in the field of oriented object detection for remote sensing images.However,existing methods still face challenges when dealing with difficult tasks such as multi-scale targ...Deep learning has made significant progress in the field of oriented object detection for remote sensing images.However,existing methods still face challenges when dealing with difficult tasks such as multi-scale targets,complex backgrounds,and small objects in remote sensing.Maintaining model lightweight to address resource constraints in remote sensing scenarios while improving task completion for remote sensing tasks remains a research hotspot.Therefore,we propose an enhanced multi-scale feature extraction lightweight network EM-YOLO based on the YOLOv8s architecture,specifically optimized for the characteristics of large target scale variations,diverse orientations,and numerous small objects in remote sensing images.Our innovations lie in two main aspects:First,a dynamic snake convolution(DSC)is introduced into the backbone network to enhance the model’s feature extraction capability for oriented targets.Second,an innovative focusing-diffusion module is designed in the feature fusion neck to effectively integrate multi-scale feature information.Finally,we introduce Layer-Adaptive Sparsity for magnitude-based Pruning(LASP)method to perform lightweight network pruning to better complete tasks in resource-constrained scenarios.Experimental results on the lightweight platform Orin demonstrate that the proposed method significantly outperforms the original YOLOv8s model in oriented remote sensing object detection tasks,and achieves comparable or superior performance to state-of-the-art methods on three authoritative remote sensing datasets(DOTA v1.0,DOTA v1.5,and HRSC2016).展开更多
Controllable synthesis of ultrathin metallene nanosheets and rational design of their spatial arrangement in favor of electrochemical catalysis are critical for their renewable energy applications.Here,a biomimetic de...Controllable synthesis of ultrathin metallene nanosheets and rational design of their spatial arrangement in favor of electrochemical catalysis are critical for their renewable energy applications.Here,a biomimetic design of“Trunk-Branch-Leaf”strategy is proposed to prepare the ultrathin edge-riched Zn-ene“leaves”with a thickness of~2.5 nm,adjacent Zn-ene cross-linked with each other,which are supported by copper nanoneedle“branches”on copper mesh“trunks,”named as Zn-ene/Cu-CM.The resulting superstructure enables the formation of an interconnected network and multiple channels,which can be used as an electrocatalytic CO_(2) reduction reaction(CO_(2)RR)electrode to allow a fast charge and mass transfer as well as a large electrolyte reservoir.By virtue of the distinctive structure,the obtained Zn-ene/Cu-CM electrode exhibits excellent selectivity and activity toward CO production with a maximum Faradaic efficiency of 91.3%and incredible partial current density up to 40 mA cm^(−2),outperforming most of the state-of-the-art Zn-based electrodes for CO_(2) reduction.The phenolphthalein color probe combined with in situ attenuated total reflection-infrared spectroscopy uncovered the formation of the localized pseudo-alkaline microenvironment at the interface of the Zn-ene/Cu-CM electrode.Theoretical calculations confirmed that the localized pH as the origin is responsible for the adsorption of CO_(2) at the interface and the generation of *COOH and *CO intermediates.This study offers valuable insights into developing efficient electrodes through synergistic regulation of reaction microenvironments and active sites,thereby facilitating the electrolysis of practical CO_(2) conversion.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
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
The hydrogen reduction kinetics of tungsten trioxide(WO_(3))was investigated via non-isothermal thermogravimetric analysis.Under the local gas-solid reduction conditions,the particle morphology of tungsten powders was...The hydrogen reduction kinetics of tungsten trioxide(WO_(3))was investigated via non-isothermal thermogravimetric analysis.Under the local gas-solid reduction conditions,the particle morphology of tungsten powders was found to be consistent with that of raw material WO_(3).The removal of oxygen from tungsten oxide during hydrogen reduction led to the formation of porous structures between the reduced particles,which were obviously different from the polyhedral single-crystal configuration of tungsten powders obtained via chemical vapor deposition.Moreover,the two-stage hydrogen reduction mechanisms of WO_(3) under the local gas-solid reduction conditions can be described using the composite autocatalytic function.The activation energies of the first and second stages of the hydrogen reduction of WO_(3) were determined to be 121 and 135 kJ/mol,respectively.展开更多
