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
Simple and efficient stereo-selective synthesis of exo-5-norbornene-2-carboxylic acid (NBCA) is reported. Preliminary studies on base promoted isomerization of methyl 5-norbornene-2-carboxylate (MNBC) revealed that ra...Simple and efficient stereo-selective synthesis of exo-5-norbornene-2-carboxylic acid (NBCA) is reported. Preliminary studies on base promoted isomerization of methyl 5-norbornene-2-carboxylate (MNBC) revealed that rapid isomerization was accomplished with sodium tert-butoxide (tBuONa), and the exo-content at the equilibrium was ca. 60%. The hydrolyses of endo-rich MNBC (endo/exo = 80/20) under various conditions were carried out. The exo selectivity for resulting NBCA was improved when the hydrolysis was conducted with equimolar water at room temperature in the presence of the stronger base (tBuONa) (endo/exo: 18/82). Whereas the use of excess amount of water led to rapid and non-selective hydrolysis affording high endo content of the product. The plausible reaction mechanism involving rapid equilibrium of thermodynamic isomerization and kinetically preferred hydrolysis of exo ester is proposed.展开更多
We were interested, along this work, in the phenomena of the quintessence and the inflation due to the F-harmonic maps, in other words, in the functions of the scalar field such as the exponential and trigo-harmonic m...We were interested, along this work, in the phenomena of the quintessence and the inflation due to the F-harmonic maps, in other words, in the functions of the scalar field such as the exponential and trigo-harmonic maps. We showed that some F-harmonic map such as the trigonometric functions instead of the scalar field in the lagrangian, allow, in the absence of term of potential, reproduce the inflation. However, there are other F-harmonic maps such as exponential maps which can’t produce the inflation;the pressure and the density of this exponential harmonic field being both of the same sign. On the other hand, these exponential harmonic fields redraw well the phenomenon of the quintessence when the variation of these fields remains weak. The problem of coincidence, however remains.展开更多
Recently, enzymatic peptide synthesis has drawn increasing attention due to its eco-friendly reagents and mild conditions, as compared to traditional chemical peptide synthesis. In this study, we successfully produced...Recently, enzymatic peptide synthesis has drawn increasing attention due to its eco-friendly reagents and mild conditions, as compared to traditional chemical peptide synthesis. In this study, we successfully produced an important antioxidant dipeptide precursor, BOC-Tyr-Ala, via a kinetically controlled enzymatic peptide synthesis reaction, catalyzed by the recombinant car- boxypeptidase Y （CPY） expressed in P. pastoris GS 115. In this reaction, the enzyme activity was 95.043 U/mL, and we used t-butyloxycarbonyl-L-tyrosine-methyl ester （BOC-Tyr-OMe） as the acyl donor and L-alanine （L-Ala） was the amino donor. We optimized the reaction conditions to be： 30 ℃, pH 9.5, organic phase （methanol）/aqueous phase = 1：20, BOC-Tyr-OMe 0.05 mol/L, Ala 0.5 mol/L, and a reaction time of 12 h. Under these conditions, the dipeptide yield reached 49.84%. Then, we established the kinetic model of the synthesis reaction in the form of Michaelis-Menten equation according to the con-centration-time curve during the process and the transpeptidation mechanism. We calculated the apparent Michaelis constant K^（app）mand the apparent maximum reaction rate r^（app）max to be 2.9946 x 10^-2 mol/L and 2.0406 x 10.2 mmol/（mL h）, respectively.展开更多
Up to now,the DNA molecule adsorbed on a surface was believed to always preserve its native structure.This belief implies a negligible contribution of lateral surface forces during and after DNA adsorption although th...Up to now,the DNA molecule adsorbed on a surface was believed to always preserve its native structure.This belief implies a negligible contribution of lateral surface forces during and after DNA adsorption although their impact has never been elucidated.High-resolution atomic force microscopy was used to observe that stiff DNA molecules kinetically trapped on monomolecular films comprising one-dimensional periodically charged lamellar templates as a single layer or as a sublayer are oversaturated by sharp discontinuous kinks and can also be locally melted and supercoiled.We argue that kink/anti-kink pairs are induced by an overcritical lateral bending stress(>30 pNnm)inevitable for the highly anisotropic 1D-1D electrostatic interaction of DNA and underlying rows of positive surface charges.In addition,the unexpected kink-inducing mechanical instability in the shape of the template-directed DNA confined between the positively charged lamellar sides is observed indicating the strong impact of helicity.The previously reported anomalously low values of the persistence length of the surface-adsorbed DNA are explained by the impact of the surface-induced low-scale bending.The sites of the local melting and supercoiling are convincingly introduced as other lateral stress-induced structural DNA anomalies by establishing a link with DNA high-force mechanics.The results open up the study in the completely unexplored area of the principally anomalous kinetically trapped DNA surface conformations in which the DNA local mechanical response to the surface-induced spatially modulated lateral electrostatic stress is essentially nonlinear.The underlying rich and complex in-plane nonlinear physics acts at the nanoscale beyond the scope of applicability of the worm-like chain approximation.展开更多
Enhancing the kinetic stability of glasses typically requires deepening their thermodynamic stability,which increases structural rigidity and degrades ductility;decoupling these properties remains a major challenge.He...Enhancing the kinetic stability of glasses typically requires deepening their thermodynamic stability,which increases structural rigidity and degrades ductility;decoupling these properties remains a major challenge.Here,we demonstrate that spatial patterning in metallic glasses produces exceptional kinetic ultrastability that coexists with a thermodynamically metastable,high-energy state and excellent plasticity.Guided by atomistic simulations using replica exchange molecular dynamics and machine learning interatomic potentials,we reveal that oxygen,through reaction-diffusion-coupled pattern dynamics,self-organizes into oxygen-centered pinned structures(OPSs)that serve as localized kinetic constraints.These motifs drastically slow structural relaxation,delivering kinetic stability comparable to ultrastable glasses even as the system retains the high inherent energy of rapidly quenched states.The OPSs’topology yields a spatially uniform activation of plastic events,promoting strain delocalization under mechanical load.By geometrically tailoring oxygen patterns,we increase the glass transition onset temperature(Tonset)by about 200 K with negligible loss of deformability.Our findings establish a practicable paradigm for decoupling kinetic and thermodynamic stability and point to a scalable,additive route for designing amorphous materials that combine hyperstability with plasticity.展开更多
