The Beijing 325 m meteorological tower stands as a pivotal research platform for exploring atmospheric boundary layer physics and atmospheric chemistry.With a legacy spanning 45 years,the tower has played a crucial ro...The Beijing 325 m meteorological tower stands as a pivotal research platform for exploring atmospheric boundary layer physics and atmospheric chemistry.With a legacy spanning 45 years,the tower has played a crucial role in unraveling the complexities of urban air pollution,atmospheric processes,and climate change in Beijing,China.This review paper provides a comprehensive overview of the measurements on the tower over the past two decades.Through long-term comprehensive observations,researchers have elucidated the intricate relationships between anthropogenic emissions,meteorological dynamics,and atmospheric composition,shedding light on the drivers of air pollution and its impacts on public health.The vertical measurements on the tower also enable detailed investigations into boundary layer dynamics,turbulent mixing,and pollutant dispersion,providing invaluable data for validating chemical transport models.Key findings from the tower’s research include the identification of positive feedback mechanisms between aerosols and the boundary layer,the characterization of pollutant sources and transport pathways,the determination of fluxes of gaseous and particulate species,and the assessment of the effectiveness of pollution control measures.Additionally,isotopic measurements have provided new insights into the sources and formation processes of particulate matter and reactive nitrogen species.Finally,the paper outlines future directions for tower-based research,emphasizing the need for long-term comprehensive measurements,the development of innovative tower platforms,and integration of emerging technologies.展开更多
In chemical science,the vertical ionization potential(VIP)is a crucial metric for understanding the electronegativity,hardness and softness of chemical material systems as well as the electronic structure and stabilit...In chemical science,the vertical ionization potential(VIP)is a crucial metric for understanding the electronegativity,hardness and softness of chemical material systems as well as the electronic structure and stability of molecules.Ever since the last century,the model chemistry composite methods have witnessed tremendous developments in computing the thermodynamic properties as well as the barrier heights.However,their performance in realm of the vertical electron processes of molecular systems has been rarely explored.In this study,we for the first time benchmarked the model chemistry composite methods(e.g.,CBS-QB3,G4 and W1BD)in comparison with the commonly used Koopmans's theorem(KT),electron propagator theory(e.g.,OVGF,D2,P3 and P3+)and CCSD(T)methods in calculating the VIP for up to 613 molecular systems with available experimental measurements.The large-scale test calculations strongly showed that the CBS-QB3 model chemistry composite technique can be well recommended to calculate VIP from the perspectives of accuracy,economy and applicability.Notably,the VIP values of up to 7 molecules were identified to have the absolute errors of larger than 0.3 e V at all calculation levels,which have strong hints that their VIP experimental values should be re-investigated.展开更多
A method for the rapid reduction of acyl chlorides to aldehydes was developed using pinacolborane(HBpin)as the reducing agent.The method exhibits excellent generality for both aromatic and aliphatic substrates,affordi...A method for the rapid reduction of acyl chlorides to aldehydes was developed using pinacolborane(HBpin)as the reducing agent.The method exhibits excellent generality for both aromatic and aliphatic substrates,affording aldehydes in isolated yields of up to 88%with broad functional group tolerance,including cyano,halogen,alkenyl,ketone,and ester groups.Moreover,the method enables gram-scale aldehyde synthesis and shows high efficiency in reducing in situ generated acyl chlorides,thereby enhancing its synthetic practicality.展开更多
A surface pyrolysis and gas-phase combustion of the Ammonium Perchlorate(AP)/Hydroxy Terminated Polybutadiene(HTPB)composite propellant reaction kinetic mechanism with five-step chemical reaction is adopted.The effect...A surface pyrolysis and gas-phase combustion of the Ammonium Perchlorate(AP)/Hydroxy Terminated Polybutadiene(HTPB)composite propellant reaction kinetic mechanism with five-step chemical reaction is adopted.The effects of helium injection on the burning rate and combustion of AP/HTPB propellant are analyzed in details,and the characteristics of motor performance are obtained.The numerical simulation results demonstrate that helium injection enhances the combustion chamber pressure,thereby increasing the burning rate of propellant.However,the primary combustion reaction of the AP/HTPB propellant takes place within a thin layer on the burning surface,so the low-temperature helium has minimal impact on the gasphase combustion.Ultimately,the helium not only elevates the nozzle exit velocity,resulting in specific impulse gain,but also reduces the exhaust plume temperature.With an increase of helium mass flow rate,the area of the velocity increase zone at the nozzle exit continuously decreases,but the average velocity in the motor exit continuously increases.Overall,when the helium flow rate is 2.5 kg/s,the specific impulse can reach 10.5%.Reducing the helium injection hole diameter enhances mixing of helium and combustion gas and expands the velocity increase zone,thereby maximizing the exit velocity gain in average velocity at the nozzle exit.When the injection hole diameter is reduced from 100 mm to 20 mm,the specific impulse gain increases from 3.1%to 10.6%.Furthermore,increasing helium injection temperature greatly boosts the velocity of the mixed gas with the same helium mass fraction ultimately improving specific impulse.展开更多
Investigating the detonation reaction zone structures of high explosives is significant for understanding detonation reaction mechanism.This study employed an integrated approach combining machine learning prediction,...Investigating the detonation reaction zone structures of high explosives is significant for understanding detonation reaction mechanism.This study employed an integrated approach combining machine learning prediction,theoretical calculation,and experimental characterization to determine the detonation reaction zone width of CL-20-based aluminized explosive.In this study,the detonation reaction zone refers to the reaction zone between the von Neumann(VN)peak and sonic point,which usually means the so-called detonation driving zone(DDZ).For the machine learning prediction,an ensemble model integrating Random Forest and Support Vector Regression was developed to predict the reaction zone width using a dataset of 19 publicly available samples.For the theoretical calculation,the Wood-Kirkwood(W-K)detonation theory model was utilized to implement numerical calculation of the reaction zone structures,incorporating chemical reaction kinetics to describe the detonation reaction progress.In experimental characterization,the Photon Doppler Velocimetry(PDV)was applied with LiF as the optical window to measure the particle velocity profile of detonation products and derive the reaction zone width.The results indicate that the reaction zone width values are 0.25 mm,0.28 mm,and 0.26 mm obtained from machine learning prediction,theoretical calculation,and experimental characterization,respectively.The corresponding velocities at the Chapman-Jouguet(CJ)point are 1,938 m/s,2,047 m/s,and 1,982 m/s,respectively.The maximum relative deviation in reaction zone width among three methods is approximately 7.7%,while that for CJ particle velocity is approximately 3.3%.These results from all three methods agree well within engineering error.This validates the effectiveness of integrating machine learning prediction,theoretical calculation and advanced experimental techniques for studying the detonation reaction zone structures of high explosives.This research provides insights into the detonation reaction mechanism and reaction zone characteristics of CL-20-based aluminized explosive.展开更多
