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 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
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
Rationally regulating the adsorption strength of reaction intermediates on the surface of copper-based electrocatalysts would influence the product selectivity in the electrochemical CO_(2)reduction reaction(eCO_(2)RR...Rationally regulating the adsorption strength of reaction intermediates on the surface of copper-based electrocatalysts would influence the product selectivity in the electrochemical CO_(2)reduction reaction(eCO_(2)RR).Herein,theoretical screening results reveal that among the twelve metals,Mg,Al,Cr,Mn,Fe,Co,Ni,Zn,Sn,Bi,Mo and Ce,the introduction of the metals Bi,Ce,Mg and Mn into CuOOH nanosheets not only modulates the Cu active center,but also leads to a certain degree of conformational distortion,resulting in an increased occupation of electrons in the antibonding state and accelerating the formation of the ratedetermining step ^(*)HCOO.In situ spectroscopies combined with theoretical calculations confirm that Bi atoms modulate the electronic structure of Cu and enhance CO_(2)activation,while Cu sites promote the adsorption of ^(*)HCOO intermediate,significantly increasing the formation of HCOOH with Faradaic efficiency exceeding 90%on the CuBiOOH.Moreover,the introduction of Mn into CuOOH nanosheets can induce the formation of key intermediates(^(*)CHO and ^(*)CO),leading to enhanced asymmetric C–C coupling to generate ethanol.Our work provides deep insights into the structural regulation strategy of Cu sites at the atomic scale for converting CO_(2)to liquid chemical products.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 separation of propylene(C_(3)H_(6))and propane(C_(3)H_(8))presents a significant industrial challenge due to their similar molecular dimensions and physicochemical properties.Among various separation methods,molec...The separation of propylene(C_(3)H_(6))and propane(C_(3)H_(8))presents a significant industrial challenge due to their similar molecular dimensions and physicochemical properties.Among various separation methods,molecular sieving emerges as the most promising approach,but it will be significantly compromised at high temperatures due to the significant thermal motion.Here,we report a thermally robust zinc-based metal-organic framework(MOF)that can be synthesized on sub-kilogram scale and achieve exceptional C_(3)H_(6)/C_(3)H_(8) separation performances across a broad temperature range(298–353 K).Unlike conventional MOFs suffering from thermal lattice expansion to give poorer selectivity,this new MOF gives the adsorption capacity of C_(3)H_(6)essentially unchanged and that of C_(3)H_(8) negligible at elevated temperatures,outperforming most state-of-the-art adsorbents,in virtue of multiple hydrogen bonds at the aperture.Column breakthrough experiments confirmed the excellent separation capability,and showed no performance degradation over multi-round adsorption-desorption cycles at 353 K.This study addresses the critical challenge of the trade-off between temperature and selectivity in adsorptive separation,which offers new insights into the design of porous structures for highly effective separation at high temperatures.展开更多
The demand for ^(238)Pu(nuclear battery heat source)drives the separation of its precursor,^(237)Np,from spent nuclear fuel(SNF).However,the co-existence of multi-valence states(IV/V/VI)of Np and similar redox behavio...The demand for ^(238)Pu(nuclear battery heat source)drives the separation of its precursor,^(237)Np,from spent nuclear fuel(SNF).However,the co-existence of multi-valence states(IV/V/VI)of Np and similar redox behavior with Pu(IV)hinder the effective separation of Np.N-Butyraldehyde(n-C_(3)H_(7)CHO)selectively reduces Np(VI)to Np(V)without reducing Pu(IV).Herein,we examined the reduction mechanisms of Np(VI)and Pu(IV)by n-C_(3)H_(7)CHO using relativistic density functional theory.Based on the results of the potential energy profiles,the reductions of both Np(VI)and Pu(IV)by n-C_(3)H_(7)CHO are thermodynamically feasible,whereas only the former is kinetically achievable.It uncovers that n-C_(3)H_(7)CHO can only reduce Np(VI)to Np(V)owing to kinetically controlled selective reduction.The analyses of spin density and bond distance indicate that the reduction nature for the first Np(VI)/Pu(IV)belongs to hydrogen atom transfer,whereas that for the second one involves outer-sphere electron transfer.Localized molecular orbitals(LMOs)analysis discloses the bonding evolution during the reduction process of Np(VI)/Pu(IV).This study elucidates the reason behind the kinetically controlled selective reduction of Np(VI)/Pu(IV)by n-C_(3)H_(7)CHO at the molecular level and offers in-depth perspectives on the isolation of specific metal ions from the view of kinetic control.展开更多