Restricting molecular motion of fluorophores is the most direct and effective approach to creating highly emissive fluorescent materials.However,attempts to limit molecular motion of conventional fluorophores in aqueo...Restricting molecular motion of fluorophores is the most direct and effective approach to creating highly emissive fluorescent materials.However,attempts to limit molecular motion of conventional fluorophores in aqueous environments often encounter undesired aggregation-caused quenching(ACQ).To address this challenge,this study presents an innovative design of a water-soluble supramolecular scaffold with a rigidmicrodomain,achieved by assembling a cyclic peptide-diblock copolymer conjugate into cylindrical nanoparticles,where the rigid microdomain is provided by the hydrophobic polymer segment with a high glass transition temperature.Supramolecular fluorophores(termed as Supra-fluorophores)are constructed by noncovalently dispersing fluorophores within the rigid microenvironment of the scaffold through a simple coassembly approach,effectively mitigating molecular motion and ACQ.This strategy accommodates a wide range of fluorophores,resulting in Supra-fluorophores with fluorescence quantum yields up to 71.6%and volume-normalized brightness reaching 19,910 M−1 cm−1 nm−3.Furthermore,increased rigidity significantly reduces dynamic exchange among assemblies by three orders of magnitude,thereby generating kinetically trapped Supra-fluorophores that exhibit minimal dye crosstalk upon mixing.This approach demonstrates substantial potential for advanced bioimaging applications,such as multicolor cell labeling,real-time tracking,and high-resolution cellular imaging.展开更多
As one of the most promising new energy sources,hydrogen energy is expected to usher in a full-fledged“hydrogen economy”in the 21st century.Compared with traditional high-pressure gaseous and cryogenic liquid hydrog...As one of the most promising new energy sources,hydrogen energy is expected to usher in a full-fledged“hydrogen economy”in the 21st century.Compared with traditional high-pressure gaseous and cryogenic liquid hydrogen storage methods,solid-state chemical hydrogen storage shows significant advantages in safety,high efficiency,and cost-effectiveness.Magnesium-based lightweight hydrogen storage materials have attracted widespread attention due to their high gravimetric hydrogen storage density(7.6%)and favorable reversibility.However,their sluggish reaction kinetics and stringent operating conditions(with H2 release temperatures exceeding 350°C and H2 absorption pressures above 4 MPa)pose major challenges for practical applications.Domestic and international researchers have conducted in-depth studies to address these issues,achieving substantial progress in the modification of magnesium-based hydrogen storage alloys.This paper systematically elaborates on major modification techniques such as alloying,nanostructuring,and catalytic material doping,providing a comprehensive analysis of the strengths and limitations of each approach.Furthermore,it offers prospects for the future development of magnesium-based hydrogen storage materials by integrating current theoretical and experimental research findings.展开更多
Under the backdrop of“Carbon Peak and Carbon Neutrality”(dual carbon)goal in China,the methane-carbon dioxide reforming reaction has attracted considerable attention due to its environmental benefits of converting t...Under the backdrop of“Carbon Peak and Carbon Neutrality”(dual carbon)goal in China,the methane-carbon dioxide reforming reaction has attracted considerable attention due to its environmental benefits of converting two greenhouse gases(methane and carbon dioxide)into syngas and its promising industrial applications.Nickel(Ni)-based catalysts,with high catalytic activity,low cost,and abundant resources,are considered ideal candidates for industrial applications.In this article,three reaction kinetic models were briefly introduced,namely the Power-Law(PL)model,the Eley-Rideal(ER)model,and the Langmuir-Hinshelwood-Hougen-Watson(LHHW)model.Based on the LHHW model,the reaction kinetics and mechanisms of different catalytic systems were systematically discussed,including the properties of supports,the doping of noble metals and transition metals,the role of promoters,and the influence of the geometric and electronic structures of Ni on the reaction mechanism.Furthermore,the kinetics of carbon deposition and elimination on various catalysts were analyzed.Based on the reaction rate expressions for carbon elimination,the reasons for the high activity of transition metal iron(Fe)-doped catalysts and core-shell structured catalysts in carbon elimination were explained.Based on the detailed collation and comparative analysis of the reaction mechanisms and kinetic characteristics across diverse Ni-based catalytic systems,a theoretical guidance for the designing of high-performance catalysts was provided in this work.展开更多
The sulfation and decomposition process has proven effective in selectively extracting lithium from lepidolite.It is essential to clarify the thermochemical behavior and kinetic parameters of decomposition reactions.A...The sulfation and decomposition process has proven effective in selectively extracting lithium from lepidolite.It is essential to clarify the thermochemical behavior and kinetic parameters of decomposition reactions.Accordingly,comprehensive kinetic study by employing thermalgravimetric analysis at various heating rates was presented in this paper.Two main weight loss regions were observed during heating.The initial region corresponded to the dehydration of crystal water,whereas the subsequent region with overlapping peaks involved complex decomposition reactions.The overlapping peaks were separated into two individual reaction peaks and the activation energy of each peak was calculated using isoconversional kinetics methods.The activation energy of peak 1 exhibited a continual increase as the reaction conversion progressed,while that of peak 2 steadily decreased.The optimal kinetic models,identified as belonging to the random nucleation and subsequent growth category,provided valuable insights into the mechanism of the decomposition reactions.Furthermore,the adjustment factor was introduced to reconstruct the kinetic mechanism models,and the reconstructed models described the kinetic mechanism model more accurately for the decomposition reactions.This study enhanced the understanding of the thermochemical behavior and kinetic parameters of the lepidolite sulfation product decomposition reactions,further providing theoretical basis for promoting the selective extraction of lithium.展开更多