Designing efficient,stable dual-functional combustion catalysts remains a key challenge in developing next-generation solid propellants,particularly in achieving wide pressure plateau combustion.Herein,we synthesize a...Designing efficient,stable dual-functional combustion catalysts remains a key challenge in developing next-generation solid propellants,particularly in achieving wide pressure plateau combustion.Herein,we synthesize a series of carbon dot-based catalysts(CDs-1,CDs-2,CDs/Cu)via oxidative etching and hydrothermal methods,and employ them to replace conventional carbon black(CB)at 0.65 wt%loading in the preparation of HMX-CMDB propellants.Systematic evaluation through combined thermochemical analysis(50–350℃),laser ignition diagnostics(50–350 W/cm^(2)),and combustion chamber testing(4–18 MPa)reveals remarkable catalytic enhancements.The optimized CDs/Cu catalyst demonstrates multifunctional superiority:(1)7.4℃ reduction in HMX-CMDB decomposition temperature at 10℃/min(from 205.2℃ to 196.0℃);(2)66.7%decrease in laser ignition delay(from 45 ms to 15 ms);(3)190.9%burning rate increase at 4 MPa(from 4.61 mm/s to 13.41 mm/s);(4)lower pressure exponent of 0.02 within 4–18 MPa range.Notably,CDs-1 induces stable"Plateau"combustion(4–14 MPa),while CDs/Cu achieves"Mesa"effects(8–12 MPa)via synergistic thermal feedback mechanisms-both phenomena ensure stable operation of the engine.Mechanistic studies integrate thermochemical kinetics,ignition combustion process,combustion flame structure,and combustion wave temperature distribution trends,which establish a new paradigm for the study of high efficiency combustion catalysts for solid propellants.展开更多
Boron has attracted increasing attention in the field of high-energy explosives and propellants due to its high volume calorific value and mass calorific value.However,the complicated combustion process and low combus...Boron has attracted increasing attention in the field of high-energy explosives and propellants due to its high volume calorific value and mass calorific value.However,the complicated combustion process and low combustion efficiency hinder its wide application.To tackle this challenge,bioinspired polydopamine(PDA)interface reinforced boron-Viton composites,with high structure stability and excellent energy releasing efficiency,are designed and prepared,combining the interface regulation of PDA biomimetic materials and combustion promotion of fluoropolymers.Firstly,the stronger adsorption energy of PDA with boron compared to Viton is demonstrated by molecular dynamics simulations.Next,B@PDA@Viton is prepared by the combination of in-situ dopamine polymerization and solvent/nonsolvent method,and the double-layer core-shell structure is confirmed by XPS,FTIR,and TEM characterizations.TG-DSC analysis shows that B@PDA@Viton possesses superior thermal properties,with a 55.48%increase in oxidation heat compared to raw B.Furthermore,ignition and combustion performance tests indicate that B@PDA@Viton reduces ignition delay by 57.56%and increases heat of combustion by 68.63%relative to raw B.These findings elucidate the ignition and combustion mechanisms of B@PDA@Viton.This work not only developed high-performance boron-based composite fuels but also provided insights into the development of boron-based fuels.展开更多
The presence of a surface oxide film(B_(2)O_(3))on boron(B)particles significantly compromises their combustion efficiency and kinetic performance in fuel-rich solid propellants.This study proposes an innovative conti...The presence of a surface oxide film(B_(2)O_(3))on boron(B)particles significantly compromises their combustion efficiency and kinetic performance in fuel-rich solid propellants.This study proposes an innovative continuous modification strategy combining non-thermal plasma(NTP)etching with fluorocarbon passivation.Characterization and kinetic analysis revealed that reactive plasma species—including atomic hydrogen(H),electronically excited molecular hydrogen(H_(2)^(*)),vibrationally excited molecular hydrogen(H_(2)v),and hydrogen ions(H^(+))—dominate the reduction of B_(2)O_(3)through lowering the transition energy barrier and shifting the reaction spontaneity.Subsequent argon plasma fragmentation of C_(8)F_(18)generates fluorocarbon radicals that form conformal passivation coatings(thickness:7 nm)on purified boron surfaces.The modified boron particles exhibit 37.5℃lower exothermic peak temperature and 27.2%higher heat release(14.8 kJ/g vs.11.6 kJ/g)compared to untreated counterparts.Combustion diagnostics reveal 194%increase in maximum flame height(135.10 mm vs.46.03 mm)and 134%enhancement in flame propagation rate(4.44 cm/s vs.1.90 cm/s).This NTP-based surface engineering approach establishes a scalable pathway for developing highperformance boron-based energetic composites.展开更多
The direct transformation of dinitrogen(N_(2)) into nitrogen-containing organic compounds holds substantial importance.In this work,we report a titanium-promoted method for the conversion of N_(2) to N-methylimides.In...The direct transformation of dinitrogen(N_(2)) into nitrogen-containing organic compounds holds substantial importance.In this work,we report a titanium-promoted method for the conversion of N_(2) to N-methylimides.Initially,the N_(2)-bridging end-on dititanium side-on dipotassium complex[{(Tren^(TMS))Ti}_(2)(μ-η^(1):η^(1):η^(2):η^(2)-N_(2)K_(2))] underwent simultaneous disproportionation and N-methylation reactions in the presence of methyl trifluoromethanesulfonate(Me OTf),yielding [{(N^(Me,TMS)NN^(TMS)_(2))Ti}(μ-NMe)]_(2) with complete cleavage of the N≡N bond.The nucleophilicity of the N-methylated intermediate allowed it to react with electrophilic reagents such as trimethylchlorosilane(TMSCl) to form heptamethyldisilazane,or with acyl chlorides to generate N-methylimides.Moreover,nitrogen-15(^(15)N) labeled experiments provided a novel approach to synthesizing ^(15)N-labeled methylimides.展开更多
Plantago major L.,commonly known as plantain,waybread,or dooryard plantain,is a versatile medicinal plant with multiple therapeutic applications.Traditionally,various parts of the plant have been formulated into syrup...Plantago major L.,commonly known as plantain,waybread,or dooryard plantain,is a versatile medicinal plant with multiple therapeutic applications.Traditionally,various parts of the plant have been formulated into syrups,drops,ointments,vaginal suppositories,gargles,and roasted preparations to treat diverse ailments,such as liver disorders,earaches,epilepsy,asthma,stomachaches,diarrhea,constipation,polymenorrhea,and uterine disorders.The plant contains clinically valuable bioactive compounds,including polysaccharides,flavonoids,lipids,iridoid glycosides,caffeic acid derivatives,terpenoids,alkaloids,and organic acids.These bioactive constituents are the primary contributors to the plant’s broad spectrum of biological activities,including antioxidant,anti-inflammatory,antibacterial,antidiarrheal,hepatoprotective,antiviral,antiphage,antinociceptive,antiulcerogenic,antigenotoxic,and immunomodulatory effects of the plant.This review comprehensively summarizes the phytochemical composition,traditional medicinal applications,and biological properties of this multifunctional medicinal plant.展开更多
