Precise control over the isomorphic selfassembly of nanocluster superstructures via weak interactions remains a fundamental challenge in materials science,primarily due to the lack of directional guidance.Inspired by ...Precise control over the isomorphic selfassembly of nanocluster superstructures via weak interactions remains a fundamental challenge in materials science,primarily due to the lack of directional guidance.Inspired by the ancient mortise-and-tenon joint,we herein report a series of crystalline nanocluster superstructures(MTC-1 and MTC-2)that were exclusively assembled by such molecular joints,representing the first paradigm of its kind.Despite alterations in functional groups(methyl and ethyl),the supramolecular packing motif remains invariant,underscoring the robustness of this directed assembly strategy.Notably,the ethyl groups in MTC-2 serve as“locking pins”,resulting in MTC-2 a fascinating Luban lock-like construction.This ingenious design endows MTC-2 with enhanced photogenerated charge migration and superior O2 adsorption capability,achieving a record-high photocatalytic H_(2)O_(2) production rate(19,978μmol·g^(-1)·h^(-1))among all isolated crystalline cluster-based materials,an order-of-magnitude enhancement over existing benchmarks.This work not only presents a record-breaking photocatalyst but also establishes a general assembly strategy,the mortise-and-tenon joint,which is expected to guide the rational design of functional superstructures across diverse nanocluster systems.展开更多
The efficient separation of acetylene gas(C_(2)H_(2))from C_(2)H_(2)/C_(2)H_(4)and C_(2)H_(2)/CH_(4)is of great significance in various applications due to its high commercial value and numerous practical production s...The efficient separation of acetylene gas(C_(2)H_(2))from C_(2)H_(2)/C_(2)H_(4)and C_(2)H_(2)/CH_(4)is of great significance in various applications due to its high commercial value and numerous practical production scenarios.In this study,a series of ultra-microporous metal-organic frameworks(MOFs)(JLU-MOF161-164)were prepared using mixed-ligand strategy.Drawing upon the principles of isoreticular chemistry,the precise control over ultra-microporous MOFs at a sub-1Åscale was achieved through functionalization of ligands.The pore sizes decreased from 5.70 to 4.90,4.24,and 3.74Åfor JLU-MOF161-164.This ultra-fine tuning in pore size significantly improved the selectivity towards C_(2)H_(2)for the series compounds.The C_(2)H_(2)adsorption capacity of JLU-MOF164 reached 76.1 cm^(3)·g^(-1)at 298 K.Notably,the selectivities for C_(2)H_(2)/C_(2)H_(4)(50/50)and C_(2)H_(2)/CH_(4)(50/50)achieved remarkable values of 10.1 and 716.7,respectively.Compared with JLU-MOF161,these selectivities were enhanced by 3.6-fold and 9.9-fold,respectively.Breakthrough experiments further validated the outstanding dynamic separation performance and excellent cycling stability of JLU-MOF164,highlighting its significant potential for industrial application.展开更多
Covalent organic frameworks(COFs)have emerged as auspicious porous adsorbents for radioiodine capture.However,their conventional solvothermal synthesis demands multiday synthetic times and anaerobic conditions,largely...Covalent organic frameworks(COFs)have emerged as auspicious porous adsorbents for radioiodine capture.However,their conventional solvothermal synthesis demands multiday synthetic times and anaerobic conditions,largely hampering their practical use.To tackle these challenges,we present a facile microwave-assisted synthesis of 2D imine-linked COFs,Mw-TFB-BD-X,(X=−CH_(3) and−OCH_(3))under air within just 1 h.The resultant COFs possessed higher crystallinity,better yields,and more uniform morphology than their solvothermal counterparts.Remarkably,Mw-TFB-BD-CH_(3) and Mw-TFB-BDOCH_(3) exhibited exceptional iodine adsorption capacities of 7.83 g g^(−1) and 7.05 g g^(−1),respectively,placing them among the bestperforming COF adsorbents for static iodine vapor capture.Moreover,Mw-TFB-BD-CH_(3) and Mw-TFB-BD-OCH_(3) can be reused 5 times with no apparent loss in the adsorption capacity.The exceptionally high iodine adsorption capacities and excellent reusability of COFs were mainly attributed to their uniform spherical morphology and enhanced chemical stability due to the in-built electron-donating groups,despite their low surface areas.This work establishes a benchmark for developing advanced iodine adsorbents that combine fast kinetics,high capacity,excellent reusability,and facile rapid synthesis,a set of appealing features that remain challenging to merge in COF adsorbents so far.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 National Natural Science Foundation of China(Nos.22575048,22101048,22271046,and 22373015)the National Science Fund for Distinguished Young Scholars of China(No.22425102)+1 种基金the Natural Science Foundation of Fujian Province(No.2025J01628)the Open Project of the National Key Laboratory of Structural Chemistry(No.20250002).