Magnesium hydride(MgH_(2)) demonstrates immense potential as a solid-state hydrogen storage material,while its commercial utilization is impeded by the elevated operating temperature and sluggish reaction kinetics.Her...Magnesium hydride(MgH_(2)) demonstrates immense potential as a solid-state hydrogen storage material,while its commercial utilization is impeded by the elevated operating temperature and sluggish reaction kinetics.Herein,a MOF derived multi-phase FeNi_(3)-S catalyst was specially designed for efficient hydrogen storage in MgH_(2).Experiments confirmed that the incorporation of FeNi_(3)-S into MgH_(2) significantly lowered the desorption temperature and accelerated the kinetics of hydrogen desorption and reabsorption.The initial dehydrogenation temperature of the MgH_(2)+10 wt% FeNi_(3)-S composite was 202 ℃,which was 123 ℃ lower than that of pure MgH_(2).At 325 ℃,the MgH_(2)+10 wt% FeNi_(3)-S composite released 6.57 wt% H_(2)(fully dehydrogenated) within 1000 s.Remarkably,MgH_(2)+ 10 wt% FeNi_(3)-S composite initiated rehydrogenation at room temperature and rapidly absorbed 2.49 wt% H_(2) within 30 min at 100 ℃.Moreover,6.3 wt% H_(2) was still retained after 20 cycles at 300 ℃,demonstrating the superior cycling performance of the MgH_(2)+10 wt% FeNi_(3)-S composite.The activation energy fitting calculations further evidenced the addition of FeNi_(3)-S enhanced the de/resorption kinetics of MgH_(2)(E_(a)= 98.6 k J/mol and 43.3 k J/mol,respectively).Through phase and microstructural analysis,it was determined that the exceptional hydrogen storage performance of the composite was attributed to the in-situ formation of Mg/Mg_(2)Ni + Fe/MgS and MgH_(2)/Mg_(2)NiH_(4)+Fe/MgS hydrogen storage systems.Further mechanistic analysis revealed that Mg_(2)Ni/Mg_(2)NiH_(4) served as “hydrogen pump” and Fe/Mg S served as “hydrogen diffusion channel”,thus accelerating the dissociation and recombination of hydrogen molecules.In conclusion,this work offers insight into catalysts combining transition metal alloys and transition metal sulfide for exerting muti-phase synergistic effect on boosting the dehydrogenation/hydrogenation reactions of MgH_(2),which can also inspire future pioneering work on designing and fabricating high efficient catalysts in other energy storage related areas.展开更多
The localization and differential diagnosis of the sentinel lymph nodes(SLNs)are particularly important for tumor staging,surgical planning and prognosis.In this work,kinetically inert manganese(II)-based hybrid micel...The localization and differential diagnosis of the sentinel lymph nodes(SLNs)are particularly important for tumor staging,surgical planning and prognosis.In this work,kinetically inert manganese(II)-based hybrid micellar complexes(MnCs)for magnetic resonance imaging(MRI)were developed using an amphiphilic manganese-based chelate(C18-PhDTA-Mn)with reliable kinetic stability and self-assembled with a series of amphiphilic PEG-C18 polymers of different molecular weights(C18En,n=10,20,50).Among them,the probes composed by 1:10 mass ratio of manganese chelate/C18En had slightly different hydrodynamic particle sizes with similar surface charges as well as considerable relaxivities(∼13 mM^(−1)s^(−1)at 1.5 T).In vivo lymph node imaging in mice revealed that the MnC MnC-20 formed by C18E20 with C18-PhDTA-Mn at a hydrodynamic particle size of 5.5 nm had significant signal intensity brightening effect and shortened T1 relaxation time.At an imaging probe dosage of 125μg Mn/kg,lymph nodes still had significant signal enhancement in 2 h,while there is no obvious signal intensity alteration in non-lymphoid regions.In 4T1 tumor metastatic mice model,SLNs showed less signal enhancement and smaller T1 relaxation time variation at 30 min post-injection,when compared with normal lymph nodes.This was favorable to differentiate normal lymph nodes from SLN under a 3.0-T clinical MRI scanner.In conclusion,the strategy of developing manganese-based MR nanoprobes was useful in lymph node imaging.展开更多
The volatilization characteristics and kinetic mechanisms of arsenic were investigated in the temperature range of 623−773 K and pressure ranges of 10−10000 Pa.The experimental results reveal that the evaporation rate...The volatilization characteristics and kinetic mechanisms of arsenic were investigated in the temperature range of 623−773 K and pressure ranges of 10−10000 Pa.The experimental results reveal that the evaporation rate increases with increasing temperature and decreasing pressure.Surface reaction control dominates at low pressures(<100 Pa),whereas diffusion control dominates at high pressures(>5000 Pa).The evaporation behavior is successfully described by an Arrhenius-type model for temperature dependence and Logistic model for pressure dependence.Key kinetic parameters,including the critical pressure,maximum evaporation rate and evaporation coefficient,were calculated.The evaporation coefficient varies between 0.010 and 0.223,and the critical pressures vary between 281 and 478 Pa with temperature.展开更多
In this article, we present a facile, direct, synthetic approach of preparing monodisperse [Au2s（SePh）ls]- nanoclusters in high yield. In this synthetic approach, two-phase Brust-Schiffrin method is used. Both PhSeH...In this article, we present a facile, direct, synthetic approach of preparing monodisperse [Au2s（SePh）ls]- nanoclusters in high yield. In this synthetic approach, two-phase Brust-Schiffrin method is used. Both PhSeH and NaBH4 should be added drop-wise to the solution of Au （III） at the same time. The formula and molecular purity of [Au25（SePh）ls] TOA＋ clusters are characterized by MALDI-TOF mass spectrometry, NMR and TGA analysis. Furthermore, some critical parameters to obtain pure [Au25（SePh）18]-TOA＋ are identified, including the NaBH4-to-Au ratio, the selenolate-to-Au ratio and the temperature. The facile, direct, high yield synthetic method can be widely applied in the theoretical research of Au clusters protected by selenol.展开更多