The pursuit of heat-resistant energetic materials(HREMs)with thermal stability beyond 450℃ presents a significant challenge that has yet to be achieved.In this work,we develop an innovative electronic delocalization ...The pursuit of heat-resistant energetic materials(HREMs)with thermal stability beyond 450℃ presents a significant challenge that has yet to be achieved.In this work,we develop an innovative electronic delocalization strategy to design and synthesize a planar dizwitterionic diamino-bistriazolotetrazine,designated as TYX-1.The unique structural feature of TYX-1,including a nitrogen-rich fused ring system,planar conformation,and dizwitterionic configuration,combined with its hydrogen-bonded organic framework(HOF)structure,confer exceptional thermal stability(The onset temperature is 428℃,and the peak temperature is 473℃),high density(1.84 g/cm^(3)),and remarkable detonation performance(detonation velocity:8616 m/s).Furthermore,TYX-1 exhibits an impressive insensitivity(impact sensitivity>40 J;friction sensitivity>360 N),surpassing all previously reported HREMs.Theoretical calculations and single-crystal clearly indicate that the delocalizedπelectrons within the dizwitterionic bistriazolotetrazine rings and the HOF structure of TYX-1 are pivotal in ensuring its high thermal stability and high energy density.The discovery of TYX-1 marks a significant advancement in the field of HREMs and is anticipated to catalyze substantial progress in various high-temperature applications reliant on energetic materials.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 b...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-C3H7CHO 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 nC3H7CHO 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
With the rapid growth of technologies requiring high-power energy storage,achieving long-term cyclic stability under ultra-high current density is a key challenge.Aqueous zinc-ion batteries(AZIBs)are promising candida...With the rapid growth of technologies requiring high-power energy storage,achieving long-term cyclic stability under ultra-high current density is a key challenge.Aqueous zinc-ion batteries(AZIBs)are promising candidates due to their intrinsic safety and low cost,but they suffer from severe interfacial instability at rates exceeding 10 mA cm^(-2),which drastically shortens their cycle life.Inspired by theoretical calculations,triglyme(TGDE)additive with strong electron-donating groups into Zn(OTf)_(2) electrolytes effectively disrupts the hydrogen-bond network among free water molecules,while the weak coordination of TGDE with Zn^(2+)promotes the entry of OTf-into the primary Zn^(2+)solvated sheath,thus decreasing the coordination number of water with Zn^(2+).As such,the hydrogen-bond network and the bulk solvated structure are reconstructed with better stability.Moreover,the strong adsorption of TGDE lying on the Zn(002)surface would induce Zn depositions along(002)together with the reduced exposed surface,further effectively inhibiting side reactions.Likewise,TGDE electrolyte induces the formation of such ZnF_(2)-ZnS dual-layer solid electrolyte interface(SEI)with superior chemical stability and ionic conductivity,thereby regulating Zn^(2+)flux with dendrite-free depositions.Based on this electrolyte,Zn‖Zn cells can be stably cycled for 1300 h at a limit of 10 mA cm^(-2) and 10 mAh cm^(-2).The assembled Zn‖V_(2)O_(5) full cells still maintain 99.9%capacity retention after 1000 cycles at 10 A g^(-1).This work provides a feasible approach for designing aqueous electrolytes to reconstruct the hydrogen-bond network and solvated structure,which can be extended to the applications of high-rate and high-temperature scenarios.展开更多
To elucidate the dispersion and explosion characteristics of multi-metal powder and liquid composite fuel formulations,high-energy metal powders(aluminum(Al),boron(B),and magnesium hydride(MgH_(2)))are incorporated in...To elucidate the dispersion and explosion characteristics of multi-metal powder and liquid composite fuel formulations,high-energy metal powders(aluminum(Al),boron(B),and magnesium hydride(MgH_(2)))are incorporated into a liquid fuel primarily composed of diethyl ether(DEE)and isopropyl nitrate(IPN).The explosion characteristics of different solid-liquid fuel-air-explosive(FAE)under unconfined conditions are investigated using a high-speed camera,infrared thermal imaging,and a pressure measurement system.Results demonstrate that high-energy metal powders significantly enhance detonation energy dissipation,with aluminum exhibiting the most pronounced effect.Fuel 5#(45.4 wt%DEE,9.2 wt%IPN,29.5 wt%Al,9.1 wt%B,6.8 wt%MgH_(2))exhibits superior explosion performance,achieving higher values of overpressure,impulse,and thermal radiation damage during the detonation stage compared to other fuels.However,Fuel 5#also displays faster decay rates,attributed to accelerated heat release rates induced by B and MgH_(2)powders.This study reveals that different metal powders in solid-liquid FAE exhibit distinct enhancements in explosion performance,providing critical insights for optimizing composite fuel design.展开更多
Developing advanced polymeric materials with enhanced mechanical properties and functionalities has been a long-standing goal in materials science.Recently,supramolecular polymeric materials (SPMs) have drawn increase...Developing advanced polymeric materials with enhanced mechanical properties and functionalities has been a long-standing goal in materials science.Recently,supramolecular polymeric materials (SPMs) have drawn increased attention due to their unique properties and potential applications in self-healing,shape memory,sensors,and flexible electronics.Here,we develop an ionic cluster-optimized microphase separation strategy to enhance the toughening and energy dissipation capabilities of polydisulfide-based supramolecular polymers.The mechanical properties,including Young’s modulus and toughness,are significantly improved by integrating the quadruple H-bonding 2-ureido-4-pyrimidone (UPy) induced microphase separation with iron(Ⅲ)-to-carboxylate ionic clusters.By combining established chemical approaches with adjustable polymer phase ratios,it is revealed that the synergistic effect of these factors expands the interchain spacing,facilitates the formation of microphase domains,and enhances the tolerance of polythioctic acid-based polymers to external mechanical and thermal stimuli,meeting the practical requirements for industrial plastic applications.Moreover,the UPy-functionalized polymers incorporating iron carboxylate clusters exhibit good one-way shape memory behavior with practical applicability at a relatively low recovery temperature.Our work demonstrates a novel strategy for constructing industrially viable shape memory dynamic SPMs and paves the way for future innovations in developing SPMs.展开更多
The infrared channels of the FY-4B advanced geosynchronous radiation imagers(AGRI) play a crucial role in temperature and humidity analyses for mesoscale numerical weather prediction, particularly in enhancing the ini...The infrared channels of the FY-4B advanced geosynchronous radiation imagers(AGRI) play a crucial role in temperature and humidity analyses for mesoscale numerical weather prediction, particularly in enhancing the initial field quality and the forecasting accuracy of the model. This study assimilated FY-4B AGRI data into the CMA-MESO model and analyzed the bias characteristics and correction methods. Analysis of the AGRI data revealed a clear diurnal variation in the bias, which was positively correlated with the solar elevation angle. However, the diurnal variation in the bias lagged behind the solar elevation angle, likely owing to temperature changes and delayed instrument responses resulting from solar radiation. To address this issue, we propose a correction method that utilizes the solar elevation angle after an optimal time shift. Using the time-shifted solar elevation angle as a predictor effectively reduces the diurnal variation in bias and significantly improves the correction effect. This approach provides theoretical support for the assimilation of FY-4B AGRI data into mesoscale numerical weather predictions, thereby enhancing the reliability of the assimilation results.展开更多
