By performing with density functional theory(DFT) method, the detailed adsorption process and the catalytic decarbonylation mechanisms of furfural over Pd(111) and M/Pd(111)(M = Ni, Cu, Ru) surfaces toward furan were ...By performing with density functional theory(DFT) method, the detailed adsorption process and the catalytic decarbonylation mechanisms of furfural over Pd(111) and M/Pd(111)(M = Ni, Cu, Ru) surfaces toward furan were clarified. The results of atomic size factor, formation energy and d-band center showed that Ru/Pd(111) surface was the most stable and active. The adsorption energies of furfural on the different surfaces followed the order Ru/Pd(111) > Cu/Pd(111) > Pd(111) > Ni/Pd(111). After analyzing Mulliken atomic charge population and the deformation density, we can find that on Ru/Pd(111) surface, the number of charge transfer was the most and the interaction was the strongest. Therefore, its adsorption energy was the highest. Furthermore, the furfural decarbonylation pathway is more kinetically feasible on bimetallic surface, and the reaction is the most likely to occur on Ru/Pd(111).展开更多
Three-dimensional graphene-based aerogels have promising applications in oil adsorption and environmental restoration.However,current research of graphene-based aerogels is often hindered by high preparation cost,poor...Three-dimensional graphene-based aerogels have promising applications in oil adsorption and environmental restoration.However,current research of graphene-based aerogels is often hindered by high preparation cost,poor mechanical properties and low recycling efficiency.Here,superelastic graphene aerogel(SGA)was prepared through one-step freezing and twice hydrothermal reduction followed by drying under ambient pressure.The simple atmospheric drying provides a possibility for large-scale preparation of high performance graphene-based aerogels.The prepared SGA not only has the ability of highly repeatable compression rebound,but also exhibits excellent oil adsorption performance.And the overall performance of SGA is better than most of graphenebased aerogels prepared by freeze drying.After the SGA was cyclically compressed with 70%strain for 300 times,it can return to the original shape and height substantially.SGA retained about 90%of the initial adsorption capacity after 50 cycles of adsorption and compression regeneration for cyclohexane.展开更多
The biomass valorization is of great importance as an alternative for the production of transport fuels and fine chemicals.Furfural hydrogenation to furfuryl alcohol is a prevailing industrial route for the utilizatio...The biomass valorization is of great importance as an alternative for the production of transport fuels and fine chemicals.Furfural hydrogenation to furfuryl alcohol is a prevailing industrial route for the utilization of hemicellulose component of biomass.The toxicity of the chromium species in commercial copper chromite catalyst for furfuryl alcohol production motivates the development of efficient chromium-free catalyst.Thus,a highly efficient silica supported copper catalyst is developed in this study.The catalyst is prepared by freeze drying of a gel precursor that is synthesized by ammonia evaporation,followed by calcination and H_(2)reduction.The catalyst exhibits higher furfural hydrogenation activity than oven dried catalyst,commercial copper chromite catalyst and a plant supplied commercial silica supported copper catalyst.The catalyst also shows good stability.The superior performance of the freeze dried catalyst has resulted from its developed pore structure and higher amount of Cu^(0)as well as Cu^(+)active sites.展开更多
The effect of drying techniques on the microstructure,morphology and pore structure of porous silica gels was studied in the paper.The gels were prepared by using sol-gel process and different drying routes:freeze-dry...The effect of drying techniques on the microstructure,morphology and pore structure of porous silica gels was studied in the paper.The gels were prepared by using sol-gel process and different drying routes:freeze-drying (FD),low pressure drying (LPD),high temperature drying (HTD) and chemical modification & ambient drying (CMD) techniques.Observation under pore distribution and structural properties showed that CMD technique leads to homogenous mesoporous silica material with specific surface area of 745 m2/g,and the average pore size around 20 nm,while LPD and HTD result in loosely packed particles with non-isotropic aggregation pattern.The specific surface areas of LPD and HTD samples are 419 and 513 m2/g respectively,and the pore size distribution of the samples are observed distributing widely in range of 10-100 nm.Freeze drying method is a new but prospective way to prepare mesoporous silica.The specific area of FD sample is around 500 m2/g.By the comparison for the properties of the gels,this paper wants to induce a further interest in finding a proper method to synthesize the porous silica gels for low price use.展开更多