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 increased ...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
Conventional electrolytic methods for separating chemically similar lanthanides(Ln)and actinides(An)are limited by thermodynamics and slow reaction kinetics,restricting their efficiency in rare-earth refining and nucl...Conventional electrolytic methods for separating chemically similar lanthanides(Ln)and actinides(An)are limited by thermodynamics and slow reaction kinetics,restricting their efficiency in rare-earth refining and nuclear fuel recycling.Herein,we report an electroextraction and oxidative back-extraction(EOB)strategy utilizing a LiCl-KCl-KAlCl_(4) molten salt that overcomes these limitations by leveraging divergent interfacial reactivity.The EOB process achieves an exceptional separation factor for Ln/An(>1000),while simultaneously increasing the separation rate by at least one order of magnitude.Through in-situ synchrotron radiation X-ray micro-computed tomography(SR-μCT)and X-ray diffraction(SR-XRD),we capture selective oxidation-induced destabilization of Ln-Al alloys while actinides retain phase stability-directly visualizing the electrochemical alloy transition mechanism.This research redefines the separation of f-block elements in molten salt systems and introduces a multimodal approach to investigating transient interfacial phenomena that are usually inaccessible to conventional metallurgical diagnostics under extreme conditions.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
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
Recent advances in high-pressure technologies and large-scale experimental and computational facilities have enabled scientists,at an unprecedented rate,to discover and predict novel states and materials under the ext...Recent advances in high-pressure technologies and large-scale experimental and computational facilities have enabled scientists,at an unprecedented rate,to discover and predict novel states and materials under the extreme pressure-temperature conditions found in deep,giant-planet interiors.Based on a well-documented body of work in this field of high-pressure research,we elucidate the fundamental principles that govern the chemistry of dense solids under extreme conditions.These include:(i)the pressure-induced evolution of chemical bonding and structure of molecular solids to extended covalent solids,ionic solids and,ultimately,metallic solids,as pressure increases to the terapascal regime;(ii)novel properties and complex transition mechanisms,arising from the subtle balance between electron hybridization(bonding)and electrostatic interaction(packing)in densely packed solids;and(iii)new dense framework solids with high energy densities,and with tunable properties and stabilities under ambient conditions.Examples are taken primarily fromlow-Z molecular systems that have scientific implications for giant-planet models,condensed materials physics,and solid-state core-electron chemistry.展开更多
An ocean biogeochemistry model was developed and incorporated into a global ocean general circulation model （LICOM） to form an ocean biogeochemistry general circulation model （OBGCM）. The model was used to study t...An ocean biogeochemistry model was developed and incorporated into a global ocean general circulation model （LICOM） to form an ocean biogeochemistry general circulation model （OBGCM）. The model was used to study the natural carbon cycle and the uptake and storage of anthropogenic CO2 in the ocean. A global export production of 12.5 Pg C yr-1 was obtained. The model estimated that in the pre-industrial era the global equatorial region within ~15~ of the equator released 0.97 Pg C yr-1 to the atmosphere, which was balanced by the gain of CO2 in other regions. The post-industrial air sea CO2 flux indicated the oceanic uptake of CO2 emitted by human activities. An increase of 20-50 ~mol kg-1 for surface dissolved inorganic carbon （DIC） concentrations in the 1990s relative to pre-industrial times was obtained in the simulation, which was consistent with data-based estimates. The model generated a total anthropogenic carbon inventory of 105 Pg C as of 1994, which was within the range of estimates by other researchers. Various transports of both natural and anthropogenic DIC as well as labile dissolved organic carbon （LDOC） were estimated from the simulation. It was realized that the Southern Ocean and the high-latitude region of the North Pacific are important export regions where accumulative air-sea CO2 fluxes are larger than the DIC inventory, whereas the subtropical regions are acceptance regions. The interhemispheric transport of total natural carbon （DIC＋LDOC） was found to be northward （0.11 Pg C yr-1）, which was just balanced by the gain of carbon from the atmosphere in the Southern Hemisphere.展开更多