Desulfurization of CaO–Al_(2)O_(3) particles in molten steel was observed in situ using high-temperature confocal scanning laser microscopy.The effects of the aluminum and silicon contents of molten steel on desulfur...Desulfurization of CaO–Al_(2)O_(3) particles in molten steel was observed in situ using high-temperature confocal scanning laser microscopy.The effects of the aluminum and silicon contents of molten steel on desulfurization were analyzed.When the total aluminum content in the steel increased from 6 to 1100 ppm,the CaS content in CaO–Al_(2)O_(3) particles increased from 2.1wt%to 84.84wt%after the reaction for 90 s.Furthermore,when the silicon content in the steel increased from 0.01wt%to 2.20wt%,the CaS content in CaO–Al_(2)O_(3) particles increased from 1.53wt%to 79.01wt%after the reaction for 90 s.This indicates that the increase in the aluminum and silicon contents of the steel promoted the desulfurization of CaO–Al_(2)O_(3) particles.A kinetic model was established to predict the CaO–Al_(2)O_(3) particles composition,and the diffusion coefficient of sulfur in CaO–Al_(2)O_(3) particles was 9.375×10^(−10)m^(2)·s^(−1) at 1600℃,which provided a new method for the calculation of diffusion coefficient.展开更多
This research explores the influence of crystallinity on gas chromatographic(GC) separation using covalent organic frameworks(COFs) as stationary phases.Three COF materials(CTF-DCBs) with varying crystallinity were sy...This research explores the influence of crystallinity on gas chromatographic(GC) separation using covalent organic frameworks(COFs) as stationary phases.Three COF materials(CTF-DCBs) with varying crystallinity were synthesized and characterized.CTF-DCB-1,with superior crystallinity,demonstrated highselectivity GC separation of benzene isomers as well as styrene/phenylacetylene mixtures,while CTFDCB-2 and CTF-DCB-3 exhibited lower crystallinity and worse separation performance.Thermodynamic and kinetic tests showed that CTF-DCB-1 had the worst thermodynamic adsorption but low diffusion mass transfer resistance,which resulted in the best separation.Therefore,optimizing the crystallinity of COFs is necessary for balancing the kinetic diffusion and thermodynamic interactions towards the analytes,achieving high-performance GC stationary phases.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
Kinetic impact is the most practical planetary-defense technique,with momentum-transfer efficiency central to deflection design.We present a Monte Carlo photometric framework that couples ejecta sampling,dynamical evo...Kinetic impact is the most practical planetary-defense technique,with momentum-transfer efficiency central to deflection design.We present a Monte Carlo photometric framework that couples ejecta sampling,dynamical evolution,and image synthesis to compare directly with HST,LICIACube,ground-based and Lucy observations of the DART impact.Decomposing ejecta into(1)a highvelocity(~1600 m/s)plume exhibiting Na/K resonance,(2)a low-velocity(~1 m/s)conical component shaped by binary gravity and solar radiation pressure,and(3)meter-scale boulders,we quantify each component’s mass and momentum.Fitting photometric decay curves and morphological evolution yields size-velocity distributions and,via scaling laws,estimates of Dimorphos’bulk density,cratering parameters,and cohesive strength that agree with dynamical constraints.Photometric ejecta modeling therefore provides a robust route to constrain momentum enhancement and target properties,improving predictive capability for kinetic-deflection missions.展开更多
The crystallization and aggregation characteristics of the active layer components in organic solar cells(OSCs)are one of the core factors determining photovoltaic performance,influencing the entire process from light...The crystallization and aggregation characteristics of the active layer components in organic solar cells(OSCs)are one of the core factors determining photovoltaic performance,influencing the entire process from light absorption to charge separation,transport,and ultimately charge collection.Dynamic changes in crystallization and aggregation states can also disrupt the microstructure of the active layer,thus shortening the lifetime of the cell.In this study,a morphology modulation strategy is proposed to regulate the crystallization kinetics of non-fullerene acceptors by employing the polymer molecule PYIT as a nucleating agent.An appropriate amount of PYIT was first completely dissolved with the non-fullerene acceptor Y6 and left to stand for 24 h,followed by the fabrication of layer-by-layer processed OSCs.Experiments demonstrated that high crystallinity of PYIT allows it to act as a crystallization nucleus,promoting the crystallization,orientation consistency,and ordered stacking of the acceptor.These nanoscale structural optimizations facilitate efficient charge transport,enhance exciton dissociation efficiency,and suppress unfavorable energetic disorder.Consequently,not only was the power conversion efficiency(PCE)of D18-Cl/Y6-based layer-by-layer processed OSC increased from 18.08%to 19.13%,but the atmospheric stability and long-term lifetime of the OSCs were also significantly improved.Notably,this strategy is also applicable to indoor OSCs,and the PYIT-optimized device can achieve a PCE of 27.0%under 1000 lux light-emitting diode(LED,3200K)irradiation,which is superior to that of the control device(24.2%).This work develops a crystal engineering strategy that is able to simultaneously optimize the microscopic morphology and charge dynamics properties in OSCs,thereby achieving simultaneous improvement in efficiency and stability.展开更多
Wide-temperature applications of sodium-ion batteries(SIBs)are severely limited by the sluggish ion insertion/diffusion kinetics of conversion-type anodes.Quantum-sized transition metal dichalcogenides possess unique ...Wide-temperature applications of sodium-ion batteries(SIBs)are severely limited by the sluggish ion insertion/diffusion kinetics of conversion-type anodes.Quantum-sized transition metal dichalcogenides possess unique advantages of charge delocalization and enrich uncoordinated electrons and short-range transfer kinetics,which are crucial to achieve rapid low-temperature charge transfer and high-temperature interface stability.Herein,a quantum-scale FeS_(2) loaded on three-dimensional Ti_(3)C_(2) MXene skeletons(FeS_(2) QD/MXene)fabricated as SIBs anode,demonstrating impressive performance under wide-temperature conditions(−35 to 65).The theoretical calculations combined with experimental characterization interprets that the unsaturated coordination edges of FeS_(2) QD can induce delocalized electronic regions,which reduces electrostatic potential and significantly facilitates efficient Na+diffusion across a broad temperature range.Moreover,the Ti_(3)C_(2) skeleton reinforces structural integrity via Fe-O-Ti bonding,while enabling excellent dispersion of FeS_(2) QD.As expected,FeS_(2) QD/MXene anode harvests capacities of 255.2 and 424.9 mAh g^(−1) at 0.1 A g^(−1) under−35 and 65,and the energy density of FeS_(2) QD/MXene//NVP full cell can reach to 162.4 Wh kg^(−1) at−35,highlighting its practical potential for wide-temperatures conditions.This work extends the uncoordinated regions induced by quantum-size effects for exceptional Na^(+)ion storage and diffusion performance at wide-temperatures environment.展开更多
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.
