Solid-aqueous interfaces and phenomena occurring at those interfaces are ubiquitously found in a plethora of chemical systems.When it comes to heterogeneous catalysis,however,our understanding of chemical transformati...Solid-aqueous interfaces and phenomena occurring at those interfaces are ubiquitously found in a plethora of chemical systems.When it comes to heterogeneous catalysis,however,our understanding of chemical transformations at solid-aqueous interfaces is relatively limited and primitive.This review phenomenologically describes a selection of water-engendered effects on the catalytic behavior for several prototypical acid-base-catalyzed reactions over solid catalysts,and critically assesses the general and special roles of water molecules,structural moieties derived from water,and ionic species that are dissolved in it,with an aim to extract novel concepts and principles that underpin heterogeneous acid-base catalysis in the aqueous phase.For alcohol dehydration catalyzed by solid Bronsted acids,rate inhibition by water is most typically related to the decrease in the acid strength and/or the preferential solvation of adsorbed species over the transition state as water molecules progressively solvate the acid site and form extended networks wherein protons are mobilized.Water also inhibits dehydration kinetics over most Lewis acid-base catalysts by competitive adsorption,but a few scattered reports reveal substantial rate enhancements due to the conversion of Lewis acid sites to Brønsted acid sites with higher catalytic activities upon the introduction of water.For aldol condensation on catalysts exposing Lewis acid-base pairs,the addition of water is generally observed to enhance the rate when C–C coupling is rate-limiting,but may result in rate inhibition by site-blocking when the initial unimolecular deprotonation is rate-limiting.Water can also promote aldol condensation on Brønsted acidic catalysts by facilitating inter-site communication between acid sites through hydrogen-bonding interactions.For metallozeolite-catalyzed sugar isomerization in aqueous media,the nucleation and networking of intrapore waters regulated by hydrophilic entities causes characteristic enthalpy-entropy tradeoffs as these water moieties interact with kinetically relevant hydride transfer transition states.The discussed examples collectively highlight the utmost importance of hydrogen-bonding interactions and ionization of covalently bonded surface moieties as the main factors underlying the uniqueness of water-mediated interfacial acid-base chemistries and the associated solvation effects in the aqueous phase or in the presence of water.A perspective is also provided for future research in this vibrant field.展开更多
The membrane method based on adaptive wettability shows great advantages in oil-water separation.At present,researches focus on the excellent application performance of the membrane material,while the quantitative ana...The membrane method based on adaptive wettability shows great advantages in oil-water separation.At present,researches focus on the excellent application performance of the membrane material,while the quantitative analysis of interactions in oil-water separation is rarely recognized.Herein,we constructed an adaptable wettability membrane with multiple polymer networks by polydopamine(PDA)and mussel-inspired amphiphilic polymer.Based on the Owens three-probe liquid method,the surface energy of the modified membrane was verified to meet the adaptive wettability conditions,with surface energies(γ-8)of 147.6 mJ m^(−2)(superhydrophilic/underwater superoleophobic)and 49.87 mJ m^(−2)(superhydrophobic/superoleophobic),respectively.The adhesion or repulsion of the membrane to the oil phase under different conditions during the separation process was quantified by the chemical probe AFM technique.In addition,the oil-water selective separation mechanism was further analyzed in a simplified membrane microchannel model.The results show that the different wetting produces capillary additional pressure in opposite directions,resulting in different energies to be overcome when the oil or water passes through the microchannels,thus achieving selective separation.展开更多
Due to the fact that ballastless tracks in highspeed railways are not only subjected to repeated train–track dynamic interaction loads,but also suffer from complex environmental loads,the fundamental understanding of...Due to the fact that ballastless tracks in highspeed railways are not only subjected to repeated train–track dynamic interaction loads,but also suffer from complex environmental loads,the fundamental understanding of mechanical performance of ballastless tracks under sophisticated service conditions is an increasingly demanding and challenging issue in high-speed railway networks.This work aims to reveal the effect of train–track interaction and environment loads on the mechanical characteristic variation of ballastless tracks in high-speed railways,particularly focusing on the typical interface damage evolution between track layers.To this end,a finite element model of a double-block