One hundred and ten samples of rainwater were collected for chemical analysis at the summit of Huangshan Mountain, a high-altitude site in East China, from July 2010 to June 2011. The volume-weighted-mean （VWM） pH f...One hundred and ten samples of rainwater were collected for chemical analysis at the summit of Huangshan Mountain, a high-altitude site in East China, from July 2010 to June 2011. The volume-weighted-mean （VWM） pH for the whole sampling period was 5.03. SO2- and Ca2＋ were the most abundant anion and cation, respectively. The ionic concentrations varied monthly with the highest concentrations in winter/spring and the lowest in summer. Evident inter-correlations were found among most ions, indicating the common sources for some species and fully mixing characteristics of the alpine precipitation chemistry. The VWM ratio of [SO]-]/[NO3] was 2.54, suggesting the acidity of rainwater comes from both nitric and sulfuric acids. Compared with contemporary observations at other alpine continental sites in China, the precipitation at Huangshan Mountain was the least polluted, with the lowest ionic concentrations. Trajectories to Huangshan Mountain on rainy days could be classified into six groups. The rainwater with influencing air masses originating in Mongolia was the most polluted with limited effect. The emissions of Jiangxi, Anhui, Zhejiang and Jiangsu provinces had a strong influence on the overall rain chemistry at Huangshan Mountain. The rainwater with influencing air masses from Inner Mongolia was heavily polluted by anthropogenic pollutants.展开更多
The complex of neodymium chloride lower hydrate with diethylammonium diethyldithiocarbamate (D-DDC) was synthesized conveniently in absolute alcohol and dry N_2 atmosphere. The title complex was identified as Et_2NH_2...The complex of neodymium chloride lower hydrate with diethylammonium diethyldithiocarbamate (D-DDC) was synthesized conveniently in absolute alcohol and dry N_2 atmosphere. The title complex was identified as Et_2NH_2[Nd(S_2CNEt_2)_4] by chemical and elemental analyses and the bonding characteristics of which was characterized by IR. The enthalpies of solution of neodymium chloride hydrate and D-DDC in absolute alcohol at 298.15 K and the enthalpies change of liquid-phase reaction of formation for Et_2NH_2[Nd (S_2CNEt_2)_4] at different temperatures were determined by microcalorimetry. On the basis of experimental and calculated results, three thermodynamic parameters (the activation enthalpy, the activation entropy and the activation free energy), the rate constant and three kinetic parameters (the apparent activation energy, the pre-exponential constant and the reaction order) of liquid-phase reaction of formation were obtained. The enthalpy change of the solid-phase title reaction at 298.15 K was calculated by a thermochemical cycle.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.
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.
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 Natural Science Foundation of Jilin Province(20220101051JC)the National Natural Science Foundation of China(22075099)。
文摘Rationally regulating the adsorption strength of reaction intermediates on the surface of copper-based electrocatalysts would influence the product selectivity in the electrochemical CO_(2)reduction reaction(eCO_(2)RR).Herein,theoretical screening results reveal that among the twelve metals,Mg,Al,Cr,Mn,Fe,Co,Ni,Zn,Sn,Bi,Mo and Ce,the introduction of the metals Bi,Ce,Mg and Mn into CuOOH nanosheets not only modulates the Cu active center,but also leads to a certain degree of conformational distortion,resulting in an increased occupation of electrons in the antibonding state and accelerating the formation of the ratedetermining step ^(*)HCOO.In situ spectroscopies combined with theoretical calculations confirm that Bi atoms modulate the electronic structure of Cu and enhance CO_(2)activation,while Cu sites promote the adsorption of ^(*)HCOO intermediate,significantly increasing the formation of HCOOH with Faradaic efficiency exceeding 90%on the CuBiOOH.Moreover,the introduction of Mn into CuOOH nanosheets can induce the formation of key intermediates(^(*)CHO and ^(*)CO),leading to enhanced asymmetric C–C coupling to generate ethanol.Our work provides deep insights into the structural regulation strategy of Cu sites at the atomic scale for converting CO_(2)to liquid chemical products.