文摘Simple and efficient stereo-selective synthesis of exo-5-norbornene-2-carboxylic acid (NBCA) is reported. Preliminary studies on base promoted isomerization of methyl 5-norbornene-2-carboxylate (MNBC) revealed that rapid isomerization was accomplished with sodium tert-butoxide (tBuONa), and the exo-content at the equilibrium was ca. 60%. The hydrolyses of endo-rich MNBC (endo/exo = 80/20) under various conditions were carried out. The exo selectivity for resulting NBCA was improved when the hydrolysis was conducted with equimolar water at room temperature in the presence of the stronger base (tBuONa) (endo/exo: 18/82). Whereas the use of excess amount of water led to rapid and non-selective hydrolysis affording high endo content of the product. The plausible reaction mechanism involving rapid equilibrium of thermodynamic isomerization and kinetically preferred hydrolysis of exo ester is proposed.
文摘We were interested, along this work, in the phenomena of the quintessence and the inflation due to the F-harmonic maps, in other words, in the functions of the scalar field such as the exponential and trigo-harmonic maps. We showed that some F-harmonic map such as the trigonometric functions instead of the scalar field in the lagrangian, allow, in the absence of term of potential, reproduce the inflation. However, there are other F-harmonic maps such as exponential maps which can’t produce the inflation;the pressure and the density of this exponential harmonic field being both of the same sign. On the other hand, these exponential harmonic fields redraw well the phenomenon of the quintessence when the variation of these fields remains weak. The problem of coincidence, however remains.
基金supported by Ministry of Science and Technology of China(No.2012YQ090194 and No.2013AA102204)the National Natural Science Foundation of China(No.21676191,No.21476165,and No.21621004)
文摘Recently, enzymatic peptide synthesis has drawn increasing attention due to its eco-friendly reagents and mild conditions, as compared to traditional chemical peptide synthesis. In this study, we successfully produced an important antioxidant dipeptide precursor, BOC-Tyr-Ala, via a kinetically controlled enzymatic peptide synthesis reaction, catalyzed by the recombinant car- boxypeptidase Y （CPY） expressed in P. pastoris GS 115. In this reaction, the enzyme activity was 95.043 U/mL, and we used t-butyloxycarbonyl-L-tyrosine-methyl ester （BOC-Tyr-OMe） as the acyl donor and L-alanine （L-Ala） was the amino donor. We optimized the reaction conditions to be： 30 ℃, pH 9.5, organic phase （methanol）/aqueous phase = 1：20, BOC-Tyr-OMe 0.05 mol/L, Ala 0.5 mol/L, and a reaction time of 12 h. Under these conditions, the dipeptide yield reached 49.84%. Then, we established the kinetic model of the synthesis reaction in the form of Michaelis-Menten equation according to the con-centration-time curve during the process and the transpeptidation mechanism. We calculated the apparent Michaelis constant K^（app）mand the apparent maximum reaction rate r^（app）max to be 2.9946 x 10^-2 mol/L and 2.0406 x 10.2 mmol/（mL h）, respectively.
基金This work was supported in part by a grant from Russian Scientific Foundation(Project No.17-75-30064).
文摘Up to now,the DNA molecule adsorbed on a surface was believed to always preserve its native structure.This belief implies a negligible contribution of lateral surface forces during and after DNA adsorption although their impact has never been elucidated.High-resolution atomic force microscopy was used to observe that stiff DNA molecules kinetically trapped on monomolecular films comprising one-dimensional periodically charged lamellar templates as a single layer or as a sublayer are oversaturated by sharp discontinuous kinks and can also be locally melted and supercoiled.We argue that kink/anti-kink pairs are induced by an overcritical lateral bending stress(>30 pNnm)inevitable for the highly anisotropic 1D-1D electrostatic interaction of DNA and underlying rows of positive surface charges.In addition,the unexpected kink-inducing mechanical instability in the shape of the template-directed DNA confined between the positively charged lamellar sides is observed indicating the strong impact of helicity.The previously reported anomalously low values of the persistence length of the surface-adsorbed DNA are explained by the impact of the surface-induced low-scale bending.The sites of the local melting and supercoiling are convincingly introduced as other lateral stress-induced structural DNA anomalies by establishing a link with DNA high-force mechanics.The results open up the study in the completely unexplored area of the principally anomalous kinetically trapped DNA surface conformations in which the DNA local mechanical response to the surface-induced spatially modulated lateral electrostatic stress is essentially nonlinear.The underlying rich and complex in-plane nonlinear physics acts at the nanoscale beyond the scope of applicability of the worm-like chain approximation.
基金supported by the National Natural Science Foundation of China(Grants Nos.T2325004)the Advanced Materials-National Science and Technology Major Project(Grant No.2024ZD0606900)+3 种基金the Talent Hub for‘AI+New Materials’Basic Researchsupported by the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant Nos.XDB0620103 and XDB0510301)the National Natural Science Foundation of China(Grant No.12472112)R.S.acknowledges the Young Scientists Fund of the National Natural Science Foundation of China(51801046).
文摘Enhancing the kinetic stability of glasses typically requires deepening their thermodynamic stability,which increases structural rigidity and degrades ductility;decoupling these properties remains a major challenge.Here,we demonstrate that spatial patterning in metallic glasses produces exceptional kinetic ultrastability that coexists with a thermodynamically metastable,high-energy state and excellent plasticity.Guided by atomistic simulations using replica exchange molecular dynamics and machine learning interatomic potentials,we reveal that oxygen,through reaction-diffusion-coupled pattern dynamics,self-organizes into oxygen-centered pinned structures(OPSs)that serve as localized kinetic constraints.These motifs drastically slow structural relaxation,delivering kinetic stability comparable to ultrastable glasses even as the system retains the high inherent energy of rapidly quenched states.The OPSs’topology yields a spatially uniform activation of plastic events,promoting strain delocalization under mechanical load.By geometrically tailoring oxygen patterns,we increase the glass transition onset temperature(Tonset)by about 200 K with negligible loss of deformability.Our findings establish a practicable paradigm for decoupling kinetic and thermodynamic stability and point to a scalable,additive route for designing amorphous materials that combine hyperstability with plasticity.
基金the assistance of SUSTech Core Research Facilities,and CSNS for the allocation of beam time(grant nos.P0121122200005 and P0124052700001).