ballastless track involving the cohesive zone model for the track interface is first established to analyze the mechanical properties of the track interface under the loading–unloading processes of the negative temperature gradient load(TGL)followed by the same cycle of the positive TGL.Subsequently,the effect of wheel–rail longitudinal interactions on the nonlinear dynamic characteristics of the track interface is investigated by using a vehicle-slab track vertical-longitudinal coupled dynamics model.Finally,the influence of dynamic water pressure induced by vehicle dynamic load on the mechanical characteristics and damage evolution of the track interface is elucidated using a fluid–solid coupling method.Results show that the loading history of the positive and negative TGLs has a great impact on the nonlinear development and distribution of the track interface stress and damage;the interface damage could be induced by the wheel–rail longitudinal vibrations at a high vehicle running speed owing to the dynamic amplification effect caused by short wave irregularities;the vehicle dynamic load could produce considerable water pressure that presents nonlinear spatial–temporal characteristics at the track interface,which would lead to the interface failure under a certain condition due to the coupled dynamic effect of vehicle load and water pressure.展开更多
The influence of pH on the partitioning behavior of REE at the water/particulate interface has been studied experimentally. At the beginning of colloid formation the adsorption of REE on iron hydroxide colloids is dom...The influence of pH on the partitioning behavior of REE at the water/particulate interface has been studied experimentally. At the beginning of colloid formation the adsorption of REE on iron hydroxide colloids is dominant, followed by REE desorption. Finally adsorption and desorption tend to reach equilibration. The capability of iron hydroxide colloids to adsorb the HREE is greater than that to adsorb the LREE. With increasing pH, LREE/HREE fractionations will take place between iron hydroxide colloids and water, leading to the reduction of their partition coefficient ratio (DLREE/DHREE). The DREE distribution patterns show Y anomalies (DY/DHo <1), with obvious REE tetrad effects appearing under low pH conditions. Experimental results have shown that there do exist REE tetrad effects in nature. In addition to pH, the chemical type of surface water and ion intensity are also the important factors controlling REE tetrad effects and leading to fractionations between particulate-adsorbed REE and dissolved REE.展开更多
文摘Solid-aqueous interfaces and phenomena occurring at those interfaces are ubiquitously found in a plethora of chemical systems.When it comes to heterogeneous catalysis,however,our understanding of chemical transformations at solid-aqueous interfaces is relatively limited and primitive.This review phenomenologically describes a selection of water-engendered effects on the catalytic behavior for several prototypical acid-base-catalyzed reactions over solid catalysts,and critically assesses the general and special roles of water molecules,structural moieties derived from water,and ionic species that are dissolved in it,with an aim to extract novel concepts and principles that underpin heterogeneous acid-base catalysis in the aqueous phase.For alcohol dehydration catalyzed by solid Bronsted acids,rate inhibition by water is most typically related to the decrease in the acid strength and/or the preferential solvation of adsorbed species over the transition state as water molecules progressively solvate the acid site and form extended networks wherein protons are mobilized.Water also inhibits dehydration kinetics over most Lewis acid-base catalysts by competitive adsorption,but a few scattered reports reveal substantial rate enhancements due to the conversion of Lewis acid sites to Brønsted acid sites with higher catalytic activities upon the introduction of water.For aldol condensation on catalysts exposing Lewis acid-base pairs,the addition of water is generally observed to enhance the rate when C–C coupling is rate-limiting,but may result in rate inhibition by site-blocking when the initial unimolecular deprotonation is rate-limiting.Water can also promote aldol condensation on Brønsted acidic catalysts by facilitating inter-site communication between acid sites through hydrogen-bonding interactions.For metallozeolite-catalyzed sugar isomerization in aqueous media,the nucleation and networking of intrapore waters regulated by hydrophilic entities causes characteristic enthalpy-entropy tradeoffs as these water moieties interact with kinetically relevant hydride transfer transition states.The discussed examples collectively highlight the utmost importance of hydrogen-bonding interactions and ionization of covalently bonded surface moieties as the main factors underlying the uniqueness of water-mediated interfacial acid-base chemistries and the associated solvation effects in the aqueous phase or in the presence of water.A perspective is also provided for future research in this vibrant field.