Thermochemical sulfate reduction(TSR)is an important organic-inorganic reaction that occurs within sedimentary basins and alters the original chemical compositions and isotopic structures of hydrocarbons in natural ga...Thermochemical sulfate reduction(TSR)is an important organic-inorganic reaction that occurs within sedimentary basins and alters the original chemical compositions and isotopic structures of hydrocarbons in natural gases.We used the GC-Py-GC-IRMS method to study TSR and obtained a novel finding related to intramolecular carbon isotope fractionation in natural propane.The results show that theΔC-T(δ^(13)C_(central)-13 C_(terminal))andδ^(13)C_(central)values significantly increased to 44.7‰and 11.9‰,respectively,with increasing TSR alteration.In contrast,the 13 C_(terminal)values of propane remained largely unaltered by the TSR reaction.This difference in position-specific isotope fractionation can be attributed to the central carbon’s reactivity being higher than that of terminal carbon during TSR.In sum,the results indicate that theδ^(13)C_(terminal)values of propane can serve as robust indicators for source rock identification of natural gas altered by post-generation reactions such as TSR and anaerobic microbial oxidation.展开更多
Seawater zinc-air batteries are promising energy storage devices due to their high energy density and utilization of seawater electrolytes.However,their efficiency is hindered by the sluggish oxygen reduction reaction...Seawater zinc-air batteries are promising energy storage devices due to their high energy density and utilization of seawater electrolytes.However,their efficiency is hindered by the sluggish oxygen reduction reaction(ORR)and chlorideinduced degradation over conventional catalysts.In this study,we proposed a universal synthetic strategy to construct heteroatom axially coordinated Fe–N_(4) single-atom seawater catalyst materials(Cl–Fe–N_(4) and S–Fe–N_(4)).X-ray absorption spectroscopy confirmed their five-coordinated square pyramidal structure.Systematic evaluation of catalytic activities revealed that compared with S–Fe–N_(4),Cl–Fe–N_(4) exhibits smaller electrochemical active surface area and specific surface area,yet demonstrates higher limiting current density(5.8 mA cm^(−2)).The assembled zinc-air batteries using Cl–Fe–N_(4) showed superior power density(187.7 mW cm^(−2) at 245.1 mA cm^(−2)),indicating that Cl axial coordination more effectively enhances the intrinsic ORR activity.Moreover,Cl–Fe–N_(4) demonstrates stronger Cl−poisoning resistance in seawater environments.Chronoamperometry tests and zinc-air battery cycling performance evaluations confirmed its enhanced stability.Density functional theory calculations revealed that the introduction of heteroatoms in the axial direction regulates the electron center of Fe single atom,leading to more active reaction intermediates and increased electron density of Fe single sites,thereby enhancing the reduction in adsorbed intermediates and hence the overall ORR catalytic activity.展开更多
基金the financial support from the National Natural Science Foundation of China(22325603)the financial support from the National Natural Science Foundation of China(22376116)+3 种基金the financial support from the National Natural Science Foundation of China(22076130)the Young Elite Scientists Sponsorship Program by China Association for Science and Technology(CAST)(2023QNRC001)the Fundamental Research Funds for the Central Universities(20826041D4117)the Natural Science Foundation of Sichuan(2025ZNSFSC0109)。
文摘The recycling of neptunium(Np)from nuclear wastes is crucial for the sustainable development of nuclear energy,yet it is still a challenging task owing to the complexity of Np chemistry.Precise control of oxidation state is highly desirable for the effective recovery of Np.In this study,we report an innovative strategy for Np recovery through in-situ coordination and reduction of Np(Ⅴ)in a biphasic extraction system.By leveraging the synergistic effects of coordination by a P=O donating ligand(trialkyl phosphine oxide,TRPO)and reduction by hydroquinone(HQ)in the organic phase,efficient Np(Ⅴ)-to-Np(Ⅳ)conversion and high distribution ratio(D)of Np were achieved in a single extraction contact.The reduction mechanism of Np was elucidated through spectroscopic and theoretical analyses.This work enriches the redox chemistry of Np and provides a novel pathway for Np recovery in advanced nuclear fuel cycles.
