The reaction between 3-substituted-4-hydroxy-2H-1.2-be 1.1-dioxides and phenyl isocyanate in the presence of different equivalents of strong base NaH has been studied. The structures of new derivatives were characteri...The reaction between 3-substituted-4-hydroxy-2H-1.2-be 1.1-dioxides and phenyl isocyanate in the presence of different equivalents of strong base NaH has been studied. The structures of new derivatives were characterized by 1H NMR. IR. elementary analysis and FeCl3 test.展开更多
In order to promote our understanding on electronic structure of actinide dioxides, we construct a tight-binding model composed of actinide 5f and oxygen 2p electrons, which is called f-p model. After the diagonalizat...In order to promote our understanding on electronic structure of actinide dioxides, we construct a tight-binding model composed of actinide 5f and oxygen 2p electrons, which is called f-p model. After the diagonalization of the f-p model, we compare the eigen-energies in the first Brillouin zone with the results of relativistic band-structure calculations. Here we emphasize a key role of f-p hybridization in order to understand the electronic structure of actinide dioxides. In particular, it is found that the position of energy levels of Г7 and Г8 states determined from crystalline electric field (CEF) potentials depends on the f-p hybridization. We investiagte the values of the Slater-Koster integrals for f-p hybridization, (fpσ) and (fpπ), which reproduce simultaneously the local CEF states and the band-structure calculation results. Then, we find that the absolute value of (fpπ) should be small in comparison with (fpσ) = 1 eV. The small value of |(fpπ)| is consistent with the condition to obtain the octupole ordering in the previous analysis of the f-p model.展开更多
A type of high visible-light active titanium oxinitride(TiO2-xNx)powder was prepared by a simple proc-ess:the calcination of the hydrated titanium dioxide at the atmosphere of ammonia-argon using a tu-bular electric f...A type of high visible-light active titanium oxinitride(TiO2-xNx)powder was prepared by a simple proc-ess:the calcination of the hydrated titanium dioxide at the atmosphere of ammonia-argon using a tu-bular electric furnace at high temperatures.The hydrated titanium dioxide was synthesized as the precursor of TiO2-xNx using titanic acid as raw material,which came from sulfate technique of produc-ing titanium white.The effects of temperature and reaction time on the nitrogen content,grain size and crystal structure were studied.The visible-light activity and photocatalysis capability of the powder were also investigated.展开更多
Lamellar compounds such as the disulfides of molybdenum and tungsten are widely used as additives in lubricant oils or as solid lubricants in aerospace industries.The dioxides of these two transition metals have ident...Lamellar compounds such as the disulfides of molybdenum and tungsten are widely used as additives in lubricant oils or as solid lubricants in aerospace industries.The dioxides of these two transition metals have identical microstructures with those of the disulfides.The differences in the lubrication behaviors of disulfide and dioxides were investigated theoretically.Tungsten dioxide and molybdenum dioxide exhibit higher bond strengths at the interface and lower interlayer interactions than those of the disulfides which indicates their superlubricity.Furthermore,the topography of the electron density of the single layer nanostructure determined their sliding potential barrier;the dioxides showed a weaker electronic cloud distribution between the two neighboring oxygen atoms,which facilitated the oxygen atoms of the counterpart to go through.For commensurate friction,the dioxides exhibited nearly the same value of friction work,and same was the case for the disulfides.The lower positive value of friction work for the dioxides confirmed their improved lubricity than the disulfides and the higher mechanical strength of the bulk dioxides demonstrated that they are excellent solid lubricants in vacuum.展开更多
Aiming at the problems of insufficient activity and selectivity of Cu-based catalysts in CO_(2)hydrogenation to methanol,Al_(2)O_(3),ZrO_(2)and CeO_(2)modified Cu-ZnO catalysts by the co-precipitation method were prep...Aiming at the problems of insufficient activity and selectivity of Cu-based catalysts in CO_(2)hydrogenation to methanol,Al_(2)O_(3),ZrO_(2)and CeO_(2)modified Cu-ZnO catalysts by the co-precipitation method were prepared,and the influence mechanism of additives on the structure-performance relationship of the catalysts was systematically explored.Through a variety of characterization methods such as XRD,N2 physical adsorption-desorption,TEM,H_(2)-TPR,CO_(2)-TPD and XPS,combined with catalytic performance evaluation experiments,the correlation between the microstructure of catalysts and the reaction performance of CO_(2)hydrogenation to methanol was analyzed in depth.The results show that metal additives significantly improve the performance of catalysts.After the introduction of additives,the specific surface area and pore volume of the catalysts increase,the grain size of Cu decreases,and its dispersion improves.The Ce-modified CZC catalyst exhibited the best performance,with the grain size of CuO as small as 11.41 nm,and the surface oxygen vacancy concentration(OⅡ/OⅠ=3.15)was significantly higher than that of other samples.The reaction performance test shows that under the conditions of 2.8 MPa,8000 h−1 and 280℃,the CO_(2)conversion of the CZC catalyst reached 18.83%,the methanol selectivity was 68.40%,and the methanol yield was 12.88%,all of which are superior to other catalysts.Its excellent performance can be attributed to the fact that CeO_(2)enhances the metal-support interaction,increases the surface basicity,promotes the adsorption and activation of CO_(2),and simultaneously inhibits the reverse water-gas shift side reaction.This study clarifies the structure-activity regulation mechanism of additive modification on Cu-ZnO catalysts,providing a theoretical basis and technical reference for the development of efficient catalysts for CO_(2)hydrogenation to methanol.展开更多
Under the backdrop of“Carbon Peak and Carbon Neutrality”(dual carbon)goal in China,the methane-carbon dioxide reforming reaction has attracted considerable attention due to its environmental benefits of converting t...Under the backdrop of“Carbon Peak and Carbon Neutrality”(dual carbon)goal in China,the methane-carbon dioxide reforming reaction has attracted considerable attention due to its environmental benefits of converting two greenhouse gases(methane and carbon dioxide)into syngas and its promising industrial applications.Nickel(Ni)-based catalysts,with high catalytic activity,low cost,and abundant resources,are considered ideal candidates for industrial applications.In this article,three reaction kinetic models were briefly introduced,namely the Power-Law(PL)model,the Eley-Rideal(ER)model,and the Langmuir-Hinshelwood-Hougen-Watson(LHHW)model.Based on the LHHW model,the reaction kinetics and mechanisms of different catalytic systems were systematically discussed,including the properties of supports,the doping of noble metals and transition metals,the role of promoters,and the influence of the geometric and electronic structures of Ni on the reaction mechanism.Furthermore,the kinetics of carbon deposition and elimination on various catalysts were analyzed.Based on the reaction rate expressions for carbon elimination,the reasons for the high activity of transition metal iron(Fe)-doped catalysts and core-shell structured catalysts in carbon elimination were explained.Based on the detailed collation and comparative analysis of the reaction mechanisms and kinetic characteristics across diverse Ni-based catalytic systems,a theoretical guidance for the designing of high-performance catalysts was provided in this work.展开更多