As a key precursor of hydroxyl(OH) radicals, the budget of nitrous acid(HONO) at different altitudes has received extensive attention. In this study, vertically resolved observations of HONO, NO_(2), O_(3), and HCHO w...As a key precursor of hydroxyl(OH) radicals, the budget of nitrous acid(HONO) at different altitudes has received extensive attention. In this study, vertically resolved observations of HONO, NO_(2), O_(3), and HCHO were conducted during an autumn field campaign in Beijing in 2019. The significant correlation between HONO and NO2, along with variations in their ratios across different altitudes, underscores the importance of aerosol surface chemistry in HONO formation and its altitude-dependent behavior. To enhance the model performance, the heterogeneous conversion of NO_(2) and its photochemical enhancement are incorporated into the 1D model. The simulations reveal that the nocturnal HONO production is dominated by the heterogeneous conversion of NO_(2) both at the surface and aloft. During the daytime, groundsurface sources of HONO are mainly driven by nitrate photolysis and light-enhanced heterogeneous conversion of NO_(2).Meanwhile, a large portion of the HONO generated at the surface is transported upwards through vertical mixing. In the higher atmosphere, HONO originates from vertical transport and in situ processes. As precursors of OH radicals, the observed concentrations of HONO, O_(3), and HCHO exhibit distinct diurnal variations and vertical distribution patterns.HONO contributes to OH radical production predominantly during the early morning across all layers and it even becomes the main contributor throughout the daytime in the lowest layer near the ground, while O_(3) and HCHO become more prominent towards midday, especially in the higher layers. These results will be beneficial for a deeper understanding of the atmospheric oxidation process within the urban boundary layer.展开更多
Carbon dioxide(CO_(2))is the main greenhouse gas(GHG)released by human activities.The substitution of fossil resources by biomass as a bio-renewable resource,has significant potential to reduce GHG emissions.The appro...Carbon dioxide(CO_(2))is the main greenhouse gas(GHG)released by human activities.The substitution of fossil resources by biomass as a bio-renewable resource,has significant potential to reduce GHG emissions.The approach to biomass,as the only true full-scale alternative to fossil resources,is progressing rapidly.Converting biomass into furanic compounds,as versatile platform chemicals for synthesizing a wide range of bio-based products is the cornerstone of sustainable technologies.The extensive body of this review combines the biomass valorization to furanic compounds by CO_(2)utilization and furanic compounds conversion by CO_(2)fixation.These processes can be strategically applied through both‘thermochemical’and‘electrochemical’pathways,by utilizing CO_(2)from the atmosphere or industrial emission point and returning it to the natural carbon cycle.In the thermochemical pathway CO_(2)acts as a carbon source(carboxylation and polymerization)or active reaction assistant in the biomass conversion(CO_(2)-assisted conversion),without altering its oxidation state,facilitating the synthesis of valuable products and polymers.Conversely,in the electrochemical pathway,CO_(2)can be used as a carbon source(electrocarboxylation)to give the corresponding carboxylic acid,or it can undergo reduction,yielding methanol,carbon monoxide(CO),formic acid,and analogous compounds,while on the other side,furanic compounds undergo oxidation yielding high-value-added chemicals.Finally,potential future research directions are suggested to promote CO_(2)utilization and fixation in the valorization of biomass-derived furanic compounds,and challenges facing further research are highlighted.展开更多
In winter 2018,an aerosol physicochemical experiment was conducted in the Western Pacific Ocean(WPO)aboard the Research Vessel KEXUE of Chinese Academy of Sciences.This study systematically investigated both natural a...In winter 2018,an aerosol physicochemical experiment was conducted in the Western Pacific Ocean(WPO)aboard the Research Vessel KEXUE of Chinese Academy of Sciences.This study systematically investigated both natural and anthropogenic effects on marine aerosols optical properties,as well as the applicability of multi-satellite products and IMPROVE equation.The averaged aerosol optical depth(AOD500 nm)was 0.31±0.16 andÅngström exponent440–675 nm was 0.29±0.30.In offshore China,significant anthropogenic emissions affected the marine environment.In remote WPO,dust aerosols transported from northern China,Siberia,Central Asia,and those settling from the upper troposphere originating from north Africa,Arabian peninsula,and western India,were dominant.The spatial trends of AOD were opposite in the mid-latitude and southern seas of WPO.The highest AOD,0.32±0.23,appeared along the coast of South Asia at mid-latitude,decreasing from offshore seas to remote oceans.In low-latitude and equatorial seas,AOD significantly increased from coast to remote oceans.Ångström exponent dropped significantly from the coast to remote oceans as anthropogenic influence diminished across the entire WPO.Correlation analysis showed that both MODIS-C6 and Himawari AOD prod-ucts showed similar applicability in coastal urban areas,while Himawari AOD is highly recommended for coastal background and marine environment due to its finer resolution.The extinction coefficient derived from PM_(2.5) chemical compositions using IMPROVE algorithm exhibited a significant correlation(R^(2)=0.58)with the con-currently measured AOD in the absence of long-distance transport,suggesting that the IMPROVE is a reasonable proxy of the columnar average of marine aerosol extinctions free from transport influences.展开更多
Localized high-concentration electrolytes(LHCEs)are considered as promising electrolyte candidates to resolve technical issues of metal batteries owing to their unique interfacial properties and solvation structures.H...Localized high-concentration electrolytes(LHCEs)are considered as promising electrolyte candidates to resolve technical issues of metal batteries owing to their unique interfacial properties and solvation structures.Herein,we propose a self-assembly chemical strategy into the LCHEs induced by ordered nanostructure of zwitterionic co-solutes for highly efficient and ultrastable zinc(Zn)metal batteries.Through the systematic screening of six zwitterionic compounds,3-(decyldimethylammonio)propanesulfonate salt(C_(10))with the decyl chain and zwitterions was determined as an optimum to construct quasi-spherical aggregates with a periodic length of 3.77 nm,as confirmed by comprehensive synchronous small-angle X-ray scattering,Guinier,pair distance distribution function,Porod,and other spectroscopic characterizations and molecular dynamic simulation.In particularly,this self-assembled structure in electrolyte environments was attributed to increasing the proportion of both contact and aggregated ion pairs for the formation of LHCEs as well as to providing fast and selective Zn^(2+)conducting channels and uniform solid electrolyte interfaces for facilitated charge transfer kinetics.Moreover,the preferential adsorption of the self-assembled C_(10)on the Zn(002)surface modulated the electrical double layer to suppress hydrogen evolution and corrosion reactions.Consequently,the Zn‖Zn symmetric cells in Zn(OTf)_(2)/C_(10)electrolytes showed long-term plating/stripping behaviors over 2800 h at 1 mA cm^(-2)and 1 mAh cm^(-2)as well as over 1200 h even at 5 mA cm^(-2)and 5 mAh cm^(-2)with a very high depth of discharge of 42.7%.Furthermore,the ZnllVO_(2)/CNT full cells in Zn(OTf)_(2)/C_(10)electrolytes delivered a record-high capacity of 8.10 mAh cm^(-2)at an ultrahigh cathode mass loading of 50 mg cm^(-2)after 150 cycles.展开更多
基金supported by the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDB0760200)the National Natural Science Foundation of China(Grant Nos.42330605 and 42377101).