Calcium fluoride(CaF_(2))is an ideal adsorbent for the dehydration of gaseous hydrogen fluoride(HF)containing water vapor.In this work,a novel CaF_(2)absorbent,spherical CaF_(2)nanoaggregates(NAs)with a closely packed...Calcium fluoride(CaF_(2))is an ideal adsorbent for the dehydration of gaseous hydrogen fluoride(HF)containing water vapor.In this work,a novel CaF_(2)absorbent,spherical CaF_(2)nanoaggregates(NAs)with a closely packed structure,was proposed and efficiently fabricated by spray drying technology.As the building blocks of CaF_(2)NAs,the CaF_(2)nanoparticles(NPs)were prepared by the addition of excess calcium ions(Ca^(2+))or fluorine ions(F−)in the synthesis.The results indicated that the CaF_(2)NPs synthesized by excess Ca^(2+)and the corresponding NAs exhibited much better water vapor adsorption properties than their counterparts by excess F−,owing to higher zeta potentials.More importantly,whether excess Ca^(2+)or F^(−),CaF_(2)NAs had further enhanced water vapor adsorption capacity compared to primary CaF_(2)NPs,possibly owing to their unique nano-micro secondary structures and higher surface areas.This work has great potential in the development of high-performance absorbents for separating moisture from corrosive gas HF.展开更多
Combustion-generated hydrogen chloride （HCl） is considered to be a very hazardous acid gaseous pollutant. This paper presents a laboratory study on the dry adsorption of HCl. The experiments were conducted in a dual...Combustion-generated hydrogen chloride （HCl） is considered to be a very hazardous acid gaseous pollutant. This paper presents a laboratory study on the dry adsorption of HCl. The experiments were conducted in a dual-layer granular bed filter, at gas temperatures of 500℃-700℃ and n（Ca）/n（Cl）molar ratios of 1.0-5.0 using the silver nitrate titration method by dry adsorbent powders Ca（OH）2. Mainly, the adsorption efficiency of HCI and utilization efficiency of Calcium were studied, by varying relevant factors including n（Ca）/n（Cl）, tempera- ture, feeding method, water vapor and CO2. With a relatively higher HCl concentration of 1000ppm, the experimental results revealed that 600℃ may be the optimum temperature for HCl adsorption when optimum n （Ca）/n（Cl） was 2.5 in our tests. The results also demonstrated that the feeding at a constant pressure was more effective, and the HCl adsorption efficiency could rapidly reach over 90% with n（Ca）/n（Cl） = 2.5 at 600℃. Furthermore, the HCl adsorption efficiency was found to be slightly promoted by water vapor, while could be impeded by CO2, and the utilization efficiency of calcium could be up to 74.4% without CO2, while was only 36.8% with CO2 when n（Ca）/n（Cl） was 2.5 at 600℃.展开更多
Nano-pore carbon aerogels were prepared by the sol-gel polymerization of resorcinol (1,3-dihydroxybenzene)(C6H4(OH)2) with formaldehyde (HCHO) in a slightly basic aqueous solution, followed by super-critical drying un...Nano-pore carbon aerogels were prepared by the sol-gel polymerization of resorcinol (1,3-dihydroxybenzene)(C6H4(OH)2) with formaldehyde (HCHO) in a slightly basic aqueous solution, followed by super-critical drying under liquid carbon dioxide as super-critical media and carbonization at 700 ℃ under N2 gas atmosphere. The key of the work is to fabricate carbon aerogels with controllable nano-pore structure, which means extremely high surface area and sharp pore size distribution. Aiming to investigate the effects of preparation conditions on the gelation process, the bulk density, and the physical and chemical structure of the resultant carbon aerogels, the molar ratio of R/C (resorcinol to catalyst) and the amount of distilled water were varied, consequently two different sets of samples, with series of R/C ratio and RF/W (Resorcinol-Formaldehyde to water, or the content of reactant) ratio, were prepared. The result of N2 adsorption/desorption experiment at 77 K shows that the pore sizes decreasing from 11.4 down to 2.2 nm with the increasing of the molar ratio of R/C from 100 to 400, and/or, the pore sizes decreasing from 3.8 down to 1.6 nm with the increasing of reactant content from 0.4 to 0.6.展开更多
基金supported by the National Natural Science Foundation of China(No.21503188)
文摘By performing with density functional theory(DFT) method, the detailed adsorption process and the catalytic decarbonylation mechanisms of furfural over Pd(111) and M/Pd(111)(M = Ni, Cu, Ru) surfaces toward furan were clarified. The results of atomic size factor, formation energy and d-band center showed that Ru/Pd(111) surface was the most stable and active. The adsorption energies of furfural on the different surfaces followed the order Ru/Pd(111) > Cu/Pd(111) > Pd(111) > Ni/Pd(111). After analyzing Mulliken atomic charge population and the deformation density, we can find that on Ru/Pd(111) surface, the number of charge transfer was the most and the interaction was the strongest. Therefore, its adsorption energy was the highest. Furthermore, the furfural decarbonylation pathway is more kinetically feasible on bimetallic surface, and the reaction is the most likely to occur on Ru/Pd(111).