The reaction of 3-substituted-4-hydroxy-2H-1,2-benzothiazine 1,1-dioxides with aryl isocyanate under different equivalents of strong base NaH was studied. Seventeen of new derivatives were obtained whose structures we...The reaction of 3-substituted-4-hydroxy-2H-1,2-benzothiazine 1,1-dioxides with aryl isocyanate under different equivalents of strong base NaH was studied. Seventeen of new derivatives were obtained whose structures were characterized by H-1 NMR, IR, MS, elementary analysis and FeCl3 test.展开更多
Controllable synthesis of ultrathin metallene nanosheets and rational design of their spatial arrangement in favor of electrochemical catalysis are critical for their renewable energy applications.Here,a biomimetic de...Controllable synthesis of ultrathin metallene nanosheets and rational design of their spatial arrangement in favor of electrochemical catalysis are critical for their renewable energy applications.Here,a biomimetic design of“Trunk-Branch-Leaf”strategy is proposed to prepare the ultrathin edge-riched Zn-ene“leaves”with a thickness of~2.5 nm,adjacent Zn-ene cross-linked with each other,which are supported by copper nanoneedle“branches”on copper mesh“trunks,”named as Zn-ene/Cu-CM.The resulting superstructure enables the formation of an interconnected network and multiple channels,which can be used as an electrocatalytic CO_(2) reduction reaction(CO_(2)RR)electrode to allow a fast charge and mass transfer as well as a large electrolyte reservoir.By virtue of the distinctive structure,the obtained Zn-ene/Cu-CM electrode exhibits excellent selectivity and activity toward CO production with a maximum Faradaic efficiency of 91.3%and incredible partial current density up to 40 mA cm^(−2),outperforming most of the state-of-the-art Zn-based electrodes for CO_(2) reduction.The phenolphthalein color probe combined with in situ attenuated total reflection-infrared spectroscopy uncovered the formation of the localized pseudo-alkaline microenvironment at the interface of the Zn-ene/Cu-CM electrode.Theoretical calculations confirmed that the localized pH as the origin is responsible for the adsorption of CO_(2) at the interface and the generation of *COOH and *CO intermediates.This study offers valuable insights into developing efficient electrodes through synergistic regulation of reaction microenvironments and active sites,thereby facilitating the electrolysis of practical CO_(2) conversion.展开更多
Pulse tube cryocoolers are widely employed in cryogenic systems,where gas contamination has become a critical factor limiting both performance and service life.To further investigate the condensation behavior of conta...Pulse tube cryocoolers are widely employed in cryogenic systems,where gas contamination has become a critical factor limiting both performance and service life.To further investigate the condensation behavior of contaminants,this study develops a two-dimensional axisymmetric model of a linear-type cryocooler to simulate the transport and deposition processes of trace CO_(2),evaluating the impact of contamination on system pressure drop under various operating conditions.Results indicate that CO_(2)diffusion is primarily driven by concentration gradients.The CO_(2)deposition rate increases markedly at low temperatures and high concentrations,with over 90%of deposition occurring in the cold-end heat exchanger.Under different concentration distributions,dry ice predominantly accumulates in the cold-end heat exchanger;however,notable differences emerge in the pulse tube.In the uniform distribution case,CO_(2)tends to deposit along the inner wall of the pulse tube,whereas in the gradual release scenario,deposition mainly occurs on the cold-end flow straightening mesh screen.Dry ice deposition significantly increases the pressure drop across the system and decreases the pressure wave amplitude,resulting in a degradation of cooling capacity.This study lays a foundation for further investigation into the thermal properties of contaminant layers and provides theoretical guidance for optimizing cold-end components to improve contamination resilience.展开更多
In this study,electrochemical C-H carboxylation of benzylamines with CO_(2) was reported.This linear paired electrolysis system enables efficient and economical synthesis of value-added α-amino acids(α-AAs) under mi...In this study,electrochemical C-H carboxylation of benzylamines with CO_(2) was reported.This linear paired electrolysis system enables efficient and economical synthesis of value-added α-amino acids(α-AAs) under mild conditions.Various substituted benzylamines containing diverse functional groups and even highly reactive moieties,such as cyano,amide and alkene groups could be successfully transformed to the carboxylated products.Notably,this method proved to be applicable to the late-stage modification of biorelevant compounds,highlighting its potential for synthetic chemistry.Mechanistic studies such as radical trapping experiments,kinetic isotope effect(KIE) tests and cyclic voltammetry(CV) studies provided useful insight into this transformation.展开更多
The catalytic transferred of small molecules into high-value chemical products in green methods are highly perused,and has obtained huge attention.In this field,great progress has been achieved during the past five ye...The catalytic transferred of small molecules into high-value chemical products in green methods are highly perused,and has obtained huge attention.In this field,great progress has been achieved during the past five years.Followed by the roadmap(Chinese Chemical Letters,2019,30,2089-2109)written by us before five years,we think that it should be updated to give more insights in this field.Thus,we write the present roadmap based on the fast changed background.In this roadmap,oxygen and carbon dioxide reduction reactions(including at high temperature),photocatalytic hydrogen generation and carbon dioxide reduction reactions,(photo)electrocatalytic reduction of O_(2)to H_(2)O_(2)and NH_(3)generated from N_(2) are discussed.The progress and challenges in above catalytic processes are given.We believe this manuscript will give the researchers more suggestions and help them to obtain useful information in this field.展开更多
