Soil hydraulic properties were mainly governed by soil structures especially when the structures is full of the connected soil macro-pores.Therefore,the good hydrological models need to be well documented for revealin...Soil hydraulic properties were mainly governed by soil structures especially when the structures is full of the connected soil macro-pores.Therefore,the good hydrological models need to be well documented for revealing the process of soil water movement affected by soil medium.The Hydrus-2D model with double domain was recommended in simulating water movement in a heterogeneous medium of soil.To evaluate the performance of the double domain Hydrus-2D model in loess soil,the dynamic of soil wetting front movement in differential loess soil columns under the constant water head were observed and the processes was simulated by Hydrus-2D model under conditions of different soil properties.The results indicated that the Hydrus-2D model was quite good in simulation of loess soil water movements,and the relative errors of simulation results are less than 15%,MRE less than 5%,and R^(2)>0.9.The results provided the appropriate infiltration parameters of loess soil.展开更多
The calcium chloride used for adsorption separation of ammonia is promising for its large adsorptive capacity and lower desorption temperature,but difficult to develop because of the liable expansion,lump and chip in ...The calcium chloride used for adsorption separation of ammonia is promising for its large adsorptive capacity and lower desorption temperature,but difficult to develop because of the liable expansion,lump and chip in the adsorption/desorption process.Composite adsorbents made by monolayer dis-persion of calcium chloride onto carriers with high surface areas exhibit better adsorptive capacity and stability.Several models were developed to confirm the maximum monolayer dispersion capacity of calcium chloride onto the carriers(the distribution threshold value),and the closely packed monolayer dispersion model was considered the most suitable for this study.The distribution threshold values given by this model were 0.60 g CaCl2/(g 10X-zeolite) and 0.38 g CaCl2/(g SiO2).When the divalent salt was dispersed onto the carriers,however,anions were separated into two types,causing that the en-tropy of the system tended to increase and the system was not stable.To minimize the entropy,a new model was put forward as the modified closely packed monolayer dispersion model.Based on this model,the distribution threshold values are 0.52 g CaCl2/(g 10X-zeolite) and 0.33 g CaCl2/(g SiO2),re-spectively.The distribution threshold values were also gained experimentally by XRD quantitative phase analysis:0.61 g CaCl2/(g 10X-zeolite) and 0.31 g CaCl2/(g SiO2).Comparison between experi-mental values of distribution threshold with theoretical ones based on two different model showed that the closely packed monolayer dispersion model fits the monolayer dispersion of calcium chloride onto micro-pore carrier - 10X-zeolite,and the modified closely packed monolayer dispersion model is more suitable for the bigger aperture carrier - macro-pore silica gel.展开更多
Optimizing active sites and enhancing mass transfer capability are of paramount importance for the improvement of electrocatalyst activity.On this basis,CoFe_(2)O_(4)/CoFe nanoparticles(NPs)loaded N-doped carbon(NC)th...Optimizing active sites and enhancing mass transfer capability are of paramount importance for the improvement of electrocatalyst activity.On this basis,CoFe_(2)O_(4)/CoFe nanoparticles(NPs)loaded N-doped carbon(NC)that featured with interconnected three-dimensional(3D)ordered porous hierarchies(3DOM FeCo/NC)are prepared,and its electrocatalytic activity is studied.Due to the open structure of 3D ordered macro-pores that greatly improves the mass transfer capacity of the catalytic process and enhances the utilization of active sites inside the catalyst,as well as the uniform distribution of Fe and Co bimetallic sites on the porous skeleton,3DOM FeCo/NC exhibits superior bi-functional catalytic activities for both hydrogen evolution reaction(HER)and oxygen reduction reaction(ORR).The overpotential of HER is lower than that of commercial Pt/C when performed at high current density(>235 mA cm^(-2))in1.0 M KOH,and the half-wave potential(0.896 V)of ORR in 0.1 M KOH is also superior to that of 20% commercial Pt/C and most other similar catalysts.The effective utilization and synergistic effect of CoFe_(2)O_(4)and CoFe hetero-metallic sites remarkably enhance the electrocatalytic activity.Furthermore,3DOM FeCo/NC is assembled as an air electrode in Zn-air battery,and exhibits satisfactory maximum power density,open-circuit voltage,and charge/discharge stability over benchmark Pt/C+IrO_(2).This work contributes new insights into the design of transition-metal-based multifunctional catalysts,and has great potential for energy conversion and storage.展开更多
