Owing to the similar physicochemical properties between ethane(C_(2)H_(6))and ethylene(C_(2)H_(4)),obtaining polymerization-grade C_(2)H_(4)(≥99.95%pure)is still a tricky problem in the petrochemical industry.Here,we...Owing to the similar physicochemical properties between ethane(C_(2)H_(6))and ethylene(C_(2)H_(4)),obtaining polymerization-grade C_(2)H_(4)(≥99.95%pure)is still a tricky problem in the petrochemical industry.Here,we report a robust scandium-based metalorganic framework(Sc BPDC),which is connected by oxygen-rich phenyl ligand with exceptionally high thermal stability(up to873 K)and capacity of C_(2)H_(6)(4.94 mmol/g at 100 k Pa and 283 K),exhibiting superior separation performance of C_(2)H_(6)/C_(2)H_(4) mixture(the IAST selectivity is up to 1.7 at 283 K).Importantly,Sc BPDC can produce 8.96 L/kg C_(2)H_(4) with≥99.99%purity while the C_(2)H_(4)/C_(2)H_(6)(50:50,v/v)as the mixture injection and the low isosteric heat of Sc BPDC(16.4 k J/mol for C_(2)H_(6))validates the facility of adsorbent regeneration.Furthermore,theoretical calculations demonstrate the C_(2)H_(6) molecules are trapped in the nonpolar pore surface via C–H···πand C–H···O interactions between multiple hydrogen atoms of C_(2)H_(6) and the host framework.展开更多
A series of metal-Al_(2)O_(3)catalysts were prepared simply by the conventional impregnation with Al_(2)O_(3)and metal chlorides,which were applied to the dehydration of fructose to 5-hydroxymethylfurfural(HMF).An agr...A series of metal-Al_(2)O_(3)catalysts were prepared simply by the conventional impregnation with Al_(2)O_(3)and metal chlorides,which were applied to the dehydration of fructose to 5-hydroxymethylfurfural(HMF).An agreeable HMF yield of 93.1%was achieved from fructose at mild conditions(100℃and 40 min)when employing Cr(III)-Al_(2)O_(3)as catalyst in 1-butyl-3-methylimidazolium chloride([Bmim]Cl).The Cr(III)-Al_(2)O_(3)catalyst was characterized via XRD,DRS and Raman spectra and the results clarified the interaction between the Cr(III)and the alumina support.Meanwhile,the reaction solvents([Bmim]Cl)collected after 1st reaction run and 5th reaction run were analyzed by ICP-OES and LC-ITMS and the results confirmed that no Cr(III)ion was dropped off from the alumina support dur-ing the fructose dehydration.Notably,Cr(III)-Al_(2)O_(3)catalyst had an excellent catalytic performance for glucose and sucrose and the HMF yields were reached to 73.7%and 84.1%at 120℃for 60 min,respectively.Furthermore,the system of Cr(III)-Al_(2)O_(3)and[Bmim]Cl exhibited a constant stability and activity at 100℃for 40 min and a fa-vorable HMF yield was maintained after ten recycles.展开更多
The separation of light hydrocarbons,including C_(2)H_(6)and C_(3)H_(8),is essential to natural gas upgrading.Meanwhile,N_(2)removal from CH_(4)is also crucial to concentrating low-quality coalbed methane,but the adso...The separation of light hydrocarbons,including C_(2)H_(6)and C_(3)H_(8),is essential to natural gas upgrading.Meanwhile,N_(2)removal from CH_(4)is also crucial to concentrating low-quality coalbed methane,but the adsorption process is challenging because of the close kinetic diameter.This work reports two hydrogen-bonded metal-nucleobase frameworks(HOF-ZJU-201 and HOF-ZJU202)capable of efficiently separating C_(3)H_(8)/CH_(4),C_(2)H_(6)/CH_(4),and CH_(4)/N_(2).Due to strong affinity for C_(3)H_(8)and C_(2)H_(6),the lowpressure capacity for C_(3)H_(8)(5 kPa)and C_(2)H_(6)(10 kPa)of HOF-ZJU-201a exceeds most adsorbents.The ideal adsorbed solution theory(IAST)selectivity of C_(3)H_(8)/CH_(4)and C_(2)H_(6)/CH_(4)is 119 and 45 at ambient conditions.According to density functional theory calculations,surface polarization environments formed by electron-rich anions and electron-deficient purine heterocyclic rings contribute to the selective capture of C_(3)H_(8)and C_(2)H_(6)with greater polarizability.Furthermore,the high CH_(4)adsorption capacity(1.73 mmol/g for HOF-ZJU-201a and 1.50 mmol/g for HOF-ZJU-202a at 298 K and 1.0 bar)and excellent CH_(4)/N_(2)selectivity(6.0 for HOF-ZJU-201 at 298 K),as well as dynamic breakthrough experiments of binary CH_(4)/N_(2)gas mixture implied their efficacy in the concentration of low-quality coalbed methane.展开更多
