Titanium phosphonate adsorbent materials with hierarchically porous structure were fabricated using the hydrolysis of tetrabutyl titanate in different organophosphonic acids solutions. Based on the macroporous structu...Titanium phosphonate adsorbent materials with hierarchically porous structure were fabricated using the hydrolysis of tetrabutyl titanate in different organophosphonic acids solutions. Based on the macroporous structure of 100-2000 nm in size, a worm-hole like mesostructure was in the macropore walls, which was supported by the scanning electron microscopy(SEM), transmission electron microscopy(TEM), and N2 sorption analysis. Fourier transform infrared spectroscopy(FT-IR) data indicated the organic groups inside the solid materials framework. NH3 adsorption detection was performed using titanium phosphonate adsorbent materials and some significant results were obtained. The adsorption mechanism was also discussed in this study. Large adsorption amount(75.2 mg/g) was mainly attributed to the acid site via acid-base reactions and the physical adsorption site via Van der Waals forces. Resultant materials could effectively restrain the desorption of adsorbent NH3 back into air causing secondary pollution, so it could make a promising potential use in decontamination of gas pollutants in the future.展开更多
The function-led design of porous hydrochar from mineral-rich biowaste for environmental applications inevitably suffers from carbon-ash recalcitrance.However,a method to alter the original carbon skeleton with ash re...The function-led design of porous hydrochar from mineral-rich biowaste for environmental applications inevitably suffers from carbon-ash recalcitrance.However,a method to alter the original carbon skeleton with ash remains elusive and hinders the availability of hydrochar.Herein,we propose a facile strategy for breaking the rigid structure of carbon-ash coupled hydrochar using phase-tunable molten carbonates.A case system was designed in which livestock manure and NaHCO3 were used to prepare the activated hydrochar,and NH3 served as the target contaminant.Due to the redox effect,we found that organic fractions significantly advanced the melting temperature of Na2CO3 below 800℃.The Na species steadily broke the carbon-ash interaction as the thermal intensity increased and transformed inorganic constituents to facilitate ash dissolution,rebuilding the hydrochar skeleton with abundant hierarchical channels and active defect edges.The surface polarity and mesopore distribution collectively governed the five cycles NH3 adsorption attenuation process.Manure hydrochar delivered favorable potential for application with a maximum overall adsorption capacity of 100.49 mg·g^(-1).Integrated spectroscopic characterization and theoretical computations revealed that incorporating NH3 on the carbon surface could transfer electrons to chemisorbed oxygen,which promoted the oxidation of pyridine-N during adsorption.This work offers deep insight into the structure function correlation of hydrochar and inspires a more rational design of engineered hydrochar from high-ash biowaste.展开更多
We put forward a new and ingenious method for the preparation of a new adsorbent by soaking, carbonizing and activating the mixture of hygroscopic salt and biomass material. The new adsorbent has high porosity, unifor...We put forward a new and ingenious method for the preparation of a new adsorbent by soaking, carbonizing and activating the mixture of hygroscopic salt and biomass material. The new adsorbent has high porosity, uniform distribution and high content of Ca Cl2, and exhibits high adsorption performance. The ammonia uptake and specific cooling power(SCP) at 5 min adsorption time can reach as high as 0.19 g·g^-1 and 793.9 W·kg^-1, respectively. The concept of utilizing the biomass materials and hygroscopic salts as raw materials for the preparation of adsorbents is of practical interest with respect to the potential quantity of biomass materials around the world, indicating that there would be a new market for biomass materials.Key words: biomass material; adsorption system; ammonia; calcium chloride; activated carbon展开更多
Metal-organic frameworks(MOFs)with inherent porosity and suspended acidic groups are promising proton conducting materials in water or aqua-ammonia media.Herein we report a new lanthanide phosphonate,namely,Dy_(2)(amp...Metal-organic frameworks(MOFs)with inherent porosity and suspended acidic groups are promising proton conducting materials in water or aqua-ammonia media.Herein we report a new lanthanide phosphonate,namely,Dy_(2)(amp_(2)H_(2))_(2)(mal)(H_(2)O)_(2)·5H2O(MDAF-6).It possesses a 3D open-framework structure,and shows a high NH_(3)adsorption capacity of 142.4 cm^(3)/g at P/P0=0.98 at 298 K due to acid-base interaction.Interestingly,the proton conductivity of MDAF-6-NH3 is enhanced by five orders of magnitude compared to MDAF-6 after 8.5 h exposure in saturated NH_(3)-H_(2)O vapor,indicating the importance of coexistent conjugate acid-base pairs of H_(3)O+-H_(2)O and NH_(4)^(+)-NH_(3)in promoting proton conduction.Magnetic studies of MDAF-6 revealed slow magnetization relaxation under zero dc field,characteristic of singlemolecule magnet behavior.This work provides not only a new multifunctional MOF material,but also a new strategy to improve proton conduction in aqua-ammonia medium.展开更多
A series of aluminumphosphate materials was prepared and used as adsorbents for the removal of ammonia at low concentrations. The influence of various preparation parameters, including the pH value of sol, calcination...A series of aluminumphosphate materials was prepared and used as adsorbents for the removal of ammonia at low concentrations. The influence of various preparation parameters, including the pH value of sol, calcination temperature and molar ratio of P/A1, on the structure and surface properties as well as adsorption capacity was investigated. The results showed that large amount of P-OH present on the surface of aluminophosphates was suitable for the removal of ammonia. They were the major source of weak Br6nsted acid sites and acted as the main active centers for capturing ammonia.展开更多
基金Funded by the National Science&Technology Pillar Program during the Twelfth Five-year Plan Period(2011BAK03B07)the Specialized Research Fund for the Technology Research Program of Ministry of Public Security(2014JSYJA024)the Specialized Research Fund for the Applications Innovation Program of Ministry of Public Security(2011YYCXWJXY131)
文摘Titanium phosphonate adsorbent materials with hierarchically porous structure were fabricated using the hydrolysis of tetrabutyl titanate in different organophosphonic acids solutions. Based on the macroporous structure of 100-2000 nm in size, a worm-hole like mesostructure was in the macropore walls, which was supported by the scanning electron microscopy(SEM), transmission electron microscopy(TEM), and N2 sorption analysis. Fourier transform infrared spectroscopy(FT-IR) data indicated the organic groups inside the solid materials framework. NH3 adsorption detection was performed using titanium phosphonate adsorbent materials and some significant results were obtained. The adsorption mechanism was also discussed in this study. Large adsorption amount(75.2 mg/g) was mainly attributed to the acid site via acid-base reactions and the physical adsorption site via Van der Waals forces. Resultant materials could effectively restrain the desorption of adsorbent NH3 back into air causing secondary pollution, so it could make a promising potential use in decontamination of gas pollutants in the future.