基金Funded by the Science and Technology Program of Gansu Province(Nos.23JRRA799 and 24JRRA213)the National Natural Science Foundation of China(Nos.52178216,52008196,and U21A20150)。
文摘In order to avoid the waste of iron caused by the direct use of ferronickel slag(FNS)in building materials,the effects of reduction iron extraction on the physical and chemical properties,cementitious reactivity and hydration reaction characteristics of FNS and ferrum extraction tailing of nickel slag(FETNS)were studied.The experimental results show that the reduction ferrum extraction method changes the mineral phase composition of the waste slag,breaks the Si-O-Si bond,forms the tetrahedral structure of Si-O-NBO or Si-O-2NBO,and increases the content of active components such as Ca,Si,Mg,and Al.Compared with FNS,the 28 d compressive strength of pastes prepared by FETNS increases by 16.12%,22.57%,33.13%,44.26%,and 57.65%,respectively.The degree of hydration reaction of the composite cementitious systems in the FETNS group is higher than that in the FNS group at different ages,and the content of hydration products such as C-S-H gel and ettringite(AFt)is also higher than that in the FNS group.More hydration products can improve the curing ability to Cr and Mn of the composite cementitious systems in the FETNS group,and reduce the leaching value of Cr and Mn.
基金Project(21376273)supported by the National Natural Science Foundation of ChinaProject(2010FJ1011)supported by the Key Program of Science and Technology of Hunan Province,China
文摘The extraction of manganese from low-grade manganese oxide ores using Ca S derived from Ca SO4 as reductant was investigated. The effects of mass ratio of Ca S to ore, reduction temperature, reduction time, liquid to solid ratio（L/S ratio）, stirring speed, leaching temperature, leaching time and H2SO4 concentration on the leaching rates of Mn and Fe during the reduction–acid leaching process were discussed. The leaching rates of 96.47% for Mn and 19.24% for Fe were obtained under the optimized conditions of mass ratio of Ca S to manganese oxide ore 1：6.7, L/S ratio 5：1, stirring speed 300 r/min, reduction temperature of 95 °C for 2.0 h in the reduction process and leaching stirring speed of 200 r/min, H2SO4 concentration of 1.5 mol/L, leaching temperature of 80 °C for 5 min in the leaching process. In addition, this process can be employed in the recovery of manganese from various manganese oxide ores, and Mn leaching rate above 95% is obtained.
文摘In order to explore the reduction pathways of zinc oxide in LiCl molten salt and the optimal process,experiments were conducted in an alumina crucible using metallic lithium as the reducing agent and lithium chloride molten salt as the reaction medium at 923 K.The study assessed the effects of lithium thermochemical reduction and electrolytic reduction of ZnO.The volatilization behavior of metal oxides in molten salts,the equivalent of a reducing agent,reduction time,amount of molten salt,stirring time,and the method of reduction feed were investigated for their impacts on the reduction yield and product composition.X-ray powder diffraction(XRD)analysis of the products showed that lithium reduction of ZnO not only produced metallic Zn but also formed a LiZn alloy.Electrolytic reduction can be used to obtain the metallic Zn product by controlling the potential below-2.2 V(vs Ag/Ag^(+)).Moreover,sintered oxides and higher electrode potentials could enhance the efficiency of electrolysis.Under the optimal reaction conditions determined experimentally,the lithium reduction experiment achieved a yield of 77.2%after a 12-h test,and the electrolytic reduction reached a yield of 85.4%after a 6-h test.
基金financially supported by the National Natural Science Foundation of China(No.52203209)the State Key Laboratory of Solid Waste Reuse for Building Materials,China(No.SWR-2022-009)the Fundamental Research Funds for the Central Universities,China(No.FRF-IDRY22-012)。
文摘Silver nanoparticles(Ag NPs)have attracted attention in the field of biomaterials due to their excellent antibacterial property.However,the reducing and stabilizing agents used for the chemical reduction of Ag NPs are usually toxic and may cause water pollution.In this work,Ag NPs(31.2 nm in diameter)were prepared using the extract of straw,an agricultural waste,as the reducing and stabilizing agent.Experimental analysis revealed that the straw extract contained lignin,the structure of which possesses phenolic hydroxyl and methoxy groups that facilitate the reduction of silver salts into Ag NPs.The surfaces of Ag NPs were negatively charged due to the encapsulation of a thin layer of lignin molecules that prevented their aggregation.After the prepared Ag NPs were added to the precursor solution of acrylamide,free radical polymerization was triggered without the need for extra heating or light irradiation,resulting in the rapid formation of an Ag NP-polyacrylamide composite hydrogel.The inhibition zone test proved that the composite hydrogel possessed excellent antibacterial ability due to the presence of Ag NPs.The prepared hydrogel may have potential applications in the fabrication of biomedical materials,such as antibacterial dressings.
