As a prototypical high-energy-density reactive material system,metastable intermolecular composites(MICs)have attracted considerable interest owing to their customizable component configurations and interfacial archit...As a prototypical high-energy-density reactive material system,metastable intermolecular composites(MICs)have attracted considerable interest owing to their customizable component configurations and interfacial architectures.Nevertheless,their energy release characteristics are fundamentally constrained by the formation of condensed-phase products with elevated boiling points,thereby diminishing their efficacy in applications requiring rapid pressure generation or shock wave propagation.Herein,we demonstrate a molecular-level fluorination approach that enables oxygen substitution by fluorine within bismuth oxide crystalline frameworks,yielding ternary BixOyFz crystals with atomically precise F/O stoichiometric control through systematic solvent polarity engineering.This energetics system,designed through a multilevel regulation strategy,realizes stepwise redox reactions of Al–F and Al–O during energy release,with the partitioning between these redox pathways being precisely allocable through hierarchical regulation.Furthermore,the pre-ignition reaction(PIR)between BixOyFz and Al2O3(the inert passivation shell of Al)weakens the passivation layer,lowering the ignition threshold.The in situ generation of low-boiling-point AlF3 promotes rapid gas expansion,leading to significantly enhanced pressurization rates and deflagration wave velocities under confinement compared to conventional strategies.To evaluate energy output capabilities and validate potential safety-protection applications,the system successfully achieved instantaneous destruction of SD chips,enabling secure data erasure.This work establishes crystalline lattice fluorination as a generalized materials design strategy to transcend intrinsic limitations of MICs systems in component selection and reaction thermodynamics,providing new paradigms for adaptive energetic architectures and transient microelectromechanical applications.展开更多
A strong built-in electric field(V_(bi))is the key to achieving rapid separation of photogenerated carriers in perovskite solar cells.This is particularly important for hole transport layer(HTL)free carbon-based perov...A strong built-in electric field(V_(bi))is the key to achieving rapid separation of photogenerated carriers in perovskite solar cells.This is particularly important for hole transport layer(HTL)free carbon-based perovskite solar cells(C-PSCs),which have a large interface energy level mismatch.The regulation of perovslite's surface energetics is an effective way to improve the V_(bi)and promote charge extraction,which is typically achieved by organic molecules.However,the insulating nature of organic molecules also negatively hinders charge transfer,resulting in a contradiction of"extraction-transport".Quantum dots(Q.Ds)have great potential for energetics regulation of perovskite film due to their semiconductor properties and inherent large dipole moments,but have not yet been explored.In this work,we propose a strategy of discrete embedding semiconductor QDs at the surface grain boundaries of the perovskite film to regulate surface energetics.The QDs change the energetics of the perovskite film surface,transforming the surface energetics from n-to p-type,thus constructing p-n homojunction at the interface.This significantly enhances the Vbi at the perovskite/carbon electrode interface,promoting hole extraction.In addition,the embedded discrete distribution of QDs at the upper surface grain boundaries ensures efficient transport of the extracted holes to the carbon electrode,overcoming the contradiction of"extraction-transport"for traditional energetics control strategies.Consequently,the fabricated planar HTL-free C-PSCs achieve an efficiency of 20.10%(certified 19.8%),which is one of the highest values reported for this kind of device.展开更多
Ocean mixing is a consequence of essential dynamic processes such as internal tides and lee waves that occur near the seafloor topography.Internal tides and lee waves are generated by barotropic tidal currents and geo...Ocean mixing is a consequence of essential dynamic processes such as internal tides and lee waves that occur near the seafloor topography.Internal tides and lee waves are generated by barotropic tidal currents and geostrophic flows,respectively.Ocean current is composed of multiple flows;thus,internal tides and lee waves occur concurrently in the real ocean.In this paper,the Massachusetts Institute of Technology general circulation model(MITgcm)is used to conduct 2D numerical experiments.By varying background flow intensities,the energy and dissipation relationship between internal tides and lee waves are investigated.The results reveal that the internal tide beams become asymmetric due to the influence of Doppler shift.The lee wave structure gradually leads the wave field when the background flow velocity rises constantly.The presence of a background flow increases the energy portion of the high-mode wave by up to 15%-20%.Moreover,strong shear,owing to the background flow,considerably increases dissipation.When the background flow velocity is higher than the barotropic tidal current velocity,the isopycnal overturn triggered by the lee wave generates a dissipation of the same order of magnitude as the shear.展开更多