Three-dimensionally ordered macro-porous （3DOM） TiO2 and ceria-modified 3DOM TiO2 supported platinum catalysts were prepared with template and impregnation methods, and the resultant samples were characterized by sc...Three-dimensionally ordered macro-porous （3DOM） TiO2 and ceria-modified 3DOM TiO2 supported platinum catalysts were prepared with template and impregnation methods, and the resultant samples were characterized by scanning electron microscopy（SEM）, X-ray diffractometer（XRD）, high-resolution transmission electron microscopy（HRTEM） and temperature programmed reducfion（TPR） techniques. The catalytic performances over the platinum-based catalysts were investigated for water-gas shift （WGS） reaction in a wide temperature range （180-360 ℃）. The results showed that 3DOM Pt/TiO2 catalyst exhibited obviously better catalytic performance than the corresponding non macro-porous catalyst, owing to the macro-porous structure favoring mass transfer. Addition of celia into 3DOM Pt/TiO2 led to improvement of catalytic activity. TPR and HRTEM results showed that the interaction existed between ceria and titanium oxide and addition of ceria promoted the reducibility of platinum oxide and TiO2 on the interface of platinum and TiO2 particles, which contributed to high activity of the celia modified catalysts. The results indicated that ceria-modified 3DOM Pt/TiO2 was a promising candidate of fuel cell oriented WGS catalyst.展开更多
Single metal atoms immobilized on a carbon substrate are of great potential for enhancing the catalytic activities for oxygen reduction and methanol oxidation reactions(ORR/MOR)owing to the maximized atom utilization....Single metal atoms immobilized on a carbon substrate are of great potential for enhancing the catalytic activities for oxygen reduction and methanol oxidation reactions(ORR/MOR)owing to the maximized atom utilization.Herein,single copper atoms(SCAs)are loaded on macro-porous nitrogen-doped carbon(Cu-NC)derived from zeolitic imidazolate framework-8(ZIF-8),which are used as catalysts for ORR and Pt-supports for MOR.For ORR,the catalyst marked as Cu-NC-3 exhibits a higher peak potential of 0.87 V(vs.Reversible hydrogen electrode)than that of commercial Pt/C(0.83 V),mainly attributing to that the 3D macro-porous structure of Cu-NC-3 provides adequate space for uniform dispersion of SCAs as the main active species,and smooth diffusion pathways for fast transport of substances(O_(2),H_(2)O),therefore reducing the overpotential and the intermediate(H_(2)O_(2))generation to enhance ORR activity.For MOR,Pt-Cu-NC-3 has a higher mass activity of 1217.4 mA/mg Pt than that of Pt/C(752.4 mA/mg Pt),and its activity maintenance(decline of 27.6%)is also better than Pt/C(decline of 44.0%)after 5000 cyclic voltammetry(CV)cycles.The interactions between SCAs and Pt nanoparticles should facilitate the generation of OH−from water molecules,which can fast eliminate the adsorbed CO to recover the Pt active sites to improve MOR performance.This synthesis strategy affords a new inspiration to prepare single metal atoms loaded on ZIFs-derived macro-structure with diverse activities for ORR/MOR.展开更多
A β-zeolite/polystyrene composite material was synthesized by co-deposition of mono-disperse polystyrene spheres and nano β-zeolite particles in aqueous suspension on a vertical substrate. Macro-porous β-zeolite wa...A β-zeolite/polystyrene composite material was synthesized by co-deposition of mono-disperse polystyrene spheres and nano β-zeolite particles in aqueous suspension on a vertical substrate. Macro-porous β-zeolite was obtained after the polystyrene template was removed by calcination. The micro/macro-pore structure of the prepared β-zeolite was highly ordered. In comparison with other assembly methods, the co-deposition method could obtain a highly ordered macro-porous material with relatively large zeolite filling particles, and therefore the co-deposition of particles with different size is a promising method for the fabrication of macro-porous materials.展开更多
Three-dimensionally ordered macro-porous （3DOM） Pt/TiO2 catalysts were prepared by template and impregnation methods, and the resultant samples were characterized by using TG-DTA, XRD, SEM, TEM, and TPR techniques. ...Three-dimensionally ordered macro-porous （3DOM） Pt/TiO2 catalysts were prepared by template and impregnation methods, and the resultant samples were characterized by using TG-DTA, XRD, SEM, TEM, and TPR techniques. The catalytic performance for water-gas shift （WGS） reaction was tested, and the influences of some conditions, such as reduction temperature of catalysts, the amount of Pt loadings and space velocity on catalytic performance were investigated. It was shown that Pt particles were homogeneously dispersed on 3DOM TiO2. The reduction of TiO2 surface was important for the catalytic performance. The activity test results showed that the 3DOM Pt/TiO2 catalysts exhibited very good catalytic performance for WGS reaction even at high space velocity, which was owing to the better mass transfer of 3DOM porous structure besides the high intrinsic activity of Pt/TiO2.展开更多