文摘Standard bacterial suspensions play a crucial role in microbiological diagnosis.Traditional prepar-ation methods,which rely heavily on manual operations,face challenges such as poor reproducibility,low ef-ficiency,and biosafety concerns.In this study,we propose a high-precision automated colony extraction and separation system that combines large-field imaging and artificial intelligence(AI)to facilitate intelligent screening and localization of colonies.Firstly,a large-field imaging system was developed to capture high-resolution images of 90 mm Petri dishes,achieving a physical resolution of 13.2μm and an imaging speed of 13 frames per second.Subsequently,AI technology was employed for the automatic recognition and localiza-tion of colonies,enabling the selection of target colonies with diameters ranging from 1.9 to 2.3 mm.Next,a three-axis motion control platform was designed,accompanied by a path planning algorithm for the efficient extraction of colonies.An electronic pipette was employed for accurate colony collection.Additionally,a bacterial suspension concentration measurement module was developed,incorporating a 650 nm laser diode as the light source,achieving a measurement accuracy of 0.01 McFarland concentration(MCF).Finally,the system’s performance was validated through the preparation of an Esckerichia coli(E.coli)suspension.After 17 hours of cultivation,E.coli was extracted four times,achieving the target concentration set by the system.This work is expected to enable rapid and accurate microbial sample preparation,significantly reducing de-tection cycles and alleviating the workload of healthcare personnel.
文摘This paper reports the preparation of three di‑iron complexes containing a thiazole moiety.Esterification of complex[Fe_(2)(CO)_(6)(μ‑SCH_(2)CH(CH_(2)OH)S)](1)with 4‑methylthiazole‑5‑carboxylic acid gave the corresponding ester[Fe_(2)(CO)_(6)(μ‑tedt)](2),where tedt=SCH_(2)CH(CH_(2)OOC(5‑C_(3)HNSCH_(3)))S.Further reactions of complex 2 with tri(ptolyl)phosphine(tp)or tris(4‑fluorophenyl)phosphine(fp)gave the phosphine‑substituted derivatives[Fe_(2)(CO)_(5)(tp)(μ‑tedt)](3)and[Fe_(2)(CO)_(5)(fp)(μ‑tedt)](4).The structures of the newly prepared complexes were elucidated by elemental analysis,NMR,IR,and X‑ray photoelectron spectroscopy.Moreover,single‑crystal X‑ray diffraction analysis confirmed their molecular structures,showing that they contain a di‑iron core ligated by a bridged dithiolate bearing a thiazole moiety and terminal carbonyls.The electrochemical and electrocatalytic proton reduction were probed by cyclic voltammetry,revealing that three complexes can catalyze the reduction of protons to H_(2) under the electrochemical conditions.For comparison,complex 4 possessed the best efficiency with a turnover frequency of 23.5 s^(-1)at 10 mmol·L^(-1)HOAc concentration.In addition,the fungicidal activity of these complexes was also investigated in this study.CCDC:2477511,2;2477512,3;2477513,4.
文摘Experts and officials shared their insights on poverty reduction cooperation and sustainable development during the 2025 International Seminar on Global Poverty Reduction Partnerships.
基金supported by the National Natural Science Foundation of China(No.52403035)the Shanghai Sailing Program(23YF1400300)+1 种基金the Fundamental Research Funds for the Central Universities(2232023D-05)the Weiqiao Teaching and Research Innovation Program.
文摘The lack of macro-continuity and mechanical strength of covalent organic frameworks(COFs)has significantly limited their practical applications.Here,we propose an“alcohol-triggered defect cleavage”strategy to precisely regulate the growth and stacking of COF grains through a moderate reversed Schiff base reaction,realizing the direct synthesis of COF nanofibers(CNFs)with high aspect ratio(L/D=103.05)and long length(>20μm).An individual CNF exhibits a biomimetic scale-like architecture,achieving superior flexibility and fatigue resistance under dynamic bending via a multiscale stress dissipation mechanism.Taking advantages of these structural features,we engineer CNF aerogels(CNF-As)with programmable porous structures(e.g.,honeycomb,lamellar,isotropic)via directional ice-template methodology.CNF-As demonstrate 100%COF content,high specific surface area(396.15 m^(2)g^(-1))and superelasticity(~0%elastic deformation after 500 compression cycles at 50%strain),outperforming most COF-based counterparts.Compared with the conventional COF aerogels,the unique structural features of CNF-A enable it to perform outstandingly in uranium extraction,with an 11.72-fold increment in adsorption capacity(920.12 mg g^(-1))and adsorption rate(89.9%),and a 2.48-fold improvement in selectivity(U/V=2.31).This study provides a direct strategy for the development of next-generation COF materials with outstanding functionality and structural robustness.