文摘Restricting molecular motion of fluorophores is the most direct and effective approach to creating highly emissive fluorescent materials.However,attempts to limit molecular motion of conventional fluorophores in aqueous environments often encounter undesired aggregation-caused quenching(ACQ).To address this challenge,this study presents an innovative design of a water-soluble supramolecular scaffold with a rigidmicrodomain,achieved by assembling a cyclic peptide-diblock copolymer conjugate into cylindrical nanoparticles,where the rigid microdomain is provided by the hydrophobic polymer segment with a high glass transition temperature.Supramolecular fluorophores(termed as Supra-fluorophores)are constructed by noncovalently dispersing fluorophores within the rigid microenvironment of the scaffold through a simple coassembly approach,effectively mitigating molecular motion and ACQ.This strategy accommodates a wide range of fluorophores,resulting in Supra-fluorophores with fluorescence quantum yields up to 71.6%and volume-normalized brightness reaching 19,910 M−1 cm−1 nm−3.Furthermore,increased rigidity significantly reduces dynamic exchange among assemblies by three orders of magnitude,thereby generating kinetically trapped Supra-fluorophores that exhibit minimal dye crosstalk upon mixing.This approach demonstrates substantial potential for advanced bioimaging applications,such as multicolor cell labeling,real-time tracking,and high-resolution cellular imaging.
基金Supported by Design and Performance Study of High-flux Metal Hydride Reactor Based on the Bionic Optimization(2078262)the‘Four-Chain’Integration Project at the Qinchuangyuan Chief Platform(S2025-YF-ZDXM)。
文摘As one of the most promising new energy sources,hydrogen energy is expected to usher in a full-fledged“hydrogen economy”in the 21st century.Compared with traditional high-pressure gaseous and cryogenic liquid hydrogen storage methods,solid-state chemical hydrogen storage shows significant advantages in safety,high efficiency,and cost-effectiveness.Magnesium-based lightweight hydrogen storage materials have attracted widespread attention due to their high gravimetric hydrogen storage density(7.6%)and favorable reversibility.However,their sluggish reaction kinetics and stringent operating conditions(with H2 release temperatures exceeding 350°C and H2 absorption pressures above 4 MPa)pose major challenges for practical applications.Domestic and international researchers have conducted in-depth studies to address these issues,achieving substantial progress in the modification of magnesium-based hydrogen storage alloys.This paper systematically elaborates on major modification techniques such as alloying,nanostructuring,and catalytic material doping,providing a comprehensive analysis of the strengths and limitations of each approach.Furthermore,it offers prospects for the future development of magnesium-based hydrogen storage materials by integrating current theoretical and experimental research findings.
基金Supported by Innovation Capability Support Program of Shaanxi(2024RS-CXTD-53,2024ZC-KJXX-096)the Key R&D Program of Shaanxi Province(2022QCY-LL-69)Xi’an Science and Technology Project(24GXFW0089)。
文摘Under the backdrop of“Carbon Peak and Carbon Neutrality”(dual carbon)goal in China,the methane-carbon dioxide reforming reaction has attracted considerable attention due to its environmental benefits of converting two greenhouse gases(methane and carbon dioxide)into syngas and its promising industrial applications.Nickel(Ni)-based catalysts,with high catalytic activity,low cost,and abundant resources,are considered ideal candidates for industrial applications.In this article,three reaction kinetic models were briefly introduced,namely the Power-Law(PL)model,the Eley-Rideal(ER)model,and the Langmuir-Hinshelwood-Hougen-Watson(LHHW)model.Based on the LHHW model,the reaction kinetics and mechanisms of different catalytic systems were systematically discussed,including the properties of supports,the doping of noble metals and transition metals,the role of promoters,and the influence of the geometric and electronic structures of Ni on the reaction mechanism.Furthermore,the kinetics of carbon deposition and elimination on various catalysts were analyzed.Based on the reaction rate expressions for carbon elimination,the reasons for the high activity of transition metal iron(Fe)-doped catalysts and core-shell structured catalysts in carbon elimination were explained.Based on the detailed collation and comparative analysis of the reaction mechanisms and kinetic characteristics across diverse Ni-based catalytic systems,a theoretical guidance for the designing of high-performance catalysts was provided in this work.
基金financially supported by the National Natural Science Foundation of China(Nos.52034002 and U2202254)the Fundamental Research Funds for the Central Universities,China(No.FRF-TT-19-001)。
文摘The sulfation and decomposition process has proven effective in selectively extracting lithium from lepidolite.It is essential to clarify the thermochemical behavior and kinetic parameters of decomposition reactions.Accordingly,comprehensive kinetic study by employing thermalgravimetric analysis at various heating rates was presented in this paper.Two main weight loss regions were observed during heating.The initial region corresponded to the dehydration of crystal water,whereas the subsequent region with overlapping peaks involved complex decomposition reactions.The overlapping peaks were separated into two individual reaction peaks and the activation energy of each peak was calculated using isoconversional kinetics methods.The activation energy of peak 1 exhibited a continual increase as the reaction conversion progressed,while that of peak 2 steadily decreased.The optimal kinetic models,identified as belonging to the random nucleation and subsequent growth category,provided valuable insights into the mechanism of the decomposition reactions.Furthermore,the adjustment factor was introduced to reconstruct the kinetic mechanism models,and the reconstructed models described the kinetic mechanism model more accurately for the decomposition reactions.This study enhanced the understanding of the thermochemical behavior and kinetic parameters of the lepidolite sulfation product decomposition reactions,further providing theoretical basis for promoting the selective extraction of lithium.