Abiotic oxygen formation predates photosynthesis,sustaining early chemical evolution,yet its elementary mechanisms remain contested.Here,we show the production pathways for molecular oxygen from doubly ionized carbon ...Abiotic oxygen formation predates photosynthesis,sustaining early chemical evolution,yet its elementary mechanisms remain contested.Here,we show the production pathways for molecular oxygen from doubly ionized carbon dioxide upon electron-impact.Through fragment ions and electron coincidence momentum imaging,we unambiguously determine the ionization mechanism by measuring the projectile energy loss in association with the C^(+) +O_(2)^(+) channel.Further potential energy and trajectory calculations enable us to elucidate the dynamical details of this fragmentation process,in which a bond rearrangement pathway is found to proceed via the structural deformation to a triangular intermediate.Moreover,we demonstrate a further roaming pathway for the formation of O_(2)^(+) from CO_(2)^(+) 2,in which a frustrated C-O bond cleavage leaves the O atom without sufficient energy to escape.The O atom then wanders around varied configuration spaces of the flat potential energy regions and forms a C-O-O_(2)^(+) intermediate prior to the final products C^(+) +O_(2)^(+).Considering the large quantities of free electrons in interstellar space,the processes revealed here are expected to be significant and should be incorporated into atmospheric evolution models.展开更多
The prediction of sea surface partial pressure of carbon dioxide(pCO_(2))in the South China Sea is crucial for understanding the region’s contribution to the global carbon budget and its interactions with climate cha...The prediction of sea surface partial pressure of carbon dioxide(pCO_(2))in the South China Sea is crucial for understanding the region’s contribution to the global carbon budget and its interactions with climate change.We applied the Spatiotemporal Convolutional Long Short-Term Memory(STConvLSTM)model,integrating key environmental factors including sea surface temperature(SST),sea surface salinity(SSS),and chlorophyll a(Chl a),to predict and analyze sea surface pCO_(2)in the South China Sea.The model demonstrated high accuracy in short-term predictions(1 month),with a mean absolute error(MAE)of 0.394,a root mean square error(RMSE)of 0.659,and a coefficient of determination(R^(2))of 0.998.For long-term predictions(12 months),the model maintained its predictive capability,with an MAE of 0.667,RMSE of 1.255,and R^(2)of 0.994.Feature importance analysis revealed that sea surface pCO_(2)and SST were the main drivers of the model’s predictions,whereas Chl a and SSS had relatively minor impacts.The model’s generalization ability was further validated in the northwest Pacific Ocean and tropical Pacific Ocean,where it successfully captured the spatiotemporal variation in pCO_(2)with small prediction errors.The ST-ConvLSTM model provides an efficient and accurate tool for forecasting and analyzing sea surface pCO_(2)in the South China Sea,offering new insights into global carbon cycling and climate change.This study demonstrates the potential of deep learning in marine science and provides a significant technical support for global changes and marine ecosystem research.展开更多
Colitis-associated colorectal cancer(CAC)is a major contributor to cancer-related mortality worldwide.Titanium dioxide(TiO_(2),E171),a widely used food additive,has been insufficiently studied regarding its effects on...Colitis-associated colorectal cancer(CAC)is a major contributor to cancer-related mortality worldwide.Titanium dioxide(TiO_(2),E171),a widely used food additive,has been insufficiently studied regarding its effects on macrophages within colon tumors during CAC development.In this study,CAC mouse models were used to investigate the biological impact of dietary E171 on macrophages in vivo,while lipopolysaccharide(LPS)-stimulated RAW264.7 macrophage cell lines were employed to elucidate the underlying mechanisms in vitro.We found that dietary E171 intake accelerated CAC development,exacerbated inflammatory responses and oxidative stress,and upregulated CAC-associated genes,including S100a8,S100a9,Lcn2,S100a11,Cxcl2,and interleukin-1α(Il-1α).E171 also increased the expression of S100A8,S100A9,NOD-like receptor family pyrin domain-containing 3(NLRP3),and gasdermin-D Nterminal(GSDMD-N)in macrophages within colon tumors.In inflammatory macrophages,E171 exposure enhanced cell viability,increased reactive oxygen species(ROS)levels,and elevated the expression and secretion of S100A8 and S100A9,consistent with in vivo histological observations.Furthermore,E171-induced secretion of S100A8 and S100A9 in macrophages was suppressed by specific inhibitors,including N-acetylcysteine(NAC,ROS inhibitor),MCC950(NLRP3 inhibitor),Z-YVAD-FMK(caspase 1 inhibitor),disulfiram(GSDMD inhibitor),and transfection of NLRP3 small interfering ribonucleic acid(siRNA).These results indicate that dietary E171 promotes CAC development by activating macrophages,with S100A8 and S100A9 serving as key mediators,and the NLRP3/caspase 1/GSDMD pathway acting as a critical mechanism.展开更多
Cu suffers from oxidation and corrosion during application due to its active chemical properties.Graphene⁃modified Cu can significantly improve its stability during application.However,copper is easily sintered at hig...Cu suffers from oxidation and corrosion during application due to its active chemical properties.Graphene⁃modified Cu can significantly improve its stability during application.However,copper is easily sintered at high temperatures,so that graphene cannot be grown inside.We demonstrate two kinds of spacers,graphite and SiO_(2),which are effective in preventing the sintering of copper and are used to assist in the growth of graphene.In the Cu⁃C system,the nucleation of graphene is scarce,and it tends to nucleate and grow on the concave surface of copper first,and then grow epitaxially to the convex surface of copper.Eventually,the obtained graphene is relatively thick.In the Cu⁃SiO_(2) system,due to the oxygen released by SiO_(2) at high temperatures,the surface of copper becomes rough.This leads to an increase in the number of graphene nucleation sites without preferred orientation,and relatively thin graphene is obtained.Two different growth mechanisms have been established for spacerseffects on graphene growth.It provides insights for graphene engineering for further applications.展开更多
For rechargeable aqueous zinc-ion batteries(ZIBs),the design of nanocomposites comprised of electrochemically active materials and carbon materials with novel structures has great prom-ise in addressing the issue of e...For rechargeable aqueous zinc-ion batteries(ZIBs),the design of nanocomposites comprised of electrochemically active materials and carbon materials with novel structures has great prom-ise in addressing the issue of electrical conductivity and structural stability in the electrode materials during electrochemical cycling.We report the production of a novel flexible electrode material,by anchoring MnO_(2) nanosheets on a B,N co-doped carbon nanotube ar-ray(BNCNTs)grown on carbon cloth(BNCNTs@MnO_(2)),which was fabricated by in-situ pyrolysis and hydrothermal growth.The generated BNCNTs were strongly bonded to the surface of the car-bon fibers in the carbon cloth which provides both excellent elec-tron transport and ion diffusion,and improves the stability and dur-ability of the cathode.Importantly,the BNCNTs offer more active sites for the hydrothermal growth of MnO_(2),ensuring a uniform dis-tribution.Electrochemical tests show that BNCNTs@MnO_(2) delivers a high specific capacity of 310.7 mAh g^(−1) at 0.1 A g^(−1),along with excellent rate capability and outstanding cycling stability,with a 79.7% capacity retention after 8000 cycles at 3 A g^(−1).展开更多