Considering the challenge of aerodynamic heating,the development of high-performance insulating ce-ramic materials with lightweight and low thermal conductivity is crucially important for aerospace vehi-cles to achiev...Considering the challenge of aerodynamic heating,the development of high-performance insulating ce-ramic materials with lightweight and low thermal conductivity is crucially important for aerospace vehi-cles to achieve flight at high speed for a long time.In this work,macro-porous silicon oxycarbide(SiOC)ceramics with directional pores(DP-SiOC)(mean pore size of 88.1μm)were prepared using polysiloxane precursors via freeze casting and photocrosslinking,followed by pyrolysis.The DP-SiOC samples were lightweight(density∼0.135 g cm^(-3))with a porosity of 90.4%,which showed good shapability through the molding of polysiloxane precursors.The DP-SiOC samples also exhibited an ultra-low thermal con-ductivity of 0.048 W(m K)^(-1)at room temperature,which can also withstand heat treatment at 1200°C for 1 h.In addition,scaffolds with triply periodic minimal surfaces(TPMS)were fabricated using digital light processing(DLP)printing,which was further filled with polysiloxane precursors for increasing the strength of DP-SiOC.The TPMS scaffolds filled with macro-porous SiOC ceramics(TPMS-DP-SiOC)showed good integration between TPMS and macro-pore structures,which had a porosity∼75%and high specific strength of 9.73×10^(3)N m kg^(-1).The thermal conductivity of TPMS-DP-SiOC samples was 0.255 W(m K)^(-1)at room temperature.The biomimetic TPMS-DP-SiOC ceramics developed in this study are likely used for thermal protection systems.展开更多
基金This study was funded by the National Natural Science Foundation of China(41471439,41171421)Chinese Academy of Sciences Visiting Professorships for Senior International Scientists(serial number:2013T2Z0027).
文摘Soil hydraulic properties were mainly governed by soil structures especially when the structures is full of the connected soil macro-pores.Therefore,the good hydrological models need to be well documented for revealing the process of soil water movement affected by soil medium.The Hydrus-2D model with double domain was recommended in simulating water movement in a heterogeneous medium of soil.To evaluate the performance of the double domain Hydrus-2D model in loess soil,the dynamic of soil wetting front movement in differential loess soil columns under the constant water head were observed and the processes was simulated by Hydrus-2D model under conditions of different soil properties.The results indicated that the Hydrus-2D model was quite good in simulation of loess soil water movements,and the relative errors of simulation results are less than 15%,MRE less than 5%,and R^(2)>0.9.The results provided the appropriate infiltration parameters of loess soil.
基金Supported by the National Natural Science Foundation of China (Grant No. 20576080)
文摘The calcium chloride used for adsorption separation of ammonia is promising for its large adsorptive capacity and lower desorption temperature,but difficult to develop because of the liable expansion,lump and chip in the adsorption/desorption process.Composite adsorbents made by monolayer dis-persion of calcium chloride onto carriers with high surface areas exhibit better adsorptive capacity and stability.Several models were developed to confirm the maximum monolayer dispersion capacity of calcium chloride onto the carriers(the distribution threshold value),and the closely packed monolayer dispersion model was considered the most suitable for this study.The distribution threshold values given by this model were 0.60 g CaCl2/(g 10X-zeolite) and 0.38 g CaCl2/(g SiO2).When the divalent salt was dispersed onto the carriers,however,anions were separated into two types,causing that the en-tropy of the system tended to increase and the system was not stable.To minimize the entropy,a new model was put forward as the modified closely packed monolayer dispersion model.Based on this model,the distribution threshold values are 0.52 g CaCl2/(g 10X-zeolite) and 0.33 g CaCl2/(g SiO2),re-spectively.The distribution threshold values were also gained experimentally by XRD quantitative phase analysis:0.61 g CaCl2/(g 10X-zeolite) and 0.31 g CaCl2/(g SiO2).Comparison between experi-mental values of distribution threshold with theoretical ones based on two different model showed that the closely packed monolayer dispersion model fits the monolayer dispersion of calcium chloride onto micro-pore carrier - 10X-zeolite,and the modified closely packed monolayer dispersion model is more suitable for the bigger aperture carrier - macro-pore silica gel.