The formations and transformations of the chemical bonds of reactants and intermediates on cata- lyst surfaces occur in conjunction with the evolution of heat during catalytic reactions. Measure- ment of this evolved ...The formations and transformations of the chemical bonds of reactants and intermediates on cata- lyst surfaces occur in conjunction with the evolution of heat during catalytic reactions. Measure- ment of this evolved heat is helpful in terms of understanding the nature of the interactions be- tween the catalyst and the adsorbed species, and provides insights into the reactivity of the catalyst. Although various techniques have previously been applied to assessments of evolved heat, direct measurements using a Tian-Calvet microcalorimeter are currently the most reliable method for this purpose. In this review, we summarize the relationship between the adsorption/reaction energetics determined by microcalorimetry and the reactivities of supported catalysts, and examine the im- portant role of microcalorimetry in understanding catalytic performance from the energetic point of view.展开更多
高效准确的机器学习模型是高通量筛选优质含能分子的基础,为此设计了完全通过结构式便可输出多项含能材料性质的多输入多输出机器学习模型(MIMO-ML)。基于478个含能分子数据集进行模型构建,通过筛选得到AMID_h、ATTS1are、OB三个优秀描...高效准确的机器学习模型是高通量筛选优质含能分子的基础,为此设计了完全通过结构式便可输出多项含能材料性质的多输入多输出机器学习模型(MIMO-ML)。基于478个含能分子数据集进行模型构建,通过筛选得到AMID_h、ATTS1are、OB三个优秀描述符,并在此基础上建立了自定义描述符集。结果表明,随机森林(RF)及多层感知机(MLP)适合被应用于含能材料性能预测多输出模型构建,输出性质包括爆速D(MAE=256 m/s),热分解温度T_(d)(MAE=34.7℃),撞击感度ln H 50(MAE=0.63)。同时,MLP模型相比于RF模型对于特征数量更敏感,且利用更少的特征可得到与RF精度相似的模型,表明MIMO-ML模型能够快速且准确地识别高性能含能材料,可应用于含能分子的设计与快速筛选。展开更多
he characteristic study,by means of in-situ IR spectroscopy, of chemisorbed species on the Ni-catalysts for the partial oxidation of methane(POM)to syngas demonstrated the existence of CH_x(a)and H_xCO(a)adspecies on...he characteristic study,by means of in-situ IR spectroscopy, of chemisorbed species on the Ni-catalysts for the partial oxidation of methane(POM)to syngas demonstrated the existence of CH_x(a)and H_xCO(a)adspecies on the functioning Ni-catalysts, Several designed experimental investigations on the reactivities of methane with CO_2 and with O_2,respectively,over the Ni-catalysts, and of CO_2 with the prereduced Ni-catalyst,ats well as of the deposited carbon with CO_2 and with O_2,respectlvely,liave been carried out and the reLqults were unfavorable to the two-step mechanistic interpretation proposed for the POM reaction. By means of tlie BOC-MP Approach,energetics of a set of elementary reactions,which may be involved in the POM process,on the clean(111)surface of Ni,Fe,Cu and Pd, re- spectively,has been studied.The result;of the experiments and the calculation of the present work favor the direct catalytic dissociation-plus-surface oxidation-plus-further debdrogenation mechanism as the dominant pathway making major contribution to the POM reaction.展开更多
基金supported by the National Natural Science Foundation of China,China(Grant No.22305100,No.22405104)the Hubei Provincial International Science and Technology Cooperation Program Project(Grant No.2023EHA014)+4 种基金the National Foreign Experts Program(Grant No.Y20240022,H20240275)the Hubei Natural Science Foundation(Grant No.2025AFB460)the Hubei Provincial Department of Education Scientific Research Project(Grant No.F2023033,Q20234414)the Wuhan Natural Science Foundation Exploration Project(Chenguang Program)(Grant No.2025040601020173)the Jianghan University Scientific Research Startup Fund(Grant No.PBSKL-2022-QD-08,No.PBSKL-2024-QD-03).
文摘As a prototypical high-energy-density reactive material system,metastable intermolecular composites(MICs)have attracted considerable interest owing to their customizable component configurations and interfacial architectures.Nevertheless,their energy release characteristics are fundamentally constrained by the formation of condensed-phase products with elevated boiling points,thereby diminishing their efficacy in applications requiring rapid pressure generation or shock wave propagation.Herein,we demonstrate a molecular-level fluorination approach that enables oxygen substitution by fluorine within bismuth oxide crystalline frameworks,yielding ternary BixOyFz crystals with atomically precise F/O stoichiometric control through systematic solvent polarity engineering.This energetics system,designed through a multilevel regulation strategy,realizes stepwise redox reactions of Al–F and Al–O during energy release,with the partitioning between these redox pathways being precisely allocable through hierarchical regulation.Furthermore,the pre-ignition reaction(PIR)between BixOyFz and Al2O3(the inert passivation shell of Al)weakens the passivation layer,lowering the ignition threshold.The in situ generation of low-boiling-point AlF3 promotes rapid gas expansion,leading to significantly enhanced pressurization rates and deflagration wave velocities under confinement compared to conventional strategies.To evaluate energy output capabilities and validate potential safety-protection applications,the system successfully achieved instantaneous destruction of SD chips,enabling secure data erasure.This work establishes crystalline lattice fluorination as a generalized materials design strategy to transcend intrinsic limitations of MICs systems in component selection and reaction thermodynamics,providing new paradigms for adaptive energetic architectures and transient microelectromechanical applications.