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(22475240,22090061,22488101)the State Key Laboratory of Catalysis(2024SKL-A-010)。
文摘The separation of propylene(C_(3)H_(6))and propane(C_(3)H_(8))presents a significant industrial challenge due to their similar molecular dimensions and physicochemical properties.Among various separation methods,molecular sieving emerges as the most promising approach,but it will be significantly compromised at high temperatures due to the significant thermal motion.Here,we report a thermally robust zinc-based metal-organic framework(MOF)that can be synthesized on sub-kilogram scale and achieve exceptional C_(3)H_(6)/C_(3)H_(8) separation performances across a broad temperature range(298–353 K).Unlike conventional MOFs suffering from thermal lattice expansion to give poorer selectivity,this new MOF gives the adsorption capacity of C_(3)H_(6)essentially unchanged and that of C_(3)H_(8) negligible at elevated temperatures,outperforming most state-of-the-art adsorbents,in virtue of multiple hydrogen bonds at the aperture.Column breakthrough experiments confirmed the excellent separation capability,and showed no performance degradation over multi-round adsorption-desorption cycles at 353 K.This study addresses the critical challenge of the trade-off between temperature and selectivity in adsorptive separation,which offers new insights into the design of porous structures for highly effective separation at high temperatures.
基金supported by the National Natural Science Foundation of China(Nos.22376197,U2441225,22076188).
文摘The demand for ^(238)Pu(nuclear battery heat source)drives the separation of its precursor,^(237)Np,from spent nuclear fuel(SNF).However,the co-existence of multi-valence states(IV/V/VI)of Np and similar redox behavior with Pu(IV)hinder the effective separation of Np.N-Butyraldehyde(n-C_(3)H_(7)CHO)selectively reduces Np(VI)to Np(V)without reducing Pu(IV).Herein,we examined the reduction mechanisms of Np(VI)and Pu(IV)by n-C_(3)H_(7)CHO using relativistic density functional theory.Based on the results of the potential energy profiles,the reductions of both Np(VI)and Pu(IV)by n-C_(3)H_(7)CHO are thermodynamically feasible,whereas only the former is kinetically achievable.It uncovers that n-C_(3)H_(7)CHO can only reduce Np(VI)to Np(V)owing to kinetically controlled selective reduction.The analyses of spin density and bond distance indicate that the reduction nature for the first Np(VI)/Pu(IV)belongs to hydrogen atom transfer,whereas that for the second one involves outer-sphere electron transfer.Localized molecular orbitals(LMOs)analysis discloses the bonding evolution during the reduction process of Np(VI)/Pu(IV).This study elucidates the reason behind the kinetically controlled selective reduction of Np(VI)/Pu(IV)by n-C_(3)H_(7)CHO at the molecular level and offers in-depth perspectives on the isolation of specific metal ions from the view of kinetic control.
基金supported by the 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.23JC140170O)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supported by the National Science Fund for Distinguished Young Scholars(21925603)the National Natural Science Foundation of China(22306185)the China Postdoctoral Science Foundation(2023M732032)。
文摘Conventional electrolytic methods for separating chemically similar lanthanides(Ln)and actinides(An)are limited by thermodynamics and slow reaction kinetics,restricting their efficiency in rare-earth refining and nuclear fuel recycling.Herein,we report an electroextraction and oxidative back-extraction(EOB)strategy utilizing a LiCl-KCl-KAlCl_(4) molten salt that overcomes these limitations by leveraging divergent interfacial reactivity.The EOB process achieves an exceptional separation factor for Ln/An(>1000),while simultaneously increasing the separation rate by at least one order of magnitude.Through in-situ synchrotron radiation X-ray micro-computed tomography(SR-μCT)and X-ray diffraction(SR-XRD),we capture selective oxidation-induced destabilization of Ln-Al alloys while actinides retain phase stability-directly visualizing the electrochemical alloy transition mechanism.This research redefines the separation of f-block elements in molten salt systems and introduces a multimodal approach to investigating transient interfacial phenomena that are usually inaccessible to conventional metallurgical diagnostics under extreme conditions.
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The present study has been performed in support of the NSF(Grant No.DMR 1701360),DOE-NNSA(Grant No.DENA0003342),ARO(Grant No.W911NF-17-1-0468),DARPA(Grant No.W31P4Q-12-1-0009),and ADD in Korea.
文摘Recent advances in high-pressure technologies and large-scale experimental and computational facilities have enabled scientists,at an unprecedented rate,to discover and predict novel states and materials under the extreme pressure-temperature conditions found in deep,giant-planet interiors.Based on a well-documented body of work in this field of high-pressure research,we elucidate the fundamental principles that govern the chemistry of dense solids under extreme conditions.These include:(i)the pressure-induced evolution of chemical bonding and structure of molecular solids to extended covalent solids,ionic solids and,ultimately,metallic solids,as pressure increases to the terapascal regime;(ii)novel properties and complex transition mechanisms,arising from the subtle balance between electron hybridization(bonding)and electrostatic interaction(packing)in densely packed solids;and(iii)new dense framework solids with high energy densities,and with tunable properties and stabilities under ambient conditions.Examples are taken primarily fromlow-Z molecular systems that have scientific implications for giant-planet models,condensed materials physics,and solid-state core-electron chemistry.