基金supported by the National Natural Science Foundation of China(52261145701 and U21A20162)the 2115 Talent Development Program of China Agricultural University.
文摘The function-led design of porous hydrochar from mineral-rich biowaste for environmental applications inevitably suffers from carbon-ash recalcitrance.However,a method to alter the original carbon skeleton with ash remains elusive and hinders the availability of hydrochar.Herein,we propose a facile strategy for breaking the rigid structure of carbon-ash coupled hydrochar using phase-tunable molten carbonates.A case system was designed in which livestock manure and NaHCO3 were used to prepare the activated hydrochar,and NH3 served as the target contaminant.Due to the redox effect,we found that organic fractions significantly advanced the melting temperature of Na2CO3 below 800℃.The Na species steadily broke the carbon-ash interaction as the thermal intensity increased and transformed inorganic constituents to facilitate ash dissolution,rebuilding the hydrochar skeleton with abundant hierarchical channels and active defect edges.The surface polarity and mesopore distribution collectively governed the five cycles NH3 adsorption attenuation process.Manure hydrochar delivered favorable potential for application with a maximum overall adsorption capacity of 100.49 mg·g^(-1).Integrated spectroscopic characterization and theoretical computations revealed that incorporating NH3 on the carbon surface could transfer electrons to chemisorbed oxygen,which promoted the oxidation of pyridine-N during adsorption.This work offers deep insight into the structure function correlation of hydrochar and inspires a more rational design of engineered hydrochar from high-ash biowaste.
基金Funded by the National Natural Science Foundation of China(No.51106161)the National Hi-Tech Research and Development Program of China(No.2012AA053003)the Guangdong Province and Chinese Academy of Sciences Comprehensive Strategic Cooperation Projects(2012B091100263)
文摘We put forward a new and ingenious method for the preparation of a new adsorbent by soaking, carbonizing and activating the mixture of hygroscopic salt and biomass material. The new adsorbent has high porosity, uniform distribution and high content of Ca Cl2, and exhibits high adsorption performance. The ammonia uptake and specific cooling power(SCP) at 5 min adsorption time can reach as high as 0.19 g·g^-1 and 793.9 W·kg^-1, respectively. The concept of utilizing the biomass materials and hygroscopic salts as raw materials for the preparation of adsorbents is of practical interest with respect to the potential quantity of biomass materials around the world, indicating that there would be a new market for biomass materials.Key words: biomass material; adsorption system; ammonia; calcium chloride; activated carbon
基金the National Natural Science Foundation of China(No.21731003).
文摘Metal-organic frameworks(MOFs)with inherent porosity and suspended acidic groups are promising proton conducting materials in water or aqua-ammonia media.Herein we report a new lanthanide phosphonate,namely,Dy_(2)(amp_(2)H_(2))_(2)(mal)(H_(2)O)_(2)·5H2O(MDAF-6).It possesses a 3D open-framework structure,and shows a high NH_(3)adsorption capacity of 142.4 cm^(3)/g at P/P0=0.98 at 298 K due to acid-base interaction.Interestingly,the proton conductivity of MDAF-6-NH3 is enhanced by five orders of magnitude compared to MDAF-6 after 8.5 h exposure in saturated NH_(3)-H_(2)O vapor,indicating the importance of coexistent conjugate acid-base pairs of H_(3)O+-H_(2)O and NH_(4)^(+)-NH_(3)in promoting proton conduction.Magnetic studies of MDAF-6 revealed slow magnetization relaxation under zero dc field,characteristic of singlemolecule magnet behavior.This work provides not only a new multifunctional MOF material,but also a new strategy to improve proton conduction in aqua-ammonia medium.
基金Supported by the National Natural Science Foundation of China(No.21473074) and the Open Project of State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, China(No.2017-03).
文摘A series of aluminumphosphate materials was prepared and used as adsorbents for the removal of ammonia at low concentrations. The influence of various preparation parameters, including the pH value of sol, calcination temperature and molar ratio of P/A1, on the structure and surface properties as well as adsorption capacity was investigated. The results showed that large amount of P-OH present on the surface of aluminophosphates was suitable for the removal of ammonia. They were the major source of weak Br6nsted acid sites and acted as the main active centers for capturing ammonia.