基金supported by the National Natural Science Foundation of China(NFSC No.22122805,U21A20310,22075090,and 22278164)the Science and Technology Program of Guangzhou,China(No.2024A04J1540)。
文摘A strong built-in electric field(V_(bi))is the key to achieving rapid separation of photogenerated carriers in perovskite solar cells.This is particularly important for hole transport layer(HTL)free carbon-based perovskite solar cells(C-PSCs),which have a large interface energy level mismatch.The regulation of perovslite's surface energetics is an effective way to improve the V_(bi)and promote charge extraction,which is typically achieved by organic molecules.However,the insulating nature of organic molecules also negatively hinders charge transfer,resulting in a contradiction of"extraction-transport".Quantum dots(Q.Ds)have great potential for energetics regulation of perovskite film due to their semiconductor properties and inherent large dipole moments,but have not yet been explored.In this work,we propose a strategy of discrete embedding semiconductor QDs at the surface grain boundaries of the perovskite film to regulate surface energetics.The QDs change the energetics of the perovskite film surface,transforming the surface energetics from n-to p-type,thus constructing p-n homojunction at the interface.This significantly enhances the Vbi at the perovskite/carbon electrode interface,promoting hole extraction.In addition,the embedded discrete distribution of QDs at the upper surface grain boundaries ensures efficient transport of the extracted holes to the carbon electrode,overcoming the contradiction of"extraction-transport"for traditional energetics control strategies.Consequently,the fabricated planar HTL-free C-PSCs achieve an efficiency of 20.10%(certified 19.8%),which is one of the highest values reported for this kind of device.
基金supported by the National Natural Science Foundation of China(No.41876015)。
文摘Ocean mixing is a consequence of essential dynamic processes such as internal tides and lee waves that occur near the seafloor topography.Internal tides and lee waves are generated by barotropic tidal currents and geostrophic flows,respectively.Ocean current is composed of multiple flows;thus,internal tides and lee waves occur concurrently in the real ocean.In this paper,the Massachusetts Institute of Technology general circulation model(MITgcm)is used to conduct 2D numerical experiments.By varying background flow intensities,the energy and dissipation relationship between internal tides and lee waves are investigated.The results reveal that the internal tide beams become asymmetric due to the influence of Doppler shift.The lee wave structure gradually leads the wave field when the background flow velocity rises constantly.The presence of a background flow increases the energy portion of the high-mode wave by up to 15%-20%.Moreover,strong shear,owing to the background flow,considerably increases dissipation.When the background flow velocity is higher than the barotropic tidal current velocity,the isopycnal overturn triggered by the lee wave generates a dissipation of the same order of magnitude as the shear.
基金supported by the National Natural Science Foundation of China (21573232, 21576251, 21676269)National Key Projects for Funda-mental Research and Development of China (2016YFA0202801)Department of Science and Technology of Liaoning province under contract of 2015020086–101~~
文摘The formations and transformations of the chemical bonds of reactants and intermediates on cata- lyst surfaces occur in conjunction with the evolution of heat during catalytic reactions. Measure- ment of this evolved heat is helpful in terms of understanding the nature of the interactions be- tween the catalyst and the adsorbed species, and provides insights into the reactivity of the catalyst. Although various techniques have previously been applied to assessments of evolved heat, direct measurements using a Tian-Calvet microcalorimeter are currently the most reliable method for this purpose. In this review, we summarize the relationship between the adsorption/reaction energetics determined by microcalorimetry and the reactivities of supported catalysts, and examine the im- portant role of microcalorimetry in understanding catalytic performance from the energetic point of view.
文摘高效准确的机器学习模型是高通量筛选优质含能分子的基础,为此设计了完全通过结构式便可输出多项含能材料性质的多输入多输出机器学习模型(MIMO-ML)。基于478个含能分子数据集进行模型构建,通过筛选得到AMID_h、ATTS1are、OB三个优秀描述符,并在此基础上建立了自定义描述符集。结果表明,随机森林(RF)及多层感知机(MLP)适合被应用于含能材料性能预测多输出模型构建,输出性质包括爆速D(MAE=256 m/s),热分解温度T_(d)(MAE=34.7℃),撞击感度ln H 50(MAE=0.63)。同时,MLP模型相比于RF模型对于特征数量更敏感,且利用更少的特征可得到与RF精度相似的模型,表明MIMO-ML模型能够快速且准确地识别高性能含能材料,可应用于含能分子的设计与快速筛选。
文摘he characteristic study,by means of in-situ IR spectroscopy, of chemisorbed species on the Ni-catalysts for the partial oxidation of methane(POM)to syngas demonstrated the existence of CH_x(a)and H_xCO(a)adspecies on the functioning Ni-catalysts, Several designed experimental investigations on the reactivities of methane with CO_2 and with O_2,respectively,over the Ni-catalysts, and of CO_2 with the prereduced Ni-catalyst,ats well as of the deposited carbon with CO_2 and with O_2,respectlvely,liave been carried out and the reLqults were unfavorable to the two-step mechanistic interpretation proposed for the POM reaction. By means of tlie BOC-MP Approach,energetics of a set of elementary reactions,which may be involved in the POM process,on the clean(111)surface of Ni,Fe,Cu and Pd, re- spectively,has been studied.The result;of the experiments and the calculation of the present work favor the direct catalytic dissociation-plus-surface oxidation-plus-further debdrogenation mechanism as the dominant pathway making major contribution to the POM reaction.