基金supported by the National Natural Science Foundation of China(Nos.22376197,U2441225,22076188).
文摘The demand for ^(238)Pu(nuclear battery heat source)drives the separation of its precursor,^(237)Np,from spent nuclear fuel(SNF).However,the co-existence of multi-valence states(IV/V/VI)of Np and similar redox behavior with Pu(IV)hinder the effective separation of Np.N-Butyraldehyde(n-C_(3)H_(7)CHO)selectively reduces Np(VI)to Np(V)without reducing Pu(IV).Herein,we examined the reduction mechanisms of Np(VI)and Pu(IV)by n-C_(3)H_(7)CHO using relativistic density functional theory.Based on the results of the potential energy profiles,the reductions of both Np(VI)and Pu(IV)by n-C_(3)H_(7)CHO are thermodynamically feasible,whereas only the former is kinetically achievable.It uncovers that n-C_(3)H_(7)CHO can only reduce Np(VI)to Np(V)owing to kinetically controlled selective reduction.The analyses of spin density and bond distance indicate that the reduction nature for the first Np(VI)/Pu(IV)belongs to hydrogen atom transfer,whereas that for the second one involves outer-sphere electron transfer.Localized molecular orbitals(LMOs)analysis discloses the bonding evolution during the reduction process of Np(VI)/Pu(IV).This study elucidates the reason behind the kinetically controlled selective reduction of Np(VI)/Pu(IV)by n-C_(3)H_(7)CHO at the molecular level and offers in-depth perspectives on the isolation of specific metal ions from the view of kinetic control.
基金supported by the Natural Science Foundation(NSF)of China(Nos.22205015,22175020,and 22235001)the National Postdoctoral Program for Innovative Talents(No.BX20220032)+2 种基金the China Postdoctoral Science Foundation Funded Project(No.2022BG013)the Fundamental Research Funds for the Central Universities(Nos.00007709,00007770,and FRFBR-23-02B)University of Science and Technology Beijing is gratefully acknowledged.
文摘In comparison with their 2D and 3D counterparts,1D covalent organic frameworks(COFs)have rarely been investigated due to the synthetic challenge arising from the strict necessary matching in the molecular symmetry between corresponding building blocks and linking units in addition to the unmanageable packing of 1D organic chains once formed.Herein,two novel imide-linked 1D COFs with phthalocyanine building blocks,namely NiPc-CZDM-COF and NiPc-CZDL-COF,were fabricated from the hydrothermal synthesis reaction of 2,3,9,10,16,17,23,24-octacarboxyphthalocyaninato nickel(II)(NiPc(COOH)_(8))with 9H-carbazole-3,6-diamine(CZDM)and 4,4′-(9H-carbazole-3,6-diyl)dianiline(CZDL),respectively.Two COFs have high crystallinity on the basis of powder X-ray diffraction analysis and high-resolution transmission electron microscopy.Due to their high ratio of exposed active centers on the edge sites of porous ribbons,both NiPc-CZDM-COF and NiPc-CZDL-COF electrodes display high utilization efficiency of NiPc electroactive sites of 8.0%and 7.5% according to the electrochemical measurement,resulting in their excellent capacity toward electrocatalytic nitrate reduction with the nitrate-to-NH3 Faradaic efficiency of nearly 100%.In particular,NiPc-CZDM-COF electrode exhibits superior electrocatalytic performance with high NH3 partial current density of−246 mA/cm^(2),ammonia yield rate of 19.5 mg cm^(−2) h^(−1),and turnover frequency of 5.8 s^(−1) at−1.2 V in an H-type cell associated with its higher conductivity.This work reveals the good potential of 1D porous crystalline materials in electrocatalysis.