China is the most important steel producer in the world,and its steel industry is one of themost carbon-intensive industries in China.Consequently,research on carbon emissions from the steel industry is crucial for Ch...China is the most important steel producer in the world,and its steel industry is one of themost carbon-intensive industries in China.Consequently,research on carbon emissions from the steel industry is crucial for China to achieve carbon neutrality and meet its sustainable global development goals.We constructed a carbon dioxide(CO_(2))emission model for China’s iron and steel industry froma life cycle perspective,conducted an empirical analysis based on data from2019,and calculated the CO_(2)emissions of the industry throughout its life cycle.Key emission reduction factors were identified using sensitivity analysis.The results demonstrated that the CO_(2)emission intensity of the steel industry was 2.33 ton CO_(2)/ton,and the production and manufacturing stages were the main sources of CO_(2)emissions,accounting for 89.84%of the total steel life-cycle emissions.Notably,fossil fuel combustion had the highest sensitivity to steel CO_(2)emissions,with a sensitivity coefficient of 0.68,reducing the amount of fossil fuel combustion by 20%and carbon emissions by 13.60%.The sensitivities of power structure optimization and scrap consumption were similar,while that of the transportation structure adjustment was the lowest,with a sensitivity coefficient of less than 0.1.Given the current strategic goals of peak carbon and carbon neutrality,it is in the best interest of the Chinese government to actively promote energy-saving and low-carbon technologies,increase the ratio of scrap steel to steelmaking,and build a new power system.展开更多
Electromagnetic interference(EMI)shielding materials with superior shielding efficiency and low-reflection properties hold promising potential for utilization across electronic components,precision instruments,and fif...Electromagnetic interference(EMI)shielding materials with superior shielding efficiency and low-reflection properties hold promising potential for utilization across electronic components,precision instruments,and fifth-generation communication equipment.In this study,multistage microcellular waterborne polyurethane(WPU)composites were constructed via gradient induction,layer-by-layer casting,and supercritical carbon dioxide foaming.The gradient-structured WPU/ironcobalt loaded reduced graphene oxide(FeCo@rGO)foam serves as an impedance-matched absorption layer,while the highly conductive WPU/silver loaded glass microspheres(Ag@GM)layer is employed as a reflection layer.Thanks to the incorporation of an asymmetric structure,as well as the introduction of gradient and porous configurations,the composite foam demonstrates excellent conductivity,outstanding EMI SE(74.9 dB),and minimal reflection characteristics(35.28%)in 8.2-12.4 GHz,implying that more than 99.99999%of electromagnetic(EM)waves were blocked and only 35.28%were reflected to the external environment.Interestingly,the reflectivity of the composite foam is reduced to 0.41%at 10.88 GHz due to the resonance for incident and reflected EM waves.Beyond that,the composite foam is characterized by low density(0.47 g/cm^(3))and great stability of EMI shielding properties.This work offers a viable approach for craft-ing lightweight,highly shielding,and minimally reflective EMI shielding composites.展开更多
Understanding the evolution of microstructures in nuclear fuels under high-burn-up conditions is critical for extending fuel refueling cycles and enhancing nuclear reactor safety.In this study,a phase-field model is p...Understanding the evolution of microstructures in nuclear fuels under high-burn-up conditions is critical for extending fuel refueling cycles and enhancing nuclear reactor safety.In this study,a phase-field model is proposed to examine the evolution of high-burn-up structures in polycrystalline UO_(2).The formation and growth of recrystallized grains were initially investigated.It was demonstrated that recrystallization kinetics adhere to the Kolmogorov–Johnson–Mehl–Avrami(KJMA)equation,and that recrystallization represents a process of free-energy reduction.Subsequently,the microstructural evolution in UO_(2) was analyzed as the burn up increased.Gas bubbles acted as additional nucleation sites,thereby augmenting the recrystallization kinetics,whereas the presence of recrystallized grains accelerated bubble growth by increasing the number of grain boundaries.The observed variations in the recrystallization kinetics and porosity with burn-up closely align with experimental findings.Furthermore,the influence of grain size on microstructure evolution was investigated.Larger grain sizes were found to decrease porosity and the occurrence of high-burn-up structures.展开更多
Due to the greenhouse effect caused by carbon dioxide(CO_(2))emission,much attention has been paid for the removal of CO_(2).Porous liquids(PLs),as new type of liquid materials,have obvious advantages in mass and heat...Due to the greenhouse effect caused by carbon dioxide(CO_(2))emission,much attention has been paid for the removal of CO_(2).Porous liquids(PLs),as new type of liquid materials,have obvious advantages in mass and heat transfer,which are widely used in gas adsorption and sep-aration.Metal–organic frameworks(MOFs)with merits like large surface area,inherent porous structure and adjustable topology have been considered as one of the best candidates for PLs construction.This review presents the state-of-the-art status on the fabrication strategy of MOFs-based PLs and their CO_(2) absorption and utilization performance,and the positive effects of porosity and functional modification on the absorption-desorption property,selectivity of target product,and regeneration ability are well summarized.Finally,the challenges and prospects for MOFs-based PLs in the optimization of preparation,the coupling of multiple removal techniques,the in situ characterization methods,the regeneration and cycle stability,the environmental impact as well as expansion of application are proposed.展开更多
文摘The reaction between 3-substituted-4-hydroxy-2H-1.2-be 1.1-dioxides and phenyl isocyanate in the presence of different equivalents of strong base NaH has been studied. The structures of new derivatives were characterized by 1H NMR. IR. elementary analysis and FeCl3 test.