基金the financial support of National Natural Science Foundation of China (22078366)
文摘Three-dimensional graphene-based aerogels have promising applications in oil adsorption and environmental restoration.However,current research of graphene-based aerogels is often hindered by high preparation cost,poor mechanical properties and low recycling efficiency.Here,superelastic graphene aerogel(SGA)was prepared through one-step freezing and twice hydrothermal reduction followed by drying under ambient pressure.The simple atmospheric drying provides a possibility for large-scale preparation of high performance graphene-based aerogels.The prepared SGA not only has the ability of highly repeatable compression rebound,but also exhibits excellent oil adsorption performance.And the overall performance of SGA is better than most of graphenebased aerogels prepared by freeze drying.After the SGA was cyclically compressed with 70%strain for 300 times,it can return to the original shape and height substantially.SGA retained about 90%of the initial adsorption capacity after 50 cycles of adsorption and compression regeneration for cyclohexane.
基金supported by the National Natural Science Foundation of China (Nos.21721004,21808217,21932005)Natural Science Foundation of Liaoning Province (No.2020-MS-018)+1 种基金Dalian Young Star of Science and Technology Project (No.2020RQ023)Dalian Institute of Chemical Physics (Nos.DICP ZZBS201812,DICPI201936)。
文摘The biomass valorization is of great importance as an alternative for the production of transport fuels and fine chemicals.Furfural hydrogenation to furfuryl alcohol is a prevailing industrial route for the utilization of hemicellulose component of biomass.The toxicity of the chromium species in commercial copper chromite catalyst for furfuryl alcohol production motivates the development of efficient chromium-free catalyst.Thus,a highly efficient silica supported copper catalyst is developed in this study.The catalyst is prepared by freeze drying of a gel precursor that is synthesized by ammonia evaporation,followed by calcination and H_(2)reduction.The catalyst exhibits higher furfural hydrogenation activity than oven dried catalyst,commercial copper chromite catalyst and a plant supplied commercial silica supported copper catalyst.The catalyst also shows good stability.The superior performance of the freeze dried catalyst has resulted from its developed pore structure and higher amount of Cu^(0)as well as Cu^(+)active sites.
基金Sponsored by the National Mega-Project of Scientific & Technical Supporting Programs,Ministry of Science &Technology of China (Grant No.2006BAJ04A04)the Science Foundation of Liaoning Province,China (Grant No. 2008S190)
文摘The effect of drying techniques on the microstructure,morphology and pore structure of porous silica gels was studied in the paper.The gels were prepared by using sol-gel process and different drying routes:freeze-drying (FD),low pressure drying (LPD),high temperature drying (HTD) and chemical modification & ambient drying (CMD) techniques.Observation under pore distribution and structural properties showed that CMD technique leads to homogenous mesoporous silica material with specific surface area of 745 m2/g,and the average pore size around 20 nm,while LPD and HTD result in loosely packed particles with non-isotropic aggregation pattern.The specific surface areas of LPD and HTD samples are 419 and 513 m2/g respectively,and the pore size distribution of the samples are observed distributing widely in range of 10-100 nm.Freeze drying method is a new but prospective way to prepare mesoporous silica.The specific area of FD sample is around 500 m2/g.By the comparison for the properties of the gels,this paper wants to induce a further interest in finding a proper method to synthesize the porous silica gels for low price use.