基金supported by the National Key R&D Program of China (No.2022YFB3803703)the National Natural Science Foundation of China (Nos.52071141,52271212,52201250,51771056,22305104)+1 种基金the Natural Science Foundation of Jiangsu Province (No.BK20210893)the Ministry of Science and Technology of the People’s Republic of China (No.G2023014022L)。
文摘Magnesium hydride(MgH_(2)) demonstrates immense potential as a solid-state hydrogen storage material,while its commercial utilization is impeded by the elevated operating temperature and sluggish reaction kinetics.Herein,a MOF derived multi-phase FeNi_(3)-S catalyst was specially designed for efficient hydrogen storage in MgH_(2).Experiments confirmed that the incorporation of FeNi_(3)-S into MgH_(2) significantly lowered the desorption temperature and accelerated the kinetics of hydrogen desorption and reabsorption.The initial dehydrogenation temperature of the MgH_(2)+10 wt% FeNi_(3)-S composite was 202 ℃,which was 123 ℃ lower than that of pure MgH_(2).At 325 ℃,the MgH_(2)+10 wt% FeNi_(3)-S composite released 6.57 wt% H_(2)(fully dehydrogenated) within 1000 s.Remarkably,MgH_(2)+ 10 wt% FeNi_(3)-S composite initiated rehydrogenation at room temperature and rapidly absorbed 2.49 wt% H_(2) within 30 min at 100 ℃.Moreover,6.3 wt% H_(2) was still retained after 20 cycles at 300 ℃,demonstrating the superior cycling performance of the MgH_(2)+10 wt% FeNi_(3)-S composite.The activation energy fitting calculations further evidenced the addition of FeNi_(3)-S enhanced the de/resorption kinetics of MgH_(2)(E_(a)= 98.6 k J/mol and 43.3 k J/mol,respectively).Through phase and microstructural analysis,it was determined that the exceptional hydrogen storage performance of the composite was attributed to the in-situ formation of Mg/Mg_(2)Ni + Fe/MgS and MgH_(2)/Mg_(2)NiH_(4)+Fe/MgS hydrogen storage systems.Further mechanistic analysis revealed that Mg_(2)Ni/Mg_(2)NiH_(4) served as “hydrogen pump” and Fe/Mg S served as “hydrogen diffusion channel”,thus accelerating the dissociation and recombination of hydrogen molecules.In conclusion,this work offers insight into catalysts combining transition metal alloys and transition metal sulfide for exerting muti-phase synergistic effect on boosting the dehydrogenation/hydrogenation reactions of MgH_(2),which can also inspire future pioneering work on designing and fabricating high efficient catalysts in other energy storage related areas.
基金supported by the National Natural Science Foundation of China(NSFC,52073192)the Innovative Research Groups of the National Natural Science Foundation of China(81621003).
文摘The localization and differential diagnosis of the sentinel lymph nodes(SLNs)are particularly important for tumor staging,surgical planning and prognosis.In this work,kinetically inert manganese(II)-based hybrid micellar complexes(MnCs)for magnetic resonance imaging(MRI)were developed using an amphiphilic manganese-based chelate(C18-PhDTA-Mn)with reliable kinetic stability and self-assembled with a series of amphiphilic PEG-C18 polymers of different molecular weights(C18En,n=10,20,50).Among them,the probes composed by 1:10 mass ratio of manganese chelate/C18En had slightly different hydrodynamic particle sizes with similar surface charges as well as considerable relaxivities(∼13 mM^(−1)s^(−1)at 1.5 T).In vivo lymph node imaging in mice revealed that the MnC MnC-20 formed by C18E20 with C18-PhDTA-Mn at a hydrodynamic particle size of 5.5 nm had significant signal intensity brightening effect and shortened T1 relaxation time.At an imaging probe dosage of 125μg Mn/kg,lymph nodes still had significant signal enhancement in 2 h,while there is no obvious signal intensity alteration in non-lymphoid regions.In 4T1 tumor metastatic mice model,SLNs showed less signal enhancement and smaller T1 relaxation time variation at 30 min post-injection,when compared with normal lymph nodes.This was favorable to differentiate normal lymph nodes from SLN under a 3.0-T clinical MRI scanner.In conclusion,the strategy of developing manganese-based MR nanoprobes was useful in lymph node imaging.
基金Yunnan Fundamental Research Project,China(No.202201BE070001-056)。
文摘The volatilization characteristics and kinetic mechanisms of arsenic were investigated in the temperature range of 623−773 K and pressure ranges of 10−10000 Pa.The experimental results reveal that the evaporation rate increases with increasing temperature and decreasing pressure.Surface reaction control dominates at low pressures(<100 Pa),whereas diffusion control dominates at high pressures(>5000 Pa).The evaporation behavior is successfully described by an Arrhenius-type model for temperature dependence and Logistic model for pressure dependence.Key kinetic parameters,including the critical pressure,maximum evaporation rate and evaporation coefficient,were calculated.The evaporation coefficient varies between 0.010 and 0.223,and the critical pressures vary between 281 and 478 Pa with temperature.
基金the financial support by the National Natural Science Foundation of China (20871112, 21072001, 21372006)Changjiang Scholars Program+1 种基金the Scientific Research Foundation for Returning Overseas Chinese Scholars, State Education Ministry, Ministry of Human Resources and Social Security, Anhui Province International Scientific and Technological Cooperation Project211 Project of Anhui University
文摘In this article, we present a facile, direct, synthetic approach of preparing monodisperse [Au2s（SePh）ls]- nanoclusters in high yield. In this synthetic approach, two-phase Brust-Schiffrin method is used. Both PhSeH and NaBH4 should be added drop-wise to the solution of Au （III） at the same time. The formula and molecular purity of [Au25（SePh）ls] TOA＋ clusters are characterized by MALDI-TOF mass spectrometry, NMR and TGA analysis. Furthermore, some critical parameters to obtain pure [Au25（SePh）18]-TOA＋ are identified, including the NaBH4-to-Au ratio, the selenolate-to-Au ratio and the temperature. The facile, direct, high yield synthetic method can be widely applied in the theoretical research of Au clusters protected by selenol.
基金supported by the National Key R&D Program of China(No.2023YFB3709900)the National Nature Science Foundation of China(No.U22A20171)+1 种基金the China Baowu Low Carbon Metallurgy Innovation Foundation(No.BWLCF202315)the High Steel Center(HSC)at North China University of Technology and University of Science and Technology Beijing,China.
文摘Desulfurization of CaO–Al_(2)O_(3) particles in molten steel was observed in situ using high-temperature confocal scanning laser microscopy.The effects of the aluminum and silicon contents of molten steel on desulfurization were analyzed.When the total aluminum content in the steel increased from 6 to 1100 ppm,the CaS content in CaO–Al_(2)O_(3) particles increased from 2.1wt%to 84.84wt%after the reaction for 90 s.Furthermore,when the silicon content in the steel increased from 0.01wt%to 2.20wt%,the CaS content in CaO–Al_(2)O_(3) particles increased from 1.53wt%to 79.01wt%after the reaction for 90 s.This indicates that the increase in the aluminum and silicon contents of the steel promoted the desulfurization of CaO–Al_(2)O_(3) particles.A kinetic model was established to predict the CaO–Al_(2)O_(3) particles composition,and the diffusion coefficient of sulfur in CaO–Al_(2)O_(3) particles was 9.375×10^(−10)m^(2)·s^(−1) at 1600℃,which provided a new method for the calculation of diffusion coefficient.