文摘The Beijing 325 m meteorological tower stands as a pivotal research platform for exploring atmospheric boundary layer physics and atmospheric chemistry.With a legacy spanning 45 years,the tower has played a crucial role in unraveling the complexities of urban air pollution,atmospheric processes,and climate change in Beijing,China.This review paper provides a comprehensive overview of the measurements on the tower over the past two decades.Through long-term comprehensive observations,researchers have elucidated the intricate relationships between anthropogenic emissions,meteorological dynamics,and atmospheric composition,shedding light on the drivers of air pollution and its impacts on public health.The vertical measurements on the tower also enable detailed investigations into boundary layer dynamics,turbulent mixing,and pollutant dispersion,providing invaluable data for validating chemical transport models.Key findings from the tower’s research include the identification of positive feedback mechanisms between aerosols and the boundary layer,the characterization of pollutant sources and transport pathways,the determination of fluxes of gaseous and particulate species,and the assessment of the effectiveness of pollution control measures.Additionally,isotopic measurements have provided new insights into the sources and formation processes of particulate matter and reactive nitrogen species.Finally,the paper outlines future directions for tower-based research,emphasizing the need for long-term comprehensive measurements,the development of innovative tower platforms,and integration of emerging technologies.
基金funded by the National Natural Science Foundation of China(Nos.22073069,21773082)Science Research Project of Hebei Education Department(No.QN2024255)。
文摘In chemical science,the vertical ionization potential(VIP)is a crucial metric for understanding the electronegativity,hardness and softness of chemical material systems as well as the electronic structure and stability of molecules.Ever since the last century,the model chemistry composite methods have witnessed tremendous developments in computing the thermodynamic properties as well as the barrier heights.However,their performance in realm of the vertical electron processes of molecular systems has been rarely explored.In this study,we for the first time benchmarked the model chemistry composite methods(e.g.,CBS-QB3,G4 and W1BD)in comparison with the commonly used Koopmans's theorem(KT),electron propagator theory(e.g.,OVGF,D2,P3 and P3+)and CCSD(T)methods in calculating the VIP for up to 613 molecular systems with available experimental measurements.The large-scale test calculations strongly showed that the CBS-QB3 model chemistry composite technique can be well recommended to calculate VIP from the perspectives of accuracy,economy and applicability.Notably,the VIP values of up to 7 molecules were identified to have the absolute errors of larger than 0.3 e V at all calculation levels,which have strong hints that their VIP experimental values should be re-investigated.
文摘A method for the rapid reduction of acyl chlorides to aldehydes was developed using pinacolborane(HBpin)as the reducing agent.The method exhibits excellent generality for both aromatic and aliphatic substrates,affording aldehydes in isolated yields of up to 88%with broad functional group tolerance,including cyano,halogen,alkenyl,ketone,and ester groups.Moreover,the method enables gram-scale aldehyde synthesis and shows high efficiency in reducing in situ generated acyl chlorides,thereby enhancing its synthetic practicality.
基金co-supported by the Fundamental Research Funds for Central Universities,China(No.3072024XX0206)the Natural Science Foundation of Heilongjiang Province,China(No.LH2024E069)。
文摘A surface pyrolysis and gas-phase combustion of the Ammonium Perchlorate(AP)/Hydroxy Terminated Polybutadiene(HTPB)composite propellant reaction kinetic mechanism with five-step chemical reaction is adopted.The effects of helium injection on the burning rate and combustion of AP/HTPB propellant are analyzed in details,and the characteristics of motor performance are obtained.The numerical simulation results demonstrate that helium injection enhances the combustion chamber pressure,thereby increasing the burning rate of propellant.However,the primary combustion reaction of the AP/HTPB propellant takes place within a thin layer on the burning surface,so the low-temperature helium has minimal impact on the gasphase combustion.Ultimately,the helium not only elevates the nozzle exit velocity,resulting in specific impulse gain,but also reduces the exhaust plume temperature.With an increase of helium mass flow rate,the area of the velocity increase zone at the nozzle exit continuously decreases,but the average velocity in the motor exit continuously increases.Overall,when the helium flow rate is 2.5 kg/s,the specific impulse can reach 10.5%.Reducing the helium injection hole diameter enhances mixing of helium and combustion gas and expands the velocity increase zone,thereby maximizing the exit velocity gain in average velocity at the nozzle exit.When the injection hole diameter is reduced from 100 mm to 20 mm,the specific impulse gain increases from 3.1%to 10.6%.Furthermore,increasing helium injection temperature greatly boosts the velocity of the mixed gas with the same helium mass fraction ultimately improving specific impulse.
文摘Investigating the detonation reaction zone structures of high explosives is significant for understanding detonation reaction mechanism.This study employed an integrated approach combining machine learning prediction,theoretical calculation,and experimental characterization to determine the detonation reaction zone width of CL-20-based aluminized explosive.In this study,the detonation reaction zone refers to the reaction zone between the von Neumann(VN)peak and sonic point,which usually means the so-called detonation driving zone(DDZ).For the machine learning prediction,an ensemble model integrating Random Forest and Support Vector Regression was developed to predict the reaction zone width using a dataset of 19 publicly available samples.For the theoretical calculation,the Wood-Kirkwood(W-K)detonation theory model was utilized to implement numerical calculation of the reaction zone structures,incorporating chemical reaction kinetics to describe the detonation reaction progress.In experimental characterization,the Photon Doppler Velocimetry(PDV)was applied with LiF as the optical window to measure the particle velocity profile of detonation products and derive the reaction zone width.The results indicate that the reaction zone width values are 0.25 mm,0.28 mm,and 0.26 mm obtained from machine learning prediction,theoretical calculation,and experimental characterization,respectively.The corresponding velocities at the Chapman-Jouguet(CJ)point are 1,938 m/s,2,047 m/s,and 1,982 m/s,respectively.The maximum relative deviation in reaction zone width among three methods is approximately 7.7%,while that for CJ particle velocity is approximately 3.3%.These results from all three methods agree well within engineering error.This validates the effectiveness of integrating machine learning prediction,theoretical calculation and advanced experimental techniques for studying the detonation reaction zone structures of high explosives.This research provides insights into the detonation reaction mechanism and reaction zone characteristics of CL-20-based aluminized explosive.
基金supported by the National Natural Science Foundation of China(Grant No.22205178).