基金financial support from the National Natural Science Foundation of China (Nos.22476178,U2067213)Natural Science Foundation of Zhejiang Province (No.LRG25B060002)。
文摘As an important class of phenanthroline derivatives containing soft N and hard O donor atoms,the laborious syntheses of unsymmetrical 1,10-phenanthroline-derived diamide ligands(DAPhen) have hindered its extensive study.In this work,we first report a convenient synthetic method for the construction of DAPhen using Friedländer reaction by two facile steps(vs.previous 12 steps).A variety of DAPhen ligands are readily available,especially unsymmetrical ones,which give us a platform to systematically study the substituent effect on f-block elements extraction performance.The performance of unsymmetrical extractants is experimentally confirmed to falls between that of their corresponding symmetrical extractants by extracting UO_(2)^(2+) as the representative f-block element.This work provides a direct and versatile method to synthesize symmetrical and unsymmetrical DAPhen,which paves way for the investigations on their coordination properties with metal ions and other applications.
基金supported by National Natural Science Foundation of China(Grant No.22378066,22108040)Collaboration&Innovation Platform Project of National Independent Innovation Demonstration Zone(Fuzhou,Xiamen&Quanzhou)(Project No:3502ZCQXT2023004).
文摘The extraction of uranium from seawater via membrane adsorption is a promising strategy for ensuring a long-term supply of uranium and the sustainability of nuclear energy.However,this approach has been hindered by the longstanding challenge of identifying sustainable membrane materials.In response,we propose a prototypal hybridization strategy to design a novel series of aminated conjugated microporous polymer(CMPN)@collagen fiber membrane(COLM).These sustainable and low-cost membrane materials allow a rapid and high-affinity kinetic to capture 90%of the uranium in just 30 min from 50 ppm with a high selectivity of Kd>105 mL·g^(−1).They also afford a robustly reusable adsorption capacity as high as 345 mg·g^(−1)that could harvest 1.61 mg·g^(−1)of uranium in a short 7-day real marine engineering in Fujian Province,even though suffered from very low uranium concentration of 3.29μg·L^(−1)and tough influence of salts such as 10.77 g·L^(−1)of Na^(+),1.75μg·L^(−1)of VO_(3)^(−)etc.in the rough seas.The structural evidence from both experimental and theoretical studies confirmed the formation of favorable chelating motifs from the amino group on CMPN-COLM,and the intensification by the synergistic effect from the size-sieving action of CMPN and the capillary inflow effect of COLM.
基金funded by the Hainan Province Science and Technology Special Fund under Grant ZDYF2024GXJS292.
文摘Deep learning has made significant progress in the field of oriented object detection for remote sensing images.However,existing methods still face challenges when dealing with difficult tasks such as multi-scale targets,complex backgrounds,and small objects in remote sensing.Maintaining model lightweight to address resource constraints in remote sensing scenarios while improving task completion for remote sensing tasks remains a research hotspot.Therefore,we propose an enhanced multi-scale feature extraction lightweight network EM-YOLO based on the YOLOv8s architecture,specifically optimized for the characteristics of large target scale variations,diverse orientations,and numerous small objects in remote sensing images.Our innovations lie in two main aspects:First,a dynamic snake convolution(DSC)is introduced into the backbone network to enhance the model’s feature extraction capability for oriented targets.Second,an innovative focusing-diffusion module is designed in the feature fusion neck to effectively integrate multi-scale feature information.Finally,we introduce Layer-Adaptive Sparsity for magnitude-based Pruning(LASP)method to perform lightweight network pruning to better complete tasks in resource-constrained scenarios.Experimental results on the lightweight platform Orin demonstrate that the proposed method significantly outperforms the original YOLOv8s model in oriented remote sensing object detection tasks,and achieves comparable or superior performance to state-of-the-art methods on three authoritative remote sensing datasets(DOTA v1.0,DOTA v1.5,and HRSC2016).
基金supports of the National Natural Science Foundation of China(NSFC)(52021004,52394202)key project of the Joint Fund for Innovation and Development of Chongqing Natural Science Foundation(CSTB2022NSCQ-LZX0013)+1 种基金the National Natural Science Foundation of China(NSFC)(52301232,and 52476056)the Natural Science Foundation of Chongqing Province(2024NSCQ-MSX1109).