文摘Precise control over the isomorphic selfassembly of nanocluster superstructures via weak interactions remains a fundamental challenge in materials science,primarily due to the lack of directional guidance.Inspired by the ancient mortise-and-tenon joint,we herein report a series of crystalline nanocluster superstructures(MTC-1 and MTC-2)that were exclusively assembled by such molecular joints,representing the first paradigm of its kind.Despite alterations in functional groups(methyl and ethyl),the supramolecular packing motif remains invariant,underscoring the robustness of this directed assembly strategy.Notably,the ethyl groups in MTC-2 serve as“locking pins”,resulting in MTC-2 a fascinating Luban lock-like construction.This ingenious design endows MTC-2 with enhanced photogenerated charge migration and superior O2 adsorption capability,achieving a record-high photocatalytic H_(2)O_(2) production rate(19,978μmol·g^(-1)·h^(-1))among all isolated crystalline cluster-based materials,an order-of-magnitude enhancement over existing benchmarks.This work not only presents a record-breaking photocatalyst but also establishes a general assembly strategy,the mortise-and-tenon joint,which is expected to guide the rational design of functional superstructures across diverse nanocluster systems.
基金supported by the National Natural Science Foundation of China(Nos.22171100 and U23A20360)the“111 Center”(No.B17020)supported by the National Natural Science Foundation of China(Nos.21771029,11811530631, 21573034).
文摘The efficient separation of acetylene gas(C_(2)H_(2))from C_(2)H_(2)/C_(2)H_(4)and C_(2)H_(2)/CH_(4)is of great significance in various applications due to its high commercial value and numerous practical production scenarios.In this study,a series of ultra-microporous metal-organic frameworks(MOFs)(JLU-MOF161-164)were prepared using mixed-ligand strategy.Drawing upon the principles of isoreticular chemistry,the precise control over ultra-microporous MOFs at a sub-1Åscale was achieved through functionalization of ligands.The pore sizes decreased from 5.70 to 4.90,4.24,and 3.74Åfor JLU-MOF161-164.This ultra-fine tuning in pore size significantly improved the selectivity towards C_(2)H_(2)for the series compounds.The C_(2)H_(2)adsorption capacity of JLU-MOF164 reached 76.1 cm^(3)·g^(-1)at 298 K.Notably,the selectivities for C_(2)H_(2)/C_(2)H_(4)(50/50)and C_(2)H_(2)/CH_(4)(50/50)achieved remarkable values of 10.1 and 716.7,respectively.Compared with JLU-MOF161,these selectivities were enhanced by 3.6-fold and 9.9-fold,respectively.Breakthrough experiments further validated the outstanding dynamic separation performance and excellent cycling stability of JLU-MOF164,highlighting its significant potential for industrial application.
基金supported by the U.S.Department of Energy Office of Science Early Career Research Program(DESC0022000)the National Science Foundation HBCU-UPRIA program(no.2100360)+2 种基金the U.S.Department of Defense,the Office of Naval Research(no:N00014-20-1-2523)supported by the Office of Science,Office of Basic Energy Sciences,of the U.S.Department of Energy under Contract No.DE-AC02-05CH11231the support from Qassim University.S.C.is grateful for the support from the National Natural Science Foundation of China(no.22171092).
文摘Covalent organic frameworks(COFs)have emerged as auspicious porous adsorbents for radioiodine capture.However,their conventional solvothermal synthesis demands multiday synthetic times and anaerobic conditions,largely hampering their practical use.To tackle these challenges,we present a facile microwave-assisted synthesis of 2D imine-linked COFs,Mw-TFB-BD-X,(X=−CH_(3) and−OCH_(3))under air within just 1 h.The resultant COFs possessed higher crystallinity,better yields,and more uniform morphology than their solvothermal counterparts.Remarkably,Mw-TFB-BD-CH_(3) and Mw-TFB-BDOCH_(3) exhibited exceptional iodine adsorption capacities of 7.83 g g^(−1) and 7.05 g g^(−1),respectively,placing them among the bestperforming COF adsorbents for static iodine vapor capture.Moreover,Mw-TFB-BD-CH_(3) and Mw-TFB-BD-OCH_(3) can be reused 5 times with no apparent loss in the adsorption capacity.The exceptionally high iodine adsorption capacities and excellent reusability of COFs were mainly attributed to their uniform spherical morphology and enhanced chemical stability due to the in-built electron-donating groups,despite their low surface areas.This work establishes a benchmark for developing advanced iodine adsorbents that combine fast kinetics,high capacity,excellent reusability,and facile rapid synthesis,a set of appealing features that remain challenging to merge in COF adsorbents so far.
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.