基金supported by the National Natural Science Foundation of China(21722609,21878260)the Zhejiang Provincial Natural Science Foundation of China(LR17B060001)。
文摘Owing to the similar physicochemical properties between ethane(C_(2)H_(6))and ethylene(C_(2)H_(4)),obtaining polymerization-grade C_(2)H_(4)(≥99.95%pure)is still a tricky problem in the petrochemical industry.Here,we report a robust scandium-based metalorganic framework(Sc BPDC),which is connected by oxygen-rich phenyl ligand with exceptionally high thermal stability(up to873 K)and capacity of C_(2)H_(6)(4.94 mmol/g at 100 k Pa and 283 K),exhibiting superior separation performance of C_(2)H_(6)/C_(2)H_(4) mixture(the IAST selectivity is up to 1.7 at 283 K).Importantly,Sc BPDC can produce 8.96 L/kg C_(2)H_(4) with≥99.99%purity while the C_(2)H_(4)/C_(2)H_(6)(50:50,v/v)as the mixture injection and the low isosteric heat of Sc BPDC(16.4 k J/mol for C_(2)H_(6))validates the facility of adsorbent regeneration.Furthermore,theoretical calculations demonstrate the C_(2)H_(6) molecules are trapped in the nonpolar pore surface via C–H···πand C–H···O interactions between multiple hydrogen atoms of C_(2)H_(6) and the host framework.
基金The authors thank the financial support for this study by the National Natural Science Foundation of China(Nos.21106057 and 21376111)Society Devel-opment Fund of Zhenjiang(SH2012009)Advanced Talents of Jiangsu University(10JDG143).
文摘A series of metal-Al_(2)O_(3)catalysts were prepared simply by the conventional impregnation with Al_(2)O_(3)and metal chlorides,which were applied to the dehydration of fructose to 5-hydroxymethylfurfural(HMF).An agreeable HMF yield of 93.1%was achieved from fructose at mild conditions(100℃and 40 min)when employing Cr(III)-Al_(2)O_(3)as catalyst in 1-butyl-3-methylimidazolium chloride([Bmim]Cl).The Cr(III)-Al_(2)O_(3)catalyst was characterized via XRD,DRS and Raman spectra and the results clarified the interaction between the Cr(III)and the alumina support.Meanwhile,the reaction solvents([Bmim]Cl)collected after 1st reaction run and 5th reaction run were analyzed by ICP-OES and LC-ITMS and the results confirmed that no Cr(III)ion was dropped off from the alumina support dur-ing the fructose dehydration.Notably,Cr(III)-Al_(2)O_(3)catalyst had an excellent catalytic performance for glucose and sucrose and the HMF yields were reached to 73.7%and 84.1%at 120℃for 60 min,respectively.Furthermore,the system of Cr(III)-Al_(2)O_(3)and[Bmim]Cl exhibited a constant stability and activity at 100℃for 40 min and a fa-vorable HMF yield was maintained after ten recycles.
基金the financial support by the National Natural Science Foundation of China(Nos.21878260,21978254,and 22141001).
文摘The separation of light hydrocarbons,including C_(2)H_(6)and C_(3)H_(8),is essential to natural gas upgrading.Meanwhile,N_(2)removal from CH_(4)is also crucial to concentrating low-quality coalbed methane,but the adsorption process is challenging because of the close kinetic diameter.This work reports two hydrogen-bonded metal-nucleobase frameworks(HOF-ZJU-201 and HOF-ZJU202)capable of efficiently separating C_(3)H_(8)/CH_(4),C_(2)H_(6)/CH_(4),and CH_(4)/N_(2).Due to strong affinity for C_(3)H_(8)and C_(2)H_(6),the lowpressure capacity for C_(3)H_(8)(5 kPa)and C_(2)H_(6)(10 kPa)of HOF-ZJU-201a exceeds most adsorbents.The ideal adsorbed solution theory(IAST)selectivity of C_(3)H_(8)/CH_(4)and C_(2)H_(6)/CH_(4)is 119 and 45 at ambient conditions.According to density functional theory calculations,surface polarization environments formed by electron-rich anions and electron-deficient purine heterocyclic rings contribute to the selective capture of C_(3)H_(8)and C_(2)H_(6)with greater polarizability.Furthermore,the high CH_(4)adsorption capacity(1.73 mmol/g for HOF-ZJU-201a and 1.50 mmol/g for HOF-ZJU-202a at 298 K and 1.0 bar)and excellent CH_(4)/N_(2)selectivity(6.0 for HOF-ZJU-201 at 298 K),as well as dynamic breakthrough experiments of binary CH_(4)/N_(2)gas mixture implied their efficacy in the concentration of low-quality coalbed methane.