基金supported by the National Basic Research Program of China("973 program",Grant No.2010CB951802)the National Natural Science Foundation of China(Grant Nos.40730106,41105087,and 41075091)
文摘An ocean biogeochemistry model was developed and incorporated into a global ocean general circulation model （LICOM） to form an ocean biogeochemistry general circulation model （OBGCM）. The model was used to study the natural carbon cycle and the uptake and storage of anthropogenic CO2 in the ocean. A global export production of 12.5 Pg C yr-1 was obtained. The model estimated that in the pre-industrial era the global equatorial region within ~15~ of the equator released 0.97 Pg C yr-1 to the atmosphere, which was balanced by the gain of CO2 in other regions. The post-industrial air sea CO2 flux indicated the oceanic uptake of CO2 emitted by human activities. An increase of 20-50 ~mol kg-1 for surface dissolved inorganic carbon （DIC） concentrations in the 1990s relative to pre-industrial times was obtained in the simulation, which was consistent with data-based estimates. The model generated a total anthropogenic carbon inventory of 105 Pg C as of 1994, which was within the range of estimates by other researchers. Various transports of both natural and anthropogenic DIC as well as labile dissolved organic carbon （LDOC） were estimated from the simulation. It was realized that the Southern Ocean and the high-latitude region of the North Pacific are important export regions where accumulative air-sea CO2 fluxes are larger than the DIC inventory, whereas the subtropical regions are acceptance regions. The interhemispheric transport of total natural carbon （DIC＋LDOC） was found to be northward （0.11 Pg C yr-1）, which was just balanced by the gain of carbon from the atmosphere in the Southern Hemisphere.
基金supported by funds from the Scientific Research Projects of High-level Talents of the Department of Human Resources and Social Security of Anhui Province (Grant No.2009Z019)the State Key Laboratory of Atmospheric Boundary Physics and Atmospheric Chemistry (Grant No.LAPC-KF-201105)
文摘One hundred and ten samples of rainwater were collected for chemical analysis at the summit of Huangshan Mountain, a high-altitude site in East China, from July 2010 to June 2011. The volume-weighted-mean （VWM） pH for the whole sampling period was 5.03. SO2- and Ca2＋ were the most abundant anion and cation, respectively. The ionic concentrations varied monthly with the highest concentrations in winter/spring and the lowest in summer. Evident inter-correlations were found among most ions, indicating the common sources for some species and fully mixing characteristics of the alpine precipitation chemistry. The VWM ratio of [SO]-]/[NO3] was 2.54, suggesting the acidity of rainwater comes from both nitric and sulfuric acids. Compared with contemporary observations at other alpine continental sites in China, the precipitation at Huangshan Mountain was the least polluted, with the lowest ionic concentrations. Trajectories to Huangshan Mountain on rainy days could be classified into six groups. The rainwater with influencing air masses originating in Mongolia was the most polluted with limited effect. The emissions of Jiangxi, Anhui, Zhejiang and Jiangsu provinces had a strong influence on the overall rain chemistry at Huangshan Mountain. The rainwater with influencing air masses from Inner Mongolia was heavily polluted by anthropogenic pollutants.
文摘The complex of neodymium chloride lower hydrate with diethylammonium diethyldithiocarbamate (D-DDC) was synthesized conveniently in absolute alcohol and dry N_2 atmosphere. The title complex was identified as Et_2NH_2[Nd(S_2CNEt_2)_4] by chemical and elemental analyses and the bonding characteristics of which was characterized by IR. The enthalpies of solution of neodymium chloride hydrate and D-DDC in absolute alcohol at 298.15 K and the enthalpies change of liquid-phase reaction of formation for Et_2NH_2[Nd (S_2CNEt_2)_4] at different temperatures were determined by microcalorimetry. On the basis of experimental and calculated results, three thermodynamic parameters (the activation enthalpy, the activation entropy and the activation free energy), the rate constant and three kinetic parameters (the apparent activation energy, the pre-exponential constant and the reaction order) of liquid-phase reaction of formation were obtained. The enthalpy change of the solid-phase title reaction at 298.15 K was calculated by a thermochemical cycle.