文摘Designing efficient,stable dual-functional combustion catalysts remains a key challenge in developing next-generation solid propellants,particularly in achieving wide pressure plateau combustion.Herein,we synthesize a series of carbon dot-based catalysts(CDs-1,CDs-2,CDs/Cu)via oxidative etching and hydrothermal methods,and employ them to replace conventional carbon black(CB)at 0.65 wt%loading in the preparation of HMX-CMDB propellants.Systematic evaluation through combined thermochemical analysis(50–350℃),laser ignition diagnostics(50–350 W/cm^(2)),and combustion chamber testing(4–18 MPa)reveals remarkable catalytic enhancements.The optimized CDs/Cu catalyst demonstrates multifunctional superiority:(1)7.4℃ reduction in HMX-CMDB decomposition temperature at 10℃/min(from 205.2℃ to 196.0℃);(2)66.7%decrease in laser ignition delay(from 45 ms to 15 ms);(3)190.9%burning rate increase at 4 MPa(from 4.61 mm/s to 13.41 mm/s);(4)lower pressure exponent of 0.02 within 4–18 MPa range.Notably,CDs-1 induces stable"Plateau"combustion(4–14 MPa),while CDs/Cu achieves"Mesa"effects(8–12 MPa)via synergistic thermal feedback mechanisms-both phenomena ensure stable operation of the engine.Mechanistic studies integrate thermochemical kinetics,ignition combustion process,combustion flame structure,and combustion wave temperature distribution trends,which establish a new paradigm for the study of high efficiency combustion catalysts for solid propellants.
基金funded by the National Natural Science Foundation of China,Grant No.22405208。
文摘Boron has attracted increasing attention in the field of high-energy explosives and propellants due to its high volume calorific value and mass calorific value.However,the complicated combustion process and low combustion efficiency hinder its wide application.To tackle this challenge,bioinspired polydopamine(PDA)interface reinforced boron-Viton composites,with high structure stability and excellent energy releasing efficiency,are designed and prepared,combining the interface regulation of PDA biomimetic materials and combustion promotion of fluoropolymers.Firstly,the stronger adsorption energy of PDA with boron compared to Viton is demonstrated by molecular dynamics simulations.Next,B@PDA@Viton is prepared by the combination of in-situ dopamine polymerization and solvent/nonsolvent method,and the double-layer core-shell structure is confirmed by XPS,FTIR,and TEM characterizations.TG-DSC analysis shows that B@PDA@Viton possesses superior thermal properties,with a 55.48%increase in oxidation heat compared to raw B.Furthermore,ignition and combustion performance tests indicate that B@PDA@Viton reduces ignition delay by 57.56%and increases heat of combustion by 68.63%relative to raw B.These findings elucidate the ignition and combustion mechanisms of B@PDA@Viton.This work not only developed high-performance boron-based composite fuels but also provided insights into the development of boron-based fuels.
基金supported by the National Natural Science Foundation of China(Nos.U2341249,12005076,22205112)the Fundamental Research Funds for the Central Universities(No.2025201012)。
文摘The presence of a surface oxide film(B_(2)O_(3))on boron(B)particles significantly compromises their combustion efficiency and kinetic performance in fuel-rich solid propellants.This study proposes an innovative continuous modification strategy combining non-thermal plasma(NTP)etching with fluorocarbon passivation.Characterization and kinetic analysis revealed that reactive plasma species—including atomic hydrogen(H),electronically excited molecular hydrogen(H_(2)^(*)),vibrationally excited molecular hydrogen(H_(2)v),and hydrogen ions(H^(+))—dominate the reduction of B_(2)O_(3)through lowering the transition energy barrier and shifting the reaction spontaneity.Subsequent argon plasma fragmentation of C_(8)F_(18)generates fluorocarbon radicals that form conformal passivation coatings(thickness:7 nm)on purified boron surfaces.The modified boron particles exhibit 37.5℃lower exothermic peak temperature and 27.2%higher heat release(14.8 kJ/g vs.11.6 kJ/g)compared to untreated counterparts.Combustion diagnostics reveal 194%increase in maximum flame height(135.10 mm vs.46.03 mm)and 134%enhancement in flame propagation rate(4.44 cm/s vs.1.90 cm/s).This NTP-based surface engineering approach establishes a scalable pathway for developing highperformance boron-based energetic composites.
基金Financial supports from the National Natural Science Foundation of China (Nos.22025109,22371283)the National Key R&D Program of China (No.2023YFA1507902)+1 种基金CAS Project for Young Scientists in Basic Research (No.YSBR-050)the State Key Laboratory of Fine Chemicals,Dalian University of Technology (No.KF2102) are gratefully acknowledged。
文摘The direct transformation of dinitrogen(N_(2)) into nitrogen-containing organic compounds holds substantial importance.In this work,we report a titanium-promoted method for the conversion of N_(2) to N-methylimides.Initially,the N_(2)-bridging end-on dititanium side-on dipotassium complex[{(Tren^(TMS))Ti}_(2)(μ-η^(1):η^(1):η^(2):η^(2)-N_(2)K_(2))] underwent simultaneous disproportionation and N-methylation reactions in the presence of methyl trifluoromethanesulfonate(Me OTf),yielding [{(N^(Me,TMS)NN^(TMS)_(2))Ti}(μ-NMe)]_(2) with complete cleavage of the N≡N bond.The nucleophilicity of the N-methylated intermediate allowed it to react with electrophilic reagents such as trimethylchlorosilane(TMSCl) to form heptamethyldisilazane,or with acyl chlorides to generate N-methylimides.Moreover,nitrogen-15(^(15)N) labeled experiments provided a novel approach to synthesizing ^(15)N-labeled methylimides.
文摘Plantago major L.,commonly known as plantain,waybread,or dooryard plantain,is a versatile medicinal plant with multiple therapeutic applications.Traditionally,various parts of the plant have been formulated into syrups,drops,ointments,vaginal suppositories,gargles,and roasted preparations to treat diverse ailments,such as liver disorders,earaches,epilepsy,asthma,stomachaches,diarrhea,constipation,polymenorrhea,and uterine disorders.The plant contains clinically valuable bioactive compounds,including polysaccharides,flavonoids,lipids,iridoid glycosides,caffeic acid derivatives,terpenoids,alkaloids,and organic acids.These bioactive constituents are the primary contributors to the plant’s broad spectrum of biological activities,including antioxidant,anti-inflammatory,antibacterial,antidiarrheal,hepatoprotective,antiviral,antiphage,antinociceptive,antiulcerogenic,antigenotoxic,and immunomodulatory effects of the plant.This review comprehensively summarizes the phytochemical composition,traditional medicinal applications,and biological properties of this multifunctional medicinal plant.