基金We gratefully acknowledge the financial support from National Key Research and Development Project,China(2019YFA0708700)the National Natural Science Foundation of China(52222403,52074333)the Innovation Fund Project for graduate students of China University of Petroleum(East China)(22CX04049A).
文摘The membrane method based on adaptive wettability shows great advantages in oil-water separation.At present,researches focus on the excellent application performance of the membrane material,while the quantitative analysis of interactions in oil-water separation is rarely recognized.Herein,we constructed an adaptable wettability membrane with multiple polymer networks by polydopamine(PDA)and mussel-inspired amphiphilic polymer.Based on the Owens three-probe liquid method,the surface energy of the modified membrane was verified to meet the adaptive wettability conditions,with surface energies(γ-8)of 147.6 mJ m^(−2)(superhydrophilic/underwater superoleophobic)and 49.87 mJ m^(−2)(superhydrophobic/superoleophobic),respectively.The adhesion or repulsion of the membrane to the oil phase under different conditions during the separation process was quantified by the chemical probe AFM technique.In addition,the oil-water selective separation mechanism was further analyzed in a simplified membrane microchannel model.The results show that the different wetting produces capillary additional pressure in opposite directions,resulting in different energies to be overcome when the oil or water passes through the microchannels,thus achieving selective separation.
基金the National Natural Science Foundation of China(Nos.51708457,11790283,and 51978587)the Fund from State Key Laboratory of Traction Power(2019TPL-T16)+1 种基金the Young Elite Scientists Sponsorship Program by CAST(2018QNRC001)the 111 Project(Grant No.B16041)。
文摘Due to the fact that ballastless tracks in highspeed railways are not only subjected to repeated train–track dynamic interaction loads,but also suffer from complex environmental loads,the fundamental understanding of mechanical performance of ballastless tracks under sophisticated service conditions is an increasingly demanding and challenging issue in high-speed railway networks.This work aims to reveal the effect of train–track interaction and environment loads on the mechanical characteristic variation of ballastless tracks in high-speed railways,particularly focusing on the typical interface damage evolution between track layers.To this end,a finite element model of a double-block ballastless track involving the cohesive zone model for the track interface is first established to analyze the mechanical properties of the track interface under the loading–unloading processes of the negative temperature gradient load(TGL)followed by the same cycle of the positive TGL.Subsequently,the effect of wheel–rail longitudinal interactions on the nonlinear dynamic characteristics of the track interface is investigated by using a vehicle-slab track vertical-longitudinal coupled dynamics model.Finally,the influence of dynamic water pressure induced by vehicle dynamic load on the mechanical characteristics and damage evolution of the track interface is elucidated using a fluid–solid coupling method.Results show that the loading history of the positive and negative TGLs has a great impact on the nonlinear development and distribution of the track interface stress and damage;the interface damage could be induced by the wheel–rail longitudinal vibrations at a high vehicle running speed owing to the dynamic amplification effect caused by short wave irregularities;the vehicle dynamic load could produce considerable water pressure that presents nonlinear spatial–temporal characteristics at the track interface,which would lead to the interface failure under a certain condition due to the coupled dynamic effect of vehicle load and water pressure.
基金This work was supported by the State Outsanding Young Scientists Foundation (Grant No. 49625304) the Pre-selected Project under the State Climbing Program of China (Grant No. 95-39).
文摘The influence of pH on the partitioning behavior of REE at the water/particulate interface has been studied experimentally. At the beginning of colloid formation the adsorption of REE on iron hydroxide colloids is dominant, followed by REE desorption. Finally adsorption and desorption tend to reach equilibration. The capability of iron hydroxide colloids to adsorb the HREE is greater than that to adsorb the LREE. With increasing pH, LREE/HREE fractionations will take place between iron hydroxide colloids and water, leading to the reduction of their partition coefficient ratio (DLREE/DHREE). The DREE distribution patterns show Y anomalies (DY/DHo <1), with obvious REE tetrad effects appearing under low pH conditions. Experimental results have shown that there do exist REE tetrad effects in nature. In addition to pH, the chemical type of surface water and ion intensity are also the important factors controlling REE tetrad effects and leading to fractionations between particulate-adsorbed REE and dissolved REE.