基金financially supported by the National Natural Science Foundation of China(51902149,51674131,22305108)the Fundamental Research Funds for Public Universities in Liaoning(LJ232410140033)the Scientific Research Funding of the Education Department of Liaoning Province(JYTZD2023070,LJKFZ20220180,LJKMZ20220453)。
文摘Optimizing active sites and enhancing mass transfer capability are of paramount importance for the improvement of electrocatalyst activity.On this basis,CoFe_(2)O_(4)/CoFe nanoparticles(NPs)loaded N-doped carbon(NC)that featured with interconnected three-dimensional(3D)ordered porous hierarchies(3DOM FeCo/NC)are prepared,and its electrocatalytic activity is studied.Due to the open structure of 3D ordered macro-pores that greatly improves the mass transfer capacity of the catalytic process and enhances the utilization of active sites inside the catalyst,as well as the uniform distribution of Fe and Co bimetallic sites on the porous skeleton,3DOM FeCo/NC exhibits superior bi-functional catalytic activities for both hydrogen evolution reaction(HER)and oxygen reduction reaction(ORR).The overpotential of HER is lower than that of commercial Pt/C when performed at high current density(>235 mA cm^(-2))in1.0 M KOH,and the half-wave potential(0.896 V)of ORR in 0.1 M KOH is also superior to that of 20% commercial Pt/C and most other similar catalysts.The effective utilization and synergistic effect of CoFe_(2)O_(4)and CoFe hetero-metallic sites remarkably enhance the electrocatalytic activity.Furthermore,3DOM FeCo/NC is assembled as an air electrode in Zn-air battery,and exhibits satisfactory maximum power density,open-circuit voltage,and charge/discharge stability over benchmark Pt/C+IrO_(2).This work contributes new insights into the design of transition-metal-based multifunctional catalysts,and has great potential for energy conversion and storage.
基金supported by the Ministry of Sciences and Technology of China (863 Programs) (2006AA05Z115, 2007AA05Z104)
文摘Three-dimensionally ordered macro-porous （3DOM） TiO2 and ceria-modified 3DOM TiO2 supported platinum catalysts were prepared with template and impregnation methods, and the resultant samples were characterized by scanning electron microscopy（SEM）, X-ray diffractometer（XRD）, high-resolution transmission electron microscopy（HRTEM） and temperature programmed reducfion（TPR） techniques. The catalytic performances over the platinum-based catalysts were investigated for water-gas shift （WGS） reaction in a wide temperature range （180-360 ℃）. The results showed that 3DOM Pt/TiO2 catalyst exhibited obviously better catalytic performance than the corresponding non macro-porous catalyst, owing to the macro-porous structure favoring mass transfer. Addition of celia into 3DOM Pt/TiO2 led to improvement of catalytic activity. TPR and HRTEM results showed that the interaction existed between ceria and titanium oxide and addition of ceria promoted the reducibility of platinum oxide and TiO2 on the interface of platinum and TiO2 particles, which contributed to high activity of the celia modified catalysts. The results indicated that ceria-modified 3DOM Pt/TiO2 was a promising candidate of fuel cell oriented WGS catalyst.
基金support by the National Natural Science Foundation of China(Nos.52070074,21806031 and 51578218)Longjiang Scholars Program(No.Q201912)the Open Project of State Key Laboratory of Urban Water Resource and Environment,Harbin Institute of Technology(No.HC202144).
