By tuning interpenetrated and non-interpenetrated frameworks,a pair of Cu-paddlewheel frameworkinterpenetration isomers(UPC-34,[Cu_(3)(L)_(2)(H_(2)O)_(3)]·2DMF·3EtOH·3H_(2)O and UPC-35,[Cu_(3)(L)_(2)(H_...By tuning interpenetrated and non-interpenetrated frameworks,a pair of Cu-paddlewheel frameworkinterpenetration isomers(UPC-34,[Cu_(3)(L)_(2)(H_(2)O)_(3)]·2DMF·3EtOH·3H_(2)O and UPC-35,[Cu_(3)(L)_(2)(H_(2)O)_(3)]·2DMF·2Diox·3H_(2)O)based on a tripodal ligand(H_(3)L=4,4’-((5-carboxy-1,3-phenylene)bis(ethyne-2,1-diyl))dibenzoic acid)has been synthesized and characterized.The interpenetrated framework(UPC-35)is more stable than the non-interpenetrated one(UPC-34).Due to the 2-fold interpenetration,UPC-35 has a pore size distribution of~4.5A,which is close to the kinetic diameters of light hydrocarbons(C_(1)-C_(3)),and thus exhibits high gas-uptake capacities for C_(3)H_(6)and C_(3)H_(8).Furthermore,UPC-35 is an effective adsorbent for the selective separation of C_(3)/C_(2)/C_(1)light hydrocarbons.展开更多
Bismuth titanate based materials have wide potential applications in thefields of dielectrics,piezoelec trics,ferroelectrics,catalysis and energy storage.In this study,a two dimensional(2-D)layered H_(1.07)Ti_(1.73)O_...Bismuth titanate based materials have wide potential applications in thefields of dielectrics,piezoelec trics,ferroelectrics,catalysis and energy storage.In this study,a two dimensional(2-D)layered H_(1.07)Ti_(1.73)O_(4)·nH_(2)O(HTO)crystal was used as a precursor to prepare 2-D bismuth titanate oriented poly crystal nanocomposites using two kinds of Bi^(3+)sources.The chemical reaction mechanisms for the for mation of bismuth titanates are proposed,and the crystal structures and their conversions are also ident ified.The formation mechanism of the discontinuous-zone-axis is revealed.The obtained bismuth tita nates are oriented polycrystals constructed from the orientation nanocrystals.In the process of forming the oriented polycrystal,the zone axis of the bismuth titanates obtained under different reaction con ditions can vary even if the same reactants are used in the reaction.The certain topological correspon dences among the oriented polycrystal,the precursor,and the intermediate,as well as the formation of bismuth titanates with a discontinuous-zone-axis based on a topochemical mesocrystal conversion reac tion,were proposed.The special arrangement structure of the TiO6 octahedral layers accommodating in the HTO crystal is the main reason for the constant change of the zone axis of the bismuth titanate nano composite.However,based on the crystallographic investigation of the reaction mechanism involved in the formation process of construction of the bismuth titanate oriented polycrystal nanocomposite from the HTO crystal,it is found that the topochemical mesocrystal conversion reaction with a discontinuous zone-axis is different from the conventional topochemical reactions.This may be attributed to the combi nation of the HTO matrix and Bi^(3+).It is vital to study the controllable preparation of bismuth titanate based nanocomposites and further understand the topochemical reaction.展开更多
Adsorptive separation of acetylene(C_(2)H_(2))from carbon dioxide(CO_(2))by adsorption is a viable method for producing high-purity C_(2)H_(2) required for industrial applications.However,separating C_(2)H_(2) and CO_...Adsorptive separation of acetylene(C_(2)H_(2))from carbon dioxide(CO_(2))by adsorption is a viable method for producing high-purity C_(2)H_(2) required for industrial applications.However,separating C_(2)H_(2) and CO_(2) is challenging due to their extremely similar molecular sizes and physical properties.Metal-Organic Frameworks(MOFs),as a novel porous material with high specific surface area and tunable pore size,have shown great potential in the separation and purification of light hydrocarbons.Herein,we synthesized three isoreticular Al-MOFs(Al-TCPP,Al-TCPP(Co),and Al-TCPP(Fe))by modulating metal ions at the porphyrin center,all of which can effectively separate C_(2)H_(2)/CO_(2).The addition of metal ions can regulate and improve the separation selectivity of C_(2)H_(2)/CO_(2).Compared with the parent Al-TCPP,the IAST selectivities of Al-TCPP(Co)and Al-TCPP(Fe)for equimolar C_(2)H_(2)/CO_(2) increased from 1.73 to 3.66 and 4.43,respectively.Breakthrough experiments validate their efficient separation of C_(2)H_(2)/CO_(2).Furthermore,they all exhibit excellent hydrothermal stability,laying the foundation for practical applications.展开更多
基金supported by the NSF of China(Grant No.21571187,21771191,and 21571137)Taishan Scholar Foundation(ts201511019)+3 种基金the Shandong Natural Science Fund(ZR2017QB012)the Fundamental Research Funds for the Central Universities(14CX02213A and 16CX05015A)the Foundation of State Key Laboratory of Structural Chemistry(20160006)the Applied Basic Research Projects of Qingdao(16-5-1-95-jch).