基金supported by the National Natural Science Foundation of China(Grant Nos.22105156,22175139,22505195,22171136,22405207 and 22302156)the China National Science Fund for Distinguished Young Scholars(Grant No.22325504)。
文摘The pursuit of heat-resistant energetic materials(HREMs)with thermal stability beyond 450℃ presents a significant challenge that has yet to be achieved.In this work,we develop an innovative electronic delocalization strategy to design and synthesize a planar dizwitterionic diamino-bistriazolotetrazine,designated as TYX-1.The unique structural feature of TYX-1,including a nitrogen-rich fused ring system,planar conformation,and dizwitterionic configuration,combined with its hydrogen-bonded organic framework(HOF)structure,confer exceptional thermal stability(The onset temperature is 428℃,and the peak temperature is 473℃),high density(1.84 g/cm^(3)),and remarkable detonation performance(detonation velocity:8616 m/s).Furthermore,TYX-1 exhibits an impressive insensitivity(impact sensitivity>40 J;friction sensitivity>360 N),surpassing all previously reported HREMs.Theoretical calculations and single-crystal clearly indicate that the delocalizedπelectrons within the dizwitterionic bistriazolotetrazine rings and the HOF structure of TYX-1 are pivotal in ensuring its high thermal stability and high energy density.The discovery of TYX-1 marks a significant advancement in the field of HREMs and is anticipated to catalyze substantial progress in various high-temperature applications reliant on energetic materials.
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-C3H7CHO 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 nC3H7CHO at the molecular level and offers in-depth perspectives on the isolation of specific metal ions from the view of kinetic control.
基金the financial support provided by the National Natural Science Foundation of China(grant no.22373032)the open research fund of Songshan Lake Materials Laboratory(grant no.2023SLABFK06)。
文摘With the rapid growth of technologies requiring high-power energy storage,achieving long-term cyclic stability under ultra-high current density is a key challenge.Aqueous zinc-ion batteries(AZIBs)are promising candidates due to their intrinsic safety and low cost,but they suffer from severe interfacial instability at rates exceeding 10 mA cm^(-2),which drastically shortens their cycle life.Inspired by theoretical calculations,triglyme(TGDE)additive with strong electron-donating groups into Zn(OTf)_(2) electrolytes effectively disrupts the hydrogen-bond network among free water molecules,while the weak coordination of TGDE with Zn^(2+)promotes the entry of OTf-into the primary Zn^(2+)solvated sheath,thus decreasing the coordination number of water with Zn^(2+).As such,the hydrogen-bond network and the bulk solvated structure are reconstructed with better stability.Moreover,the strong adsorption of TGDE lying on the Zn(002)surface would induce Zn depositions along(002)together with the reduced exposed surface,further effectively inhibiting side reactions.Likewise,TGDE electrolyte induces the formation of such ZnF_(2)-ZnS dual-layer solid electrolyte interface(SEI)with superior chemical stability and ionic conductivity,thereby regulating Zn^(2+)flux with dendrite-free depositions.Based on this electrolyte,Zn‖Zn cells can be stably cycled for 1300 h at a limit of 10 mA cm^(-2) and 10 mAh cm^(-2).The assembled Zn‖V_(2)O_(5) full cells still maintain 99.9%capacity retention after 1000 cycles at 10 A g^(-1).This work provides a feasible approach for designing aqueous electrolytes to reconstruct the hydrogen-bond network and solvated structure,which can be extended to the applications of high-rate and high-temperature scenarios.
基金supported by the National Natural Science Foundation of China(Grant No.12402432)Natural Science Foundation of Jiangsu Province of China(Grant No.BK20230936)Graduate Education and Teaching Reform Project of Nanjing University of Science and Technology(Grant No.KT2024_C14)。
文摘To elucidate the dispersion and explosion characteristics of multi-metal powder and liquid composite fuel formulations,high-energy metal powders(aluminum(Al),boron(B),and magnesium hydride(MgH_(2)))are incorporated into a liquid fuel primarily composed of diethyl ether(DEE)and isopropyl nitrate(IPN).The explosion characteristics of different solid-liquid fuel-air-explosive(FAE)under unconfined conditions are investigated using a high-speed camera,infrared thermal imaging,and a pressure measurement system.Results demonstrate that high-energy metal powders significantly enhance detonation energy dissipation,with aluminum exhibiting the most pronounced effect.Fuel 5#(45.4 wt%DEE,9.2 wt%IPN,29.5 wt%Al,9.1 wt%B,6.8 wt%MgH_(2))exhibits superior explosion performance,achieving higher values of overpressure,impulse,and thermal radiation damage during the detonation stage compared to other fuels.However,Fuel 5#also displays faster decay rates,attributed to accelerated heat release rates induced by B and MgH_(2)powders.This study reveals that different metal powders in solid-liquid FAE exhibit distinct enhancements in explosion performance,providing critical insights for optimizing composite fuel design.
基金supported by the National Natural Science Foundation of China(No.22375063)Science and Technology Commission of Shanghai Municipality(No.23JC1401700)the Fundamental Research Funds for the Central Universities.
文摘Developing advanced polymeric materials with enhanced mechanical properties and functionalities has been a long-standing goal in materials science.Recently,supramolecular polymeric materials (SPMs) have drawn increased attention due to their unique properties and potential applications in self-healing,shape memory,sensors,and flexible electronics.Here,we develop an ionic cluster-optimized microphase separation strategy to enhance the toughening and energy dissipation capabilities of polydisulfide-based supramolecular polymers.The mechanical properties,including Young’s modulus and toughness,are significantly improved by integrating the quadruple H-bonding 2-ureido-4-pyrimidone (UPy) induced microphase separation with iron(Ⅲ)-to-carboxylate ionic clusters.By combining established chemical approaches with adjustable polymer phase ratios,it is revealed that the synergistic effect of these factors expands the interchain spacing,facilitates the formation of microphase domains,and enhances the tolerance of polythioctic acid-based polymers to external mechanical and thermal stimuli,meeting the practical requirements for industrial plastic applications.Moreover,the UPy-functionalized polymers incorporating iron carboxylate clusters exhibit good one-way shape memory behavior with practical applicability at a relatively low recovery temperature.Our work demonstrates a novel strategy for constructing industrially viable shape memory dynamic SPMs and paves the way for future innovations in developing SPMs.
基金National Key Research and Development Program of China (2022YFC3004004)National Natural Science Foundation of China (42075155,12241104)National Natural Science Foundation of China Joint Fund (U2342213)。
文摘The infrared channels of the FY-4B advanced geosynchronous radiation imagers(AGRI) play a crucial role in temperature and humidity analyses for mesoscale numerical weather prediction, particularly in enhancing the initial field quality and the forecasting accuracy of the model. This study assimilated FY-4B AGRI data into the CMA-MESO model and analyzed the bias characteristics and correction methods. Analysis of the AGRI data revealed a clear diurnal variation in the bias, which was positively correlated with the solar elevation angle. However, the diurnal variation in the bias lagged behind the solar elevation angle, likely owing to temperature changes and delayed instrument responses resulting from solar radiation. To address this issue, we propose a correction method that utilizes the solar elevation angle after an optimal time shift. Using the time-shifted solar elevation angle as a predictor effectively reduces the diurnal variation in bias and significantly improves the correction effect. This approach provides theoretical support for the assimilation of FY-4B AGRI data into mesoscale numerical weather predictions, thereby enhancing the reliability of the assimilation results.