基金supported by the National Natural Science Foundation of China (Nos.22174067,22204078,and 22374077)the Natural Science Foundation of Jiangsu Province of China (No.BK20220370)+3 种基金Jiangsu Provincial Department of Education (No.22KJB150009)State Key Laboratory of Analytical Chemistry for Life Science (No.SKLACLS2218)the Priority Academic Program Development of Jiangsu Higher Education Institutions,Jiangsu Association for Science and Technology (No.TJ-2023-076)Shanghai Synchrotron Radiation Facility Beamline BL17B1 (No.2021-NFPSPT-006657)。
文摘This research explores the influence of crystallinity on gas chromatographic(GC) separation using covalent organic frameworks(COFs) as stationary phases.Three COF materials(CTF-DCBs) with varying crystallinity were synthesized and characterized.CTF-DCB-1,with superior crystallinity,demonstrated highselectivity GC separation of benzene isomers as well as styrene/phenylacetylene mixtures,while CTFDCB-2 and CTF-DCB-3 exhibited lower crystallinity and worse separation performance.Thermodynamic and kinetic tests showed that CTF-DCB-1 had the worst thermodynamic adsorption but low diffusion mass transfer resistance,which resulted in the best separation.Therefore,optimizing the crystallinity of COFs is necessary for balancing the kinetic diffusion and thermodynamic interactions towards the analytes,achieving high-performance GC stationary phases.
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 National Natural Science Foundation of China(Grant No.12272018)the National Key Basic Research Project(2022JCJQZD20600).
文摘Kinetic impact is the most practical planetary-defense technique,with momentum-transfer efficiency central to deflection design.We present a Monte Carlo photometric framework that couples ejecta sampling,dynamical evolution,and image synthesis to compare directly with HST,LICIACube,ground-based and Lucy observations of the DART impact.Decomposing ejecta into(1)a highvelocity(~1600 m/s)plume exhibiting Na/K resonance,(2)a low-velocity(~1 m/s)conical component shaped by binary gravity and solar radiation pressure,and(3)meter-scale boulders,we quantify each component’s mass and momentum.Fitting photometric decay curves and morphological evolution yields size-velocity distributions and,via scaling laws,estimates of Dimorphos’bulk density,cratering parameters,and cohesive strength that agree with dynamical constraints.Photometric ejecta modeling therefore provides a robust route to constrain momentum enhancement and target properties,improving predictive capability for kinetic-deflection missions.
基金supported by the National Natural Science Foundation of China (NSFC grant no. 62474028, 52130304, and62222503)the Natural Science Foundation of Sichuan Province(2025ZNSFSC0037, 2025ZNSFSC1460, and 2024NSFSC1447)+1 种基金the National Key R and D Program of China (2023YFB2604101)sponsored by the Sichuan Province Key Laboratory of Display Science and Technology
文摘The crystallization and aggregation characteristics of the active layer components in organic solar cells(OSCs)are one of the core factors determining photovoltaic performance,influencing the entire process from light absorption to charge separation,transport,and ultimately charge collection.Dynamic changes in crystallization and aggregation states can also disrupt the microstructure of the active layer,thus shortening the lifetime of the cell.In this study,a morphology modulation strategy is proposed to regulate the crystallization kinetics of non-fullerene acceptors by employing the polymer molecule PYIT as a nucleating agent.An appropriate amount of PYIT was first completely dissolved with the non-fullerene acceptor Y6 and left to stand for 24 h,followed by the fabrication of layer-by-layer processed OSCs.Experiments demonstrated that high crystallinity of PYIT allows it to act as a crystallization nucleus,promoting the crystallization,orientation consistency,and ordered stacking of the acceptor.These nanoscale structural optimizations facilitate efficient charge transport,enhance exciton dissociation efficiency,and suppress unfavorable energetic disorder.Consequently,not only was the power conversion efficiency(PCE)of D18-Cl/Y6-based layer-by-layer processed OSC increased from 18.08%to 19.13%,but the atmospheric stability and long-term lifetime of the OSCs were also significantly improved.Notably,this strategy is also applicable to indoor OSCs,and the PYIT-optimized device can achieve a PCE of 27.0%under 1000 lux light-emitting diode(LED,3200K)irradiation,which is superior to that of the control device(24.2%).This work develops a crystal engineering strategy that is able to simultaneously optimize the microscopic morphology and charge dynamics properties in OSCs,thereby achieving simultaneous improvement in efficiency and stability.
基金supported by the National Nature Science Foundation of China(Nos.52202335 and 52171227)Natural Science Foundation of Jiangsu Province(No.BK20221137)National Key R&D Program of China(2024YFE0108500).
文摘Wide-temperature applications of sodium-ion batteries(SIBs)are severely limited by the sluggish ion insertion/diffusion kinetics of conversion-type anodes.Quantum-sized transition metal dichalcogenides possess unique advantages of charge delocalization and enrich uncoordinated electrons and short-range transfer kinetics,which are crucial to achieve rapid low-temperature charge transfer and high-temperature interface stability.Herein,a quantum-scale FeS_(2) loaded on three-dimensional Ti_(3)C_(2) MXene skeletons(FeS_(2) QD/MXene)fabricated as SIBs anode,demonstrating impressive performance under wide-temperature conditions(−35 to 65).The theoretical calculations combined with experimental characterization interprets that the unsaturated coordination edges of FeS_(2) QD can induce delocalized electronic regions,which reduces electrostatic potential and significantly facilitates efficient Na+diffusion across a broad temperature range.Moreover,the Ti_(3)C_(2) skeleton reinforces structural integrity via Fe-O-Ti bonding,while enabling excellent dispersion of FeS_(2) QD.As expected,FeS_(2) QD/MXene anode harvests capacities of 255.2 and 424.9 mAh g^(−1) at 0.1 A g^(−1) under−35 and 65,and the energy density of FeS_(2) QD/MXene//NVP full cell can reach to 162.4 Wh kg^(−1) at−35,highlighting its practical potential for wide-temperatures conditions.This work extends the uncoordinated regions induced by quantum-size effects for exceptional Na^(+)ion storage and diffusion performance at wide-temperatures environment.