基金supported by the National Key Research and Development Program of China(grant No.2021YFA1201301)the National Natural Science Foundation of China(grant No.22288102).
文摘Calcium fluoride(CaF_(2))is an ideal adsorbent for the dehydration of gaseous hydrogen fluoride(HF)containing water vapor.In this work,a novel CaF_(2)absorbent,spherical CaF_(2)nanoaggregates(NAs)with a closely packed structure,was proposed and efficiently fabricated by spray drying technology.As the building blocks of CaF_(2)NAs,the CaF_(2)nanoparticles(NPs)were prepared by the addition of excess calcium ions(Ca^(2+))or fluorine ions(F−)in the synthesis.The results indicated that the CaF_(2)NPs synthesized by excess Ca^(2+)and the corresponding NAs exhibited much better water vapor adsorption properties than their counterparts by excess F−,owing to higher zeta potentials.More importantly,whether excess Ca^(2+)or F^(−),CaF_(2)NAs had further enhanced water vapor adsorption capacity compared to primary CaF_(2)NPs,possibly owing to their unique nano-micro secondary structures and higher surface areas.This work has great potential in the development of high-performance absorbents for separating moisture from corrosive gas HF.
文摘Combustion-generated hydrogen chloride （HCl） is considered to be a very hazardous acid gaseous pollutant. This paper presents a laboratory study on the dry adsorption of HCl. The experiments were conducted in a dual-layer granular bed filter, at gas temperatures of 500℃-700℃ and n（Ca）/n（Cl）molar ratios of 1.0-5.0 using the silver nitrate titration method by dry adsorbent powders Ca（OH）2. Mainly, the adsorption efficiency of HCI and utilization efficiency of Calcium were studied, by varying relevant factors including n（Ca）/n（Cl）, tempera- ture, feeding method, water vapor and CO2. With a relatively higher HCl concentration of 1000ppm, the experimental results revealed that 600℃ may be the optimum temperature for HCl adsorption when optimum n （Ca）/n（Cl） was 2.5 in our tests. The results also demonstrated that the feeding at a constant pressure was more effective, and the HCl adsorption efficiency could rapidly reach over 90% with n（Ca）/n（Cl） = 2.5 at 600℃. Furthermore, the HCl adsorption efficiency was found to be slightly promoted by water vapor, while could be impeded by CO2, and the utilization efficiency of calcium could be up to 74.4% without CO2, while was only 36.8% with CO2 when n（Ca）/n（Cl） was 2.5 at 600℃.
基金This project was financially supported by a grant from the NITECH 21st Century COE Program, "World Ceramics Center for Environmental Harmony".
文摘Nano-pore carbon aerogels were prepared by the sol-gel polymerization of resorcinol (1,3-dihydroxybenzene)(C6H4(OH)2) with formaldehyde (HCHO) in a slightly basic aqueous solution, followed by super-critical drying under liquid carbon dioxide as super-critical media and carbonization at 700 ℃ under N2 gas atmosphere. The key of the work is to fabricate carbon aerogels with controllable nano-pore structure, which means extremely high surface area and sharp pore size distribution. Aiming to investigate the effects of preparation conditions on the gelation process, the bulk density, and the physical and chemical structure of the resultant carbon aerogels, the molar ratio of R/C (resorcinol to catalyst) and the amount of distilled water were varied, consequently two different sets of samples, with series of R/C ratio and RF/W (Resorcinol-Formaldehyde to water, or the content of reactant) ratio, were prepared. The result of N2 adsorption/desorption experiment at 77 K shows that the pore sizes decreasing from 11.4 down to 2.2 nm with the increasing of the molar ratio of R/C from 100 to 400, and/or, the pore sizes decreasing from 3.8 down to 1.6 nm with the increasing of reactant content from 0.4 to 0.6.