基金supported by the National Natural Science Foundation of China (Grant Nos.42075097,42177081 and 22176037)。
文摘As a key precursor of hydroxyl(OH) radicals, the budget of nitrous acid(HONO) at different altitudes has received extensive attention. In this study, vertically resolved observations of HONO, NO_(2), O_(3), and HCHO were conducted during an autumn field campaign in Beijing in 2019. The significant correlation between HONO and NO2, along with variations in their ratios across different altitudes, underscores the importance of aerosol surface chemistry in HONO formation and its altitude-dependent behavior. To enhance the model performance, the heterogeneous conversion of NO_(2) and its photochemical enhancement are incorporated into the 1D model. The simulations reveal that the nocturnal HONO production is dominated by the heterogeneous conversion of NO_(2) both at the surface and aloft. During the daytime, groundsurface sources of HONO are mainly driven by nitrate photolysis and light-enhanced heterogeneous conversion of NO_(2).Meanwhile, a large portion of the HONO generated at the surface is transported upwards through vertical mixing. In the higher atmosphere, HONO originates from vertical transport and in situ processes. As precursors of OH radicals, the observed concentrations of HONO, O_(3), and HCHO exhibit distinct diurnal variations and vertical distribution patterns.HONO contributes to OH radical production predominantly during the early morning across all layers and it even becomes the main contributor throughout the daytime in the lowest layer near the ground, while O_(3) and HCHO become more prominent towards midday, especially in the higher layers. These results will be beneficial for a deeper understanding of the atmospheric oxidation process within the urban boundary layer.
基金the National Key R&D Program of China(No.2021YFC2101604)National Natural Science Foundation of China(Nos.U23A20123,22278339)+1 种基金Fujian Provincial Key Science and Technology Program of China(No.2022YZ037013)Xiamen University for the financial support.
文摘Carbon dioxide(CO_(2))is the main greenhouse gas(GHG)released by human activities.The substitution of fossil resources by biomass as a bio-renewable resource,has significant potential to reduce GHG emissions.The approach to biomass,as the only true full-scale alternative to fossil resources,is progressing rapidly.Converting biomass into furanic compounds,as versatile platform chemicals for synthesizing a wide range of bio-based products is the cornerstone of sustainable technologies.The extensive body of this review combines the biomass valorization to furanic compounds by CO_(2)utilization and furanic compounds conversion by CO_(2)fixation.These processes can be strategically applied through both‘thermochemical’and‘electrochemical’pathways,by utilizing CO_(2)from the atmosphere or industrial emission point and returning it to the natural carbon cycle.In the thermochemical pathway CO_(2)acts as a carbon source(carboxylation and polymerization)or active reaction assistant in the biomass conversion(CO_(2)-assisted conversion),without altering its oxidation state,facilitating the synthesis of valuable products and polymers.Conversely,in the electrochemical pathway,CO_(2)can be used as a carbon source(electrocarboxylation)to give the corresponding carboxylic acid,or it can undergo reduction,yielding methanol,carbon monoxide(CO),formic acid,and analogous compounds,while on the other side,furanic compounds undergo oxidation yielding high-value-added chemicals.Finally,potential future research directions are suggested to promote CO_(2)utilization and fixation in the valorization of biomass-derived furanic compounds,and challenges facing further research are highlighted.
基金supported by the CAS Strategic Priority Research Program(No.XDB0760102),the Ministry of Science and Technology of China(No.2022YFF0802501)the Major Science and Technology Infrastructure Maintenance and Transformation Project of the Chinese Academy of Sciences,Shanghai Science and Technology Innovation Action Plan-Phospherus Project(No.23YF1426200)the National Key Research and Development Program of China(No.2024YFE0212200).
文摘In winter 2018,an aerosol physicochemical experiment was conducted in the Western Pacific Ocean(WPO)aboard the Research Vessel KEXUE of Chinese Academy of Sciences.This study systematically investigated both natural and anthropogenic effects on marine aerosols optical properties,as well as the applicability of multi-satellite products and IMPROVE equation.The averaged aerosol optical depth(AOD500 nm)was 0.31±0.16 andÅngström exponent440–675 nm was 0.29±0.30.In offshore China,significant anthropogenic emissions affected the marine environment.In remote WPO,dust aerosols transported from northern China,Siberia,Central Asia,and those settling from the upper troposphere originating from north Africa,Arabian peninsula,and western India,were dominant.The spatial trends of AOD were opposite in the mid-latitude and southern seas of WPO.The highest AOD,0.32±0.23,appeared along the coast of South Asia at mid-latitude,decreasing from offshore seas to remote oceans.In low-latitude and equatorial seas,AOD significantly increased from coast to remote oceans.Ångström exponent dropped significantly from the coast to remote oceans as anthropogenic influence diminished across the entire WPO.Correlation analysis showed that both MODIS-C6 and Himawari AOD prod-ucts showed similar applicability in coastal urban areas,while Himawari AOD is highly recommended for coastal background and marine environment due to its finer resolution.The extinction coefficient derived from PM_(2.5) chemical compositions using IMPROVE algorithm exhibited a significant correlation(R^(2)=0.58)with the con-currently measured AOD in the absence of long-distance transport,suggesting that the IMPROVE is a reasonable proxy of the columnar average of marine aerosol extinctions free from transport influences.
基金financially supported by the National Research Foundation of Korea(NRF)grant funded by the Korean government(MSIT)(No.NRF-2020R1A3B2079803 and No.RS-2024-00453815),Republic of Korea。
文摘Localized high-concentration electrolytes(LHCEs)are considered as promising electrolyte candidates to resolve technical issues of metal batteries owing to their unique interfacial properties and solvation structures.Herein,we propose a self-assembly chemical strategy into the LCHEs induced by ordered nanostructure of zwitterionic co-solutes for highly efficient and ultrastable zinc(Zn)metal batteries.Through the systematic screening of six zwitterionic compounds,3-(decyldimethylammonio)propanesulfonate salt(C_(10))with the decyl chain and zwitterions was determined as an optimum to construct quasi-spherical aggregates with a periodic length of 3.77 nm,as confirmed by comprehensive synchronous small-angle X-ray scattering,Guinier,pair distance distribution function,Porod,and other spectroscopic characterizations and molecular dynamic simulation.In particularly,this self-assembled structure in electrolyte environments was attributed to increasing the proportion of both contact and aggregated ion pairs for the formation of LHCEs as well as to providing fast and selective Zn^(2+)conducting channels and uniform solid electrolyte interfaces for facilitated charge transfer kinetics.Moreover,the preferential adsorption of the self-assembled C_(10)on the Zn(002)surface modulated the electrical double layer to suppress hydrogen evolution and corrosion reactions.Consequently,the Zn‖Zn symmetric cells in Zn(OTf)_(2)/C_(10)electrolytes showed long-term plating/stripping behaviors over 2800 h at 1 mA cm^(-2)and 1 mAh cm^(-2)as well as over 1200 h even at 5 mA cm^(-2)and 5 mAh cm^(-2)with a very high depth of discharge of 42.7%.Furthermore,the ZnllVO_(2)/CNT full cells in Zn(OTf)_(2)/C_(10)electrolytes delivered a record-high capacity of 8.10 mAh cm^(-2)at an ultrahigh cathode mass loading of 50 mg cm^(-2)after 150 cycles.