文摘By tuning interpenetrated and non-interpenetrated frameworks,a pair of Cu-paddlewheel frameworkinterpenetration isomers(UPC-34,[Cu_(3)(L)_(2)(H_(2)O)_(3)]·2DMF·3EtOH·3H_(2)O and UPC-35,[Cu_(3)(L)_(2)(H_(2)O)_(3)]·2DMF·2Diox·3H_(2)O)based on a tripodal ligand(H_(3)L=4,4’-((5-carboxy-1,3-phenylene)bis(ethyne-2,1-diyl))dibenzoic acid)has been synthesized and characterized.The interpenetrated framework(UPC-35)is more stable than the non-interpenetrated one(UPC-34).Due to the 2-fold interpenetration,UPC-35 has a pore size distribution of~4.5A,which is close to the kinetic diameters of light hydrocarbons(C_(1)-C_(3)),and thus exhibits high gas-uptake capacities for C_(3)H_(6)and C_(3)H_(8).Furthermore,UPC-35 is an effective adsorbent for the selective separation of C_(3)/C_(2)/C_(1)light hydrocarbons.
基金supported in part by the National Natural Science Foundation of China(No.21005003)the Natural Science Basic Research Plan in Shaanxi Province of China(2019JM-091)+2 种基金the Industrial Science and Technology Plan in Shaanxi Province of China(19JC002)the Doctoral Scientific Research Starting Foundation of Baoji University of Arts and Sciences(No.ZK2018059)Baoji University of Arts and Sciences Postgraduate Innovative Research Projects(YJSCX19ZC11).
文摘Bismuth titanate based materials have wide potential applications in thefields of dielectrics,piezoelec trics,ferroelectrics,catalysis and energy storage.In this study,a two dimensional(2-D)layered H_(1.07)Ti_(1.73)O_(4)·nH_(2)O(HTO)crystal was used as a precursor to prepare 2-D bismuth titanate oriented poly crystal nanocomposites using two kinds of Bi^(3+)sources.The chemical reaction mechanisms for the for mation of bismuth titanates are proposed,and the crystal structures and their conversions are also ident ified.The formation mechanism of the discontinuous-zone-axis is revealed.The obtained bismuth tita nates are oriented polycrystals constructed from the orientation nanocrystals.In the process of forming the oriented polycrystal,the zone axis of the bismuth titanates obtained under different reaction con ditions can vary even if the same reactants are used in the reaction.The certain topological correspon dences among the oriented polycrystal,the precursor,and the intermediate,as well as the formation of bismuth titanates with a discontinuous-zone-axis based on a topochemical mesocrystal conversion reac tion,were proposed.The special arrangement structure of the TiO6 octahedral layers accommodating in the HTO crystal is the main reason for the constant change of the zone axis of the bismuth titanate nano composite.However,based on the crystallographic investigation of the reaction mechanism involved in the formation process of construction of the bismuth titanate oriented polycrystal nanocomposite from the HTO crystal,it is found that the topochemical mesocrystal conversion reaction with a discontinuous zone-axis is different from the conventional topochemical reactions.This may be attributed to the combi nation of the HTO matrix and Bi^(3+).It is vital to study the controllable preparation of bismuth titanate based nanocomposites and further understand the topochemical reaction.
基金supported by the National Natural Science Foundation of China(No.22201305,22275210)the Fundamental Research Funds for the Central Universities(22CX06024A,23CX04001A)+1 种基金the Outstanding Youth Science Fund Projects of Shandong Province(2022HWYQ-070)Natural Science Foundation of Shandong Province(ZR2021MB060).
文摘Adsorptive separation of acetylene(C_(2)H_(2))from carbon dioxide(CO_(2))by adsorption is a viable method for producing high-purity C_(2)H_(2) required for industrial applications.However,separating C_(2)H_(2) and CO_(2) is challenging due to their extremely similar molecular sizes and physical properties.Metal-Organic Frameworks(MOFs),as a novel porous material with high specific surface area and tunable pore size,have shown great potential in the separation and purification of light hydrocarbons.Herein,we synthesized three isoreticular Al-MOFs(Al-TCPP,Al-TCPP(Co),and Al-TCPP(Fe))by modulating metal ions at the porphyrin center,all of which can effectively separate C_(2)H_(2)/CO_(2).The addition of metal ions can regulate and improve the separation selectivity of C_(2)H_(2)/CO_(2).Compared with the parent Al-TCPP,the IAST selectivities of Al-TCPP(Co)and Al-TCPP(Fe)for equimolar C_(2)H_(2)/CO_(2) increased from 1.73 to 3.66 and 4.43,respectively.Breakthrough experiments validate their efficient separation of C_(2)H_(2)/CO_(2).Furthermore,they all exhibit excellent hydrothermal stability,laying the foundation for practical applications.