文摘In order to promote our understanding on electronic structure of actinide dioxides, we construct a tight-binding model composed of actinide 5f and oxygen 2p electrons, which is called f-p model. After the diagonalization of the f-p model, we compare the eigen-energies in the first Brillouin zone with the results of relativistic band-structure calculations. Here we emphasize a key role of f-p hybridization in order to understand the electronic structure of actinide dioxides. In particular, it is found that the position of energy levels of Г7 and Г8 states determined from crystalline electric field (CEF) potentials depends on the f-p hybridization. We investiagte the values of the Slater-Koster integrals for f-p hybridization, (fpσ) and (fpπ), which reproduce simultaneously the local CEF states and the band-structure calculation results. Then, we find that the absolute value of (fpπ) should be small in comparison with (fpσ) = 1 eV. The small value of |(fpπ)| is consistent with the condition to obtain the octupole ordering in the previous analysis of the f-p model.
文摘A type of high visible-light active titanium oxinitride(TiO2-xNx)powder was prepared by a simple proc-ess:the calcination of the hydrated titanium dioxide at the atmosphere of ammonia-argon using a tu-bular electric furnace at high temperatures.The hydrated titanium dioxide was synthesized as the precursor of TiO2-xNx using titanic acid as raw material,which came from sulfate technique of produc-ing titanium white.The effects of temperature and reaction time on the nitrogen content,grain size and crystal structure were studied.The visible-light activity and photocatalysis capability of the powder were also investigated.
基金the National Nature Science Foundation of China，the 'Top Hundred Talents' Program of Chinese Academy of Sciences and the National Key Basic Research and Development (973) Program of China (2013CB632300) for financial support
文摘Lamellar compounds such as the disulfides of molybdenum and tungsten are widely used as additives in lubricant oils or as solid lubricants in aerospace industries.The dioxides of these two transition metals have identical microstructures with those of the disulfides.The differences in the lubrication behaviors of disulfide and dioxides were investigated theoretically.Tungsten dioxide and molybdenum dioxide exhibit higher bond strengths at the interface and lower interlayer interactions than those of the disulfides which indicates their superlubricity.Furthermore,the topography of the electron density of the single layer nanostructure determined their sliding potential barrier;the dioxides showed a weaker electronic cloud distribution between the two neighboring oxygen atoms,which facilitated the oxygen atoms of the counterpart to go through.For commensurate friction,the dioxides exhibited nearly the same value of friction work,and same was the case for the disulfides.The lower positive value of friction work for the dioxides confirmed their improved lubricity than the disulfides and the higher mechanical strength of the bulk dioxides demonstrated that they are excellent solid lubricants in vacuum.
基金Supported by National Key R&D Program of China(2022YFA1503400)。
文摘Aiming at the problems of insufficient activity and selectivity of Cu-based catalysts in CO_(2)hydrogenation to methanol,Al_(2)O_(3),ZrO_(2)and CeO_(2)modified Cu-ZnO catalysts by the co-precipitation method were prepared,and the influence mechanism of additives on the structure-performance relationship of the catalysts was systematically explored.Through a variety of characterization methods such as XRD,N2 physical adsorption-desorption,TEM,H_(2)-TPR,CO_(2)-TPD and XPS,combined with catalytic performance evaluation experiments,the correlation between the microstructure of catalysts and the reaction performance of CO_(2)hydrogenation to methanol was analyzed in depth.The results show that metal additives significantly improve the performance of catalysts.After the introduction of additives,the specific surface area and pore volume of the catalysts increase,the grain size of Cu decreases,and its dispersion improves.The Ce-modified CZC catalyst exhibited the best performance,with the grain size of CuO as small as 11.41 nm,and the surface oxygen vacancy concentration(OⅡ/OⅠ=3.15)was significantly higher than that of other samples.The reaction performance test shows that under the conditions of 2.8 MPa,8000 h−1 and 280℃,the CO_(2)conversion of the CZC catalyst reached 18.83%,the methanol selectivity was 68.40%,and the methanol yield was 12.88%,all of which are superior to other catalysts.Its excellent performance can be attributed to the fact that CeO_(2)enhances the metal-support interaction,increases the surface basicity,promotes the adsorption and activation of CO_(2),and simultaneously inhibits the reverse water-gas shift side reaction.This study clarifies the structure-activity regulation mechanism of additive modification on Cu-ZnO catalysts,providing a theoretical basis and technical reference for the development of efficient catalysts for CO_(2)hydrogenation to methanol.
基金Supported by Innovation Capability Support Program of Shaanxi(2024RS-CXTD-53,2024ZC-KJXX-096)the Key R&D Program of Shaanxi Province(2022QCY-LL-69)Xi’an Science and Technology Project(24GXFW0089)。
文摘Under the backdrop of“Carbon Peak and Carbon Neutrality”(dual carbon)goal in China,the methane-carbon dioxide reforming reaction has attracted considerable attention due to its environmental benefits of converting two greenhouse gases(methane and carbon dioxide)into syngas and its promising industrial applications.Nickel(Ni)-based catalysts,with high catalytic activity,low cost,and abundant resources,are considered ideal candidates for industrial applications.In this article,three reaction kinetic models were briefly introduced,namely the Power-Law(PL)model,the Eley-Rideal(ER)model,and the Langmuir-Hinshelwood-Hougen-Watson(LHHW)model.Based on the LHHW model,the reaction kinetics and mechanisms of different catalytic systems were systematically discussed,including the properties of supports,the doping of noble metals and transition metals,the role of promoters,and the influence of the geometric and electronic structures of Ni on the reaction mechanism.Furthermore,the kinetics of carbon deposition and elimination on various catalysts were analyzed.Based on the reaction rate expressions for carbon elimination,the reasons for the high activity of transition metal iron(Fe)-doped catalysts and core-shell structured catalysts in carbon elimination were explained.Based on the detailed collation and comparative analysis of the reaction mechanisms and kinetic characteristics across diverse Ni-based catalytic systems,a theoretical guidance for the designing of high-performance catalysts was provided in this work.
基金Project supported by the National Natural Science Foundation of China.
文摘The reaction of 3-substituted-4-hydroxy-2H-1,2-benzothiazine 1,1-dioxides with aryl isocyanate under different equivalents of strong base NaH was studied. Seventeen of new derivatives were obtained whose structures were characterized by H-1 NMR, IR, MS, elementary analysis and FeCl3 test.
