Nanoscale metal-organic frameworks （NMOFs） have attracted increased attention in recent years for miniaturized and/or biological applications.However,the synthesis of ultrasmall NMOFs with good stability is a great ...Nanoscale metal-organic frameworks （NMOFs） have attracted increased attention in recent years for miniaturized and/or biological applications.However,the synthesis of ultrasmall NMOFs with good stability is a great challenge.In this study,sub-5-nm nano-HKUST-1 was prepared for the first time via a mild metalorganic gel route without surfactants or capping agents.Controlling the gelation process via anion-ligand self-assembly is the key to the formation of NMOFs.The Tyndall effect,zeta potential,and liquid adsorption indicated strong stability of the obtained nano-HKUST-1,even in water.Adsorption experiments were performed using different dyes （crystal violet and methylene blue） to demonstrate the size-dependent adsorption thermodynamics and kinetics of this famous MOF.The results of this study provide new insights regarding the synthesis of NMOFs and their efficient applications.展开更多
An unexpected in-situ hydrolysis reaction occurred during the solvothermal reaction of N,N’-bis(4-carboxy-2-methylphenyl)pyromellitic di-imide)and Ba(NO3)2,and a novel porous Ba-MOF,[H_(2)N(CH_(3))_(2)]_(0.5)[Ba_(1.5...An unexpected in-situ hydrolysis reaction occurred during the solvothermal reaction of N,N’-bis(4-carboxy-2-methylphenyl)pyromellitic di-imide)and Ba(NO3)2,and a novel porous Ba-MOF,[H_(2)N(CH_(3))_(2)]_(0.5)[Ba_(1.5)(L)(DMA)]·1.5 DMA·1.5 H_(2)O(UPC-70,H_(3)L=2-(4-ca rboxy-2-methylphenyl)-1,3-dioxoisoindoline-5,6-dicarboxylic acid,DMA=N,N-dimethylacetamide),was obtained on the basis of the partial hydrolysate.The as-synthesized 3 D network with 1 D open channels of different sizes(24 A and 10 A)contains abundant open metal sites after removal of solvents,which is conducive to the preferential adsorption of CO_(2).The subsequent gas sorption measurement reveals the high separation selectivity of UPC-70 for CO_(2)/CH_(4)(15)and CO_(2)/N_(2)(32)at ambient conditions,and GCMC theoretical simulation provides good verification of the experimental results,indicating that UPC-70 is a potential candidate for CO_(2)capture from flue gas and natural gas.展开更多
基金This work was supported by the National Natural Science Foundation of China （No. 21571193）, Open Funds of the state key Laboratory of Rare Earth Resource Utilization （No. RERU2013012）, Science Foundation of Guangdong Province （No. 2015A030312007） and National Postdoctoral Program for Innovative Talents （No. BX201600195）.
文摘Nanoscale metal-organic frameworks （NMOFs） have attracted increased attention in recent years for miniaturized and/or biological applications.However,the synthesis of ultrasmall NMOFs with good stability is a great challenge.In this study,sub-5-nm nano-HKUST-1 was prepared for the first time via a mild metalorganic gel route without surfactants or capping agents.Controlling the gelation process via anion-ligand self-assembly is the key to the formation of NMOFs.The Tyndall effect,zeta potential,and liquid adsorption indicated strong stability of the obtained nano-HKUST-1,even in water.Adsorption experiments were performed using different dyes （crystal violet and methylene blue） to demonstrate the size-dependent adsorption thermodynamics and kinetics of this famous MOF.The results of this study provide new insights regarding the synthesis of NMOFs and their efficient applications.
基金supported by the National Natural Science Foundation of China(NSFC,No.21771191)the Fundamental Research Funds for the Central Universities(No.19CX05001A)。
文摘An unexpected in-situ hydrolysis reaction occurred during the solvothermal reaction of N,N’-bis(4-carboxy-2-methylphenyl)pyromellitic di-imide)and Ba(NO3)2,and a novel porous Ba-MOF,[H_(2)N(CH_(3))_(2)]_(0.5)[Ba_(1.5)(L)(DMA)]·1.5 DMA·1.5 H_(2)O(UPC-70,H_(3)L=2-(4-ca rboxy-2-methylphenyl)-1,3-dioxoisoindoline-5,6-dicarboxylic acid,DMA=N,N-dimethylacetamide),was obtained on the basis of the partial hydrolysate.The as-synthesized 3 D network with 1 D open channels of different sizes(24 A and 10 A)contains abundant open metal sites after removal of solvents,which is conducive to the preferential adsorption of CO_(2).The subsequent gas sorption measurement reveals the high separation selectivity of UPC-70 for CO_(2)/CH_(4)(15)and CO_(2)/N_(2)(32)at ambient conditions,and GCMC theoretical simulation provides good verification of the experimental results,indicating that UPC-70 is a potential candidate for CO_(2)capture from flue gas and natural gas.