文摘Controllable synthesis of ultrathin metallene nanosheets and rational design of their spatial arrangement in favor of electrochemical catalysis are critical for their renewable energy applications.Here,a biomimetic design of“Trunk-Branch-Leaf”strategy is proposed to prepare the ultrathin edge-riched Zn-ene“leaves”with a thickness of~2.5 nm,adjacent Zn-ene cross-linked with each other,which are supported by copper nanoneedle“branches”on copper mesh“trunks,”named as Zn-ene/Cu-CM.The resulting superstructure enables the formation of an interconnected network and multiple channels,which can be used as an electrocatalytic CO_(2) reduction reaction(CO_(2)RR)electrode to allow a fast charge and mass transfer as well as a large electrolyte reservoir.By virtue of the distinctive structure,the obtained Zn-ene/Cu-CM electrode exhibits excellent selectivity and activity toward CO production with a maximum Faradaic efficiency of 91.3%and incredible partial current density up to 40 mA cm^(−2),outperforming most of the state-of-the-art Zn-based electrodes for CO_(2) reduction.The phenolphthalein color probe combined with in situ attenuated total reflection-infrared spectroscopy uncovered the formation of the localized pseudo-alkaline microenvironment at the interface of the Zn-ene/Cu-CM electrode.Theoretical calculations confirmed that the localized pH as the origin is responsible for the adsorption of CO_(2) at the interface and the generation of *COOH and *CO intermediates.This study offers valuable insights into developing efficient electrodes through synergistic regulation of reaction microenvironments and active sites,thereby facilitating the electrolysis of practical CO_(2) conversion.
基金financial support of the National Natural Science Foundation of China(No.52472271)the National Key Research and Development Program of China(No.2023YFE0115800)。
文摘Heteroatom-doped carbon is considered a promising alternative to commercial Pt/C as an efficient catalyst for the oxygen reduction reaction(ORR).This study presents the synthesis of iron-loaded,sulfur and nitrogen co-doped carbon(Fe/SNC)via in situ incorporation of 2-aminothiazole molecules into zeolitic imidazolate framework-8(ZIF-8)through coordination between metal ions and organic ligands.Sulfur and nitrogen doping in carbon supports effectively modulates the electronic structure of the catalyst,increases the Brunauer-Emmett-Teller surface area,and exposes more Fe-N_(x)active centers.Fe-loaded,S and N co-doped carbon with Fe/S molar ratio of 1:10(Fe/SNC-10)exhibits a half-wave potential of 0.902 V vs.RHE.After 5000 cycles of cyclic voltammetry,its half-wave potential decreases by only 20 mV vs.RHE,indicating excellent stability.Due to sulfur s lower electronegativity,the electronic structure of the Fe-N_(x)active center is modulated.Additionally,the larger atomic radius of sulfur introduces defects into the carbon support.As a result,Fe/SNC-10 demonstrates superior ORR activity and stability in alkaline solution compared with Fe-loaded N-doped carbon(Fe/NC).Furthermore,the zinc-air battery assembled with the Fe/SNC-10 catalyst shows enhanced performance relative to those assembled with Fe/NC and Pt/C catalysts.This work offers a novel design strategy for advanced energy storage and conversion applications.
基金Funded by the 111 Project(No.B17034)Open Project of Hubei Key Laboratory of Power System Design and Test for Electrical Vehicle(No.ZDSYS202212)+1 种基金Innovative Research Team Development Program of Ministry of Education of China(No.IRT_17R83)the Science and Technology Project of China Southern Power Grid Co.,Ltd.(No.GDKJXM20222546)。
文摘The development of Pt-free catalysts for the oxygen reduction reaction(ORR)is a great issue for meeting the cost challenges of proton exchange membrane fuel cells(PEMFCs)in commercial applications.In this work,a series of RuCo/C catalysts were synthesized by NaBH4 reduction method under the premise that the total metal mass percentage was 20%.X-ray diffraction(XRD)patterns and scanning electron microscopy(SEM)confirmed the formation of single-phase nanoparticles with an average size of 33 nm.Cyclic voltammograms(CV)and linear sweep voltammograms(LSV)tests indicated that RuCo(2:1)/C catalyst had the optimal ORR properties.Additionally,the RuCo(2:1)/C catalyst remarkably sustained 98.1% of its activity even after 3000 cycles,surpassing the performance of Pt/C(84.8%).Analysis of the elemental state of the catalyst surface after cycling using X-ray photoelectron spectroscopy(XPS)revealed that the Ru^(0) percentage of RuCo(2:1)/C decreased by 2.2%(from 66.3% to 64.1%),while the Pt^(0) percentage of Pt/C decreased by 7.1%(from 53.3% to 46.2%).It is suggested that the synergy between Ru and Co holds the potential to pave the way for future low-cost and highly stable ORR catalysts,offering significant promise in the context of PEMFCs.