基金supports of the National Natural Science Foundation of China(NSFC)(52021004,52394202)key project of the Joint Fund for Innovation and Development of Chongqing Natural Science Foundation(CSTB2022NSCQ-LZX0013)+1 种基金the National Natural Science Foundation of China(NSFC)(52301232,and 52476056)the Natural Science Foundation of Chongqing Province(2024NSCQ-MSX1109).
文摘Controllable synthesis of ultrathin metallene nanosheets and rational design of their spatial arrangement in favor of electrochemical catalysis are critical for their renewable energy applications.Here,a biomimetic design of“Trunk-Branch-Leaf”strategy is proposed to prepare the ultrathin edge-riched Zn-ene“leaves”with a thickness of~2.5 nm,adjacent Zn-ene cross-linked with each other,which are supported by copper nanoneedle“branches”on copper mesh“trunks,”named as Zn-ene/Cu-CM.The resulting superstructure enables the formation of an interconnected network and multiple channels,which can be used as an electrocatalytic CO_(2) reduction reaction(CO_(2)RR)electrode to allow a fast charge and mass transfer as well as a large electrolyte reservoir.By virtue of the distinctive structure,the obtained Zn-ene/Cu-CM electrode exhibits excellent selectivity and activity toward CO production with a maximum Faradaic efficiency of 91.3%and incredible partial current density up to 40 mA cm^(−2),outperforming most of the state-of-the-art Zn-based electrodes for CO_(2) reduction.The phenolphthalein color probe combined with in situ attenuated total reflection-infrared spectroscopy uncovered the formation of the localized pseudo-alkaline microenvironment at the interface of the Zn-ene/Cu-CM electrode.Theoretical calculations confirmed that the localized pH as the origin is responsible for the adsorption of CO_(2) at the interface and the generation of *COOH and *CO intermediates.This study offers valuable insights into developing efficient electrodes through synergistic regulation of reaction microenvironments and active sites,thereby facilitating the electrolysis of practical CO_(2) conversion.
基金supported by the National Natural Science Foundation of China(No.52376012)the Aeronautical Science Foundation of China(20230024047001).
文摘Pulse tube cryocoolers are widely employed in cryogenic systems,where gas contamination has become a critical factor limiting both performance and service life.To further investigate the condensation behavior of contaminants,this study develops a two-dimensional axisymmetric model of a linear-type cryocooler to simulate the transport and deposition processes of trace CO_(2),evaluating the impact of contamination on system pressure drop under various operating conditions.Results indicate that CO_(2)diffusion is primarily driven by concentration gradients.The CO_(2)deposition rate increases markedly at low temperatures and high concentrations,with over 90%of deposition occurring in the cold-end heat exchanger.Under different concentration distributions,dry ice predominantly accumulates in the cold-end heat exchanger;however,notable differences emerge in the pulse tube.In the uniform distribution case,CO_(2)tends to deposit along the inner wall of the pulse tube,whereas in the gradual release scenario,deposition mainly occurs on the cold-end flow straightening mesh screen.Dry ice deposition significantly increases the pressure drop across the system and decreases the pressure wave amplitude,resulting in a degradation of cooling capacity.This study lays a foundation for further investigation into the thermal properties of contaminant layers and provides theoretical guidance for optimizing cold-end components to improve contamination resilience.
基金Financial support from National Key R&D Program of China (No.2023YFA1507203)National Natural Science Foundation of China (Nos.22371149 and 22188101)+3 种基金the Fundamental Research Funds for the Central Universities (No.63224098)Frontiers Science Center for New Organic Matter,Nankai University (No.63181206)Nankai University are gratefully acknowledgedthe Haihe Laboratory of Sustainable Chemical Transformations for financial support。
文摘In this study,electrochemical C-H carboxylation of benzylamines with CO_(2) was reported.This linear paired electrolysis system enables efficient and economical synthesis of value-added α-amino acids(α-AAs) under mild conditions.Various substituted benzylamines containing diverse functional groups and even highly reactive moieties,such as cyano,amide and alkene groups could be successfully transformed to the carboxylated products.Notably,this method proved to be applicable to the late-stage modification of biorelevant compounds,highlighting its potential for synthetic chemistry.Mechanistic studies such as radical trapping experiments,kinetic isotope effect(KIE) tests and cyclic voltammetry(CV) studies provided useful insight into this transformation.
基金supported by the National Natural Science Foundation of China(Nos.22268003,22102095,52204320,U20A20246 and 12275199,U22A20418,22075196,21972110,52202208)National Key Research and Development Program of China(Nos.2023YFA1507903,2022YFB3803600,2022YFB4002501)+9 种基金SINOPEC(Beijing)Research Institute of Chemical Industry Co.,Ltd.(No.223239)the Fundamental Research Funds for the Central Universities(No.CCNU22JC017)the Postdoctoral Science Foundation of China(No.2021M692535)the Natural Science Foundation of Shaanxi Province(No.2022JQ-095)the Basic Research Project Foundation of Xi’an Jiaotong University(No.xzy012024012)the Youth Foundation of State Key Laboratory of Electrical Insulation and Power Equipment(No.EIPE2131)the Russian Science Foundation(No.22-13-00035)the Ministry of Science and Higher Education within the framework of a State Assignment of the Ioffe Institute,Russian Academy of Sciences(No.FFUG-2024-0036)Yunnan Fundamental Research Projects(No.202305AF150116)the Research Project Supported by Shanxi Scholarship Council of China(No.2022-050)。
文摘The catalytic transferred of small molecules into high-value chemical products in green methods are highly perused,and has obtained huge attention.In this field,great progress has been achieved during the past five years.Followed by the roadmap(Chinese Chemical Letters,2019,30,2089-2109)written by us before five years,we think that it should be updated to give more insights in this field.Thus,we write the present roadmap based on the fast changed background.In this roadmap,oxygen and carbon dioxide reduction reactions(including at high temperature),photocatalytic hydrogen generation and carbon dioxide reduction reactions,(photo)electrocatalytic reduction of O_(2)to H_(2)O_(2)and NH_(3)generated from N_(2) are discussed.The progress and challenges in above catalytic processes are given.We believe this manuscript will give the researchers more suggestions and help them to obtain useful information in this field.