文摘Single metal atoms immobilized on a carbon substrate are of great potential for enhancing the catalytic activities for oxygen reduction and methanol oxidation reactions(ORR/MOR)owing to the maximized atom utilization.Herein,single copper atoms(SCAs)are loaded on macro-porous nitrogen-doped carbon(Cu-NC)derived from zeolitic imidazolate framework-8(ZIF-8),which are used as catalysts for ORR and Pt-supports for MOR.For ORR,the catalyst marked as Cu-NC-3 exhibits a higher peak potential of 0.87 V(vs.Reversible hydrogen electrode)than that of commercial Pt/C(0.83 V),mainly attributing to that the 3D macro-porous structure of Cu-NC-3 provides adequate space for uniform dispersion of SCAs as the main active species,and smooth diffusion pathways for fast transport of substances(O_(2),H_(2)O),therefore reducing the overpotential and the intermediate(H_(2)O_(2))generation to enhance ORR activity.For MOR,Pt-Cu-NC-3 has a higher mass activity of 1217.4 mA/mg Pt than that of Pt/C(752.4 mA/mg Pt),and its activity maintenance(decline of 27.6%)is also better than Pt/C(decline of 44.0%)after 5000 cyclic voltammetry(CV)cycles.The interactions between SCAs and Pt nanoparticles should facilitate the generation of OH−from water molecules,which can fast eliminate the adsorbed CO to recover the Pt active sites to improve MOR performance.This synthesis strategy affords a new inspiration to prepare single metal atoms loaded on ZIFs-derived macro-structure with diverse activities for ORR/MOR.
基金the National Basic Research Program of China （No. 2004CB217808） the National Natural Science Foundation of China （No. 20376046）.
文摘A β-zeolite/polystyrene composite material was synthesized by co-deposition of mono-disperse polystyrene spheres and nano β-zeolite particles in aqueous suspension on a vertical substrate. Macro-porous β-zeolite was obtained after the polystyrene template was removed by calcination. The micro/macro-pore structure of the prepared β-zeolite was highly ordered. In comparison with other assembly methods, the co-deposition method could obtain a highly ordered macro-porous material with relatively large zeolite filling particles, and therefore the co-deposition of particles with different size is a promising method for the fabrication of macro-porous materials.
基金supported by the Ministry of Sciences and Technology of China(863 programs,No 2006AA05Z115 and 2007AA05Z104)
文摘Three-dimensionally ordered macro-porous （3DOM） Pt/TiO2 catalysts were prepared by template and impregnation methods, and the resultant samples were characterized by using TG-DTA, XRD, SEM, TEM, and TPR techniques. The catalytic performance for water-gas shift （WGS） reaction was tested, and the influences of some conditions, such as reduction temperature of catalysts, the amount of Pt loadings and space velocity on catalytic performance were investigated. It was shown that Pt particles were homogeneously dispersed on 3DOM TiO2. The reduction of TiO2 surface was important for the catalytic performance. The activity test results showed that the 3DOM Pt/TiO2 catalysts exhibited very good catalytic performance for WGS reaction even at high space velocity, which was owing to the better mass transfer of 3DOM porous structure besides the high intrinsic activity of Pt/TiO2.
基金supported by the CAS Interdisciplinary Innova-tion Team Project(No.JCTD-2020-10)of the Chinese Academy of SciencesChina and the Defense Industrial Technology Develop-ment Program(No.JCKY2021130B039).
文摘Considering the challenge of aerodynamic heating,the development of high-performance insulating ce-ramic materials with lightweight and low thermal conductivity is crucially important for aerospace vehi-cles to achieve flight at high speed for a long time.In this work,macro-porous silicon oxycarbide(SiOC)ceramics with directional pores(DP-SiOC)(mean pore size of 88.1μm)were prepared using polysiloxane precursors via freeze casting and photocrosslinking,followed by pyrolysis.The DP-SiOC samples were lightweight(density∼0.135 g cm^(-3))with a porosity of 90.4%,which showed good shapability through the molding of polysiloxane precursors.The DP-SiOC samples also exhibited an ultra-low thermal con-ductivity of 0.048 W(m K)^(-1)at room temperature,which can also withstand heat treatment at 1200°C for 1 h.In addition,scaffolds with triply periodic minimal surfaces(TPMS)were fabricated using digital light processing(DLP)printing,which was further filled with polysiloxane precursors for increasing the strength of DP-SiOC.The TPMS scaffolds filled with macro-porous SiOC ceramics(TPMS-DP-SiOC)showed good integration between TPMS and macro-pore structures,which had a porosity∼75%and high specific strength of 9.73×10^(3)N m kg^(-1).The thermal conductivity of TPMS-DP-SiOC samples was 0.255 W(m K)^(-1)at room temperature.The biomimetic TPMS-DP-SiOC ceramics developed in this study are likely used for thermal protection systems.