基金supported by the National Key Research&Development Program of China(No.2022YFC2904905)the National Natural Science Foundation of China(No.52274400)+1 种基金the Project of Zhongyuan Critical Metals Laboratory,China(No.GJJSGFZD202302)the Science and Technology Project of Henan Province,China(No.232102230044)。
文摘The hydrogen reduction kinetics of tungsten trioxide(WO_(3))was investigated via non-isothermal thermogravimetric analysis.Under the local gas-solid reduction conditions,the particle morphology of tungsten powders was found to be consistent with that of raw material WO_(3).The removal of oxygen from tungsten oxide during hydrogen reduction led to the formation of porous structures between the reduced particles,which were obviously different from the polyhedral single-crystal configuration of tungsten powders obtained via chemical vapor deposition.Moreover,the two-stage hydrogen reduction mechanisms of WO_(3) under the local gas-solid reduction conditions can be described using the composite autocatalytic function.The activation energies of the first and second stages of the hydrogen reduction of WO_(3) were determined to be 121 and 135 kJ/mol,respectively.
基金supported by the Helium Enrichment and Detection in Natural Gas Reservoirs Related to Oil and Gas Fields project(Grant No.2025ZD1010500)the Deep Earth Probe and Mineral Resources Exploration―National Science and Technology Major Project.-。
文摘Thermochemical sulfate reduction(TSR)is an important organic-inorganic reaction that occurs within sedimentary basins and alters the original chemical compositions and isotopic structures of hydrocarbons in natural gases.We used the GC-Py-GC-IRMS method to study TSR and obtained a novel finding related to intramolecular carbon isotope fractionation in natural propane.The results show that theΔC-T(δ^(13)C_(central)-13 C_(terminal))andδ^(13)C_(central)values significantly increased to 44.7‰and 11.9‰,respectively,with increasing TSR alteration.In contrast,the 13 C_(terminal)values of propane remained largely unaltered by the TSR reaction.This difference in position-specific isotope fractionation can be attributed to the central carbon’s reactivity being higher than that of terminal carbon during TSR.In sum,the results indicate that theδ^(13)C_(terminal)values of propane can serve as robust indicators for source rock identification of natural gas altered by post-generation reactions such as TSR and anaerobic microbial oxidation.
基金funded by the Innovative Research Group Project of the National Natural Science Foundation of China(52121004)the Research Development Fund(No.RDF-21-02-060)by Xi’an Jiaotong-Liverpool University+1 种基金support received from the Suzhou Industrial Park High Quality Innovation Platform of Functional Molecular Materials and Devices(YZCXPT2023105)the XJTLU Advanced Materials Research Center(AMRC).
文摘Seawater zinc-air batteries are promising energy storage devices due to their high energy density and utilization of seawater electrolytes.However,their efficiency is hindered by the sluggish oxygen reduction reaction(ORR)and chlorideinduced degradation over conventional catalysts.In this study,we proposed a universal synthetic strategy to construct heteroatom axially coordinated Fe–N_(4) single-atom seawater catalyst materials(Cl–Fe–N_(4) and S–Fe–N_(4)).X-ray absorption spectroscopy confirmed their five-coordinated square pyramidal structure.Systematic evaluation of catalytic activities revealed that compared with S–Fe–N_(4),Cl–Fe–N_(4) exhibits smaller electrochemical active surface area and specific surface area,yet demonstrates higher limiting current density(5.8 mA cm^(−2)).The assembled zinc-air batteries using Cl–Fe–N_(4) showed superior power density(187.7 mW cm^(−2) at 245.1 mA cm^(−2)),indicating that Cl axial coordination more effectively enhances the intrinsic ORR activity.Moreover,Cl–Fe–N_(4) demonstrates stronger Cl−poisoning resistance in seawater environments.Chronoamperometry tests and zinc-air battery cycling performance evaluations confirmed its enhanced stability.Density functional theory calculations revealed that the introduction of heteroatoms in the axial direction regulates the electron center of Fe single atom,leading to more active reaction intermediates and increased electron density of Fe single sites,thereby enhancing the reduction in adsorbed intermediates and hence the overall ORR catalytic activity.