基金supported by the National Natural Science Foundation of China (Grant Nos.12325406,92261201,12404305,and W2512072)the Shaanxi Province Natural Science Fundamental Research Project (Grant Nos.2023JC-XJ-03 and23JSQ013)the China Postdoctoral Science Foundation (Grant Nos.BX20240286 and 2024M7625)。
文摘Abiotic oxygen formation predates photosynthesis,sustaining early chemical evolution,yet its elementary mechanisms remain contested.Here,we show the production pathways for molecular oxygen from doubly ionized carbon dioxide upon electron-impact.Through fragment ions and electron coincidence momentum imaging,we unambiguously determine the ionization mechanism by measuring the projectile energy loss in association with the C^(+) +O_(2)^(+) channel.Further potential energy and trajectory calculations enable us to elucidate the dynamical details of this fragmentation process,in which a bond rearrangement pathway is found to proceed via the structural deformation to a triangular intermediate.Moreover,we demonstrate a further roaming pathway for the formation of O_(2)^(+) from CO_(2)^(+) 2,in which a frustrated C-O bond cleavage leaves the O atom without sufficient energy to escape.The O atom then wanders around varied configuration spaces of the flat potential energy regions and forms a C-O-O_(2)^(+) intermediate prior to the final products C^(+) +O_(2)^(+).Considering the large quantities of free electrons in interstellar space,the processes revealed here are expected to be significant and should be incorporated into atmospheric evolution models.
基金Supported by the National Key Research and Development Program of China(No.2023YFC3008202)the National Natural Science Foundation of China(No.42406019)the Scientific Research Fund of Zhejiang Provincial Education Department(No.Y202353066)。
文摘The prediction of sea surface partial pressure of carbon dioxide(pCO_(2))in the South China Sea is crucial for understanding the region’s contribution to the global carbon budget and its interactions with climate change.We applied the Spatiotemporal Convolutional Long Short-Term Memory(STConvLSTM)model,integrating key environmental factors including sea surface temperature(SST),sea surface salinity(SSS),and chlorophyll a(Chl a),to predict and analyze sea surface pCO_(2)in the South China Sea.The model demonstrated high accuracy in short-term predictions(1 month),with a mean absolute error(MAE)of 0.394,a root mean square error(RMSE)of 0.659,and a coefficient of determination(R^(2))of 0.998.For long-term predictions(12 months),the model maintained its predictive capability,with an MAE of 0.667,RMSE of 1.255,and R^(2)of 0.994.Feature importance analysis revealed that sea surface pCO_(2)and SST were the main drivers of the model’s predictions,whereas Chl a and SSS had relatively minor impacts.The model’s generalization ability was further validated in the northwest Pacific Ocean and tropical Pacific Ocean,where it successfully captured the spatiotemporal variation in pCO_(2)with small prediction errors.The ST-ConvLSTM model provides an efficient and accurate tool for forecasting and analyzing sea surface pCO_(2)in the South China Sea,offering new insights into global carbon cycling and climate change.This study demonstrates the potential of deep learning in marine science and provides a significant technical support for global changes and marine ecosystem research.
基金supported by the National Natural Science Foundation of China(Nos.81974441 and 82203619)the Science and Technology Planning Project of Shenzhen Municipality(Nos.JCYJ20190814105619048 and JCYJ20220530154202005)。
文摘Colitis-associated colorectal cancer(CAC)is a major contributor to cancer-related mortality worldwide.Titanium dioxide(TiO_(2),E171),a widely used food additive,has been insufficiently studied regarding its effects on macrophages within colon tumors during CAC development.In this study,CAC mouse models were used to investigate the biological impact of dietary E171 on macrophages in vivo,while lipopolysaccharide(LPS)-stimulated RAW264.7 macrophage cell lines were employed to elucidate the underlying mechanisms in vitro.We found that dietary E171 intake accelerated CAC development,exacerbated inflammatory responses and oxidative stress,and upregulated CAC-associated genes,including S100a8,S100a9,Lcn2,S100a11,Cxcl2,and interleukin-1α(Il-1α).E171 also increased the expression of S100A8,S100A9,NOD-like receptor family pyrin domain-containing 3(NLRP3),and gasdermin-D Nterminal(GSDMD-N)in macrophages within colon tumors.In inflammatory macrophages,E171 exposure enhanced cell viability,increased reactive oxygen species(ROS)levels,and elevated the expression and secretion of S100A8 and S100A9,consistent with in vivo histological observations.Furthermore,E171-induced secretion of S100A8 and S100A9 in macrophages was suppressed by specific inhibitors,including N-acetylcysteine(NAC,ROS inhibitor),MCC950(NLRP3 inhibitor),Z-YVAD-FMK(caspase 1 inhibitor),disulfiram(GSDMD inhibitor),and transfection of NLRP3 small interfering ribonucleic acid(siRNA).These results indicate that dietary E171 promotes CAC development by activating macrophages,with S100A8 and S100A9 serving as key mediators,and the NLRP3/caspase 1/GSDMD pathway acting as a critical mechanism.
文摘Cu suffers from oxidation and corrosion during application due to its active chemical properties.Graphene⁃modified Cu can significantly improve its stability during application.However,copper is easily sintered at high temperatures,so that graphene cannot be grown inside.We demonstrate two kinds of spacers,graphite and SiO_(2),which are effective in preventing the sintering of copper and are used to assist in the growth of graphene.In the Cu⁃C system,the nucleation of graphene is scarce,and it tends to nucleate and grow on the concave surface of copper first,and then grow epitaxially to the convex surface of copper.Eventually,the obtained graphene is relatively thick.In the Cu⁃SiO_(2) system,due to the oxygen released by SiO_(2) at high temperatures,the surface of copper becomes rough.This leads to an increase in the number of graphene nucleation sites without preferred orientation,and relatively thin graphene is obtained.Two different growth mechanisms have been established for spacerseffects on graphene growth.It provides insights for graphene engineering for further applications.
基金financial support from projects funded by the National Natural Science Foundation of China(52172038,22179017)the National Key Research and Development Program of China(2022YFB4101600,2022YFB4101601)。
文摘For rechargeable aqueous zinc-ion batteries(ZIBs),the design of nanocomposites comprised of electrochemically active materials and carbon materials with novel structures has great prom-ise in addressing the issue of electrical conductivity and structural stability in the electrode materials during electrochemical cycling.We report the production of a novel flexible electrode material,by anchoring MnO_(2) nanosheets on a B,N co-doped carbon nanotube ar-ray(BNCNTs)grown on carbon cloth(BNCNTs@MnO_(2)),which was fabricated by in-situ pyrolysis and hydrothermal growth.The generated BNCNTs were strongly bonded to the surface of the car-bon fibers in the carbon cloth which provides both excellent elec-tron transport and ion diffusion,and improves the stability and dur-ability of the cathode.Importantly,the BNCNTs offer more active sites for the hydrothermal growth of MnO_(2),ensuring a uniform dis-tribution.Electrochemical tests show that BNCNTs@MnO_(2) delivers a high specific capacity of 310.7 mAh g^(−1) at 0.1 A g^(−1),along with excellent rate capability and outstanding cycling stability,with a 79.7% capacity retention after 8000 cycles at 3 A g^(−1).
基金supported by Ningbo’s major scientific and technological breakthrough project“Research and Demonstration on the Technology of Collaborative Disposal of Secondary Ash in Typical Industrial Furnaces” (No.20212ZDYF020047)the central balance fund project“Research on Carbon Emission Accounting and Emission Reduction Potential Assessment for the Whole Life Cycle of Iron and Steel Industry” (No.2021-JY-07).
文摘China is the most important steel producer in the world,and its steel industry is one of themost carbon-intensive industries in China.Consequently,research on carbon emissions from the steel industry is crucial for China to achieve carbon neutrality and meet its sustainable global development goals.We constructed a carbon dioxide(CO_(2))emission model for China’s iron and steel industry froma life cycle perspective,conducted an empirical analysis based on data from2019,and calculated the CO_(2)emissions of the industry throughout its life cycle.Key emission reduction factors were identified using sensitivity analysis.The results demonstrated that the CO_(2)emission intensity of the steel industry was 2.33 ton CO_(2)/ton,and the production and manufacturing stages were the main sources of CO_(2)emissions,accounting for 89.84%of the total steel life-cycle emissions.Notably,fossil fuel combustion had the highest sensitivity to steel CO_(2)emissions,with a sensitivity coefficient of 0.68,reducing the amount of fossil fuel combustion by 20%and carbon emissions by 13.60%.The sensitivities of power structure optimization and scrap consumption were similar,while that of the transportation structure adjustment was the lowest,with a sensitivity coefficient of less than 0.1.Given the current strategic goals of peak carbon and carbon neutrality,it is in the best interest of the Chinese government to actively promote energy-saving and low-carbon technologies,increase the ratio of scrap steel to steelmaking,and build a new power system.
基金supported by the Natural Science Foundation of Anhui Province(No.2308085QE146 and 2208085ME116)the National Natural Science Foundation of China(No.52173039)+1 种基金the Natural Science Foundation of Jiangsu Province(No.BK20210894)the Anhui Provincial Universities Outstanding Youth Research Project(No.2023AH020018).
文摘Electromagnetic interference(EMI)shielding materials with superior shielding efficiency and low-reflection properties hold promising potential for utilization across electronic components,precision instruments,and fifth-generation communication equipment.In this study,multistage microcellular waterborne polyurethane(WPU)composites were constructed via gradient induction,layer-by-layer casting,and supercritical carbon dioxide foaming.The gradient-structured WPU/ironcobalt loaded reduced graphene oxide(FeCo@rGO)foam serves as an impedance-matched absorption layer,while the highly conductive WPU/silver loaded glass microspheres(Ag@GM)layer is employed as a reflection layer.Thanks to the incorporation of an asymmetric structure,as well as the introduction of gradient and porous configurations,the composite foam demonstrates excellent conductivity,outstanding EMI SE(74.9 dB),and minimal reflection characteristics(35.28%)in 8.2-12.4 GHz,implying that more than 99.99999%of electromagnetic(EM)waves were blocked and only 35.28%were reflected to the external environment.Interestingly,the reflectivity of the composite foam is reduced to 0.41%at 10.88 GHz due to the resonance for incident and reflected EM waves.Beyond that,the composite foam is characterized by low density(0.47 g/cm^(3))and great stability of EMI shielding properties.This work offers a viable approach for craft-ing lightweight,highly shielding,and minimally reflective EMI shielding composites.
基金supported by the National Natural Science Foundation of China(Grant Nos.U20B2013 and 12205286)the National Key Research and Development Program of China(Grant No.2022YFB1902401)。
文摘Understanding the evolution of microstructures in nuclear fuels under high-burn-up conditions is critical for extending fuel refueling cycles and enhancing nuclear reactor safety.In this study,a phase-field model is proposed to examine the evolution of high-burn-up structures in polycrystalline UO_(2).The formation and growth of recrystallized grains were initially investigated.It was demonstrated that recrystallization kinetics adhere to the Kolmogorov–Johnson–Mehl–Avrami(KJMA)equation,and that recrystallization represents a process of free-energy reduction.Subsequently,the microstructural evolution in UO_(2) was analyzed as the burn up increased.Gas bubbles acted as additional nucleation sites,thereby augmenting the recrystallization kinetics,whereas the presence of recrystallized grains accelerated bubble growth by increasing the number of grain boundaries.The observed variations in the recrystallization kinetics and porosity with burn-up closely align with experimental findings.Furthermore,the influence of grain size on microstructure evolution was investigated.Larger grain sizes were found to decrease porosity and the occurrence of high-burn-up structures.
基金supported by the Natural Science Foundation of China(22106007 and U23A20120)Beijing Natural Science Foundation(8244060)+2 种基金China Postdoctoral Science Foundation(2023M730143)R&D Program of BeijingMunicipal Education Commission(KZ202210005011)Natural Science Foundation of Hebei Province(B2021208033).
文摘Due to the greenhouse effect caused by carbon dioxide(CO_(2))emission,much attention has been paid for the removal of CO_(2).Porous liquids(PLs),as new type of liquid materials,have obvious advantages in mass and heat transfer,which are widely used in gas adsorption and sep-aration.Metal–organic frameworks(MOFs)with merits like large surface area,inherent porous structure and adjustable topology have been considered as one of the best candidates for PLs construction.This review presents the state-of-the-art status on the fabrication strategy of MOFs-based PLs and their CO_(2) absorption and utilization performance,and the positive effects of porosity and functional modification on the absorption-desorption property,selectivity of target product,and regeneration ability are well summarized.Finally,the challenges and prospects for MOFs-based PLs in the optimization of preparation,the coupling of multiple removal techniques,the in situ characterization methods,the regeneration and cycle stability,the environmental impact as well as expansion of application are proposed.
