A new series of metal complex carboxylates（MCC）made of [Co（en）3]3＋（MC）and either 2,6-naphthalenedicarboxylic（NDC）or 4,4-biphenyldicarboxylic（BPDC）were synthesized and structurally characterized.The four new...A new series of metal complex carboxylates（MCC）made of [Co（en）3]3＋（MC）and either 2,6-naphthalenedicarboxylic（NDC）or 4,4-biphenyldicarboxylic（BPDC）were synthesized and structurally characterized.The four new compounds have a general formula（MC）2（C）3·n（vip）with the vips of dimethylformamide（DMF）and dimethyl sulfoxide（DMSO）and water.All the structures represent a pillared-layer type,where the layer consists of MC cations,carboxylate anions or water molecules via a large number of hydrogen bonds.The layers are pillared by the organic residues of NDC or BPDC,resulting in the inclusion cavities where the vip molecules reside.Although their topological structures are similar,they crystallize in different crystal structures due to the rearrangement of pillars and hydrogen-bonded layers.展开更多
Using the deep eutectic solvent formed of oxalic acid and choline chloride, a new charge-assisted hydrogen-bonded host framework [Co（en）312[Zr2（C2O4）7]·2H2O （1） has been obtained. The title complex crystall...Using the deep eutectic solvent formed of oxalic acid and choline chloride, a new charge-assisted hydrogen-bonded host framework [Co（en）312[Zr2（C2O4）7]·2H2O （1） has been obtained. The title complex crystallizes in the monoclinic, space group P21/n （No. 14） with a = 7.7448（10）, b = 14.5683（19）, c = 19.375（3） A, fl = 92.124（2）°, V= 2184.5（5） A3, Z = 4, Dc = 1.996 gcm-3, F（000） = 1332, μ = 1.328 mm＂1, R = 0.0353 and wR = 0.0718 （1 〉 2α（I））. Single-crystal structure analysis reveals that the title complex possesses a 3D network assembled through a multitude of charge-assisted hydrogen bonds between the in situ generated anionic coordination complexes [Zr2（C204）7]6- and metal complexes Co（en）33＋.展开更多
In cluster-based MOF materials,although clusters with open metal sites(OMSs)play a critical role in separation processes,excessively strong OMSs can lead to significant co-adsorption with the counterpart gases and res...In cluster-based MOF materials,although clusters with open metal sites(OMSs)play a critical role in separation processes,excessively strong OMSs can lead to significant co-adsorption with the counterpart gases and result in reduced selectivity.Coordinated water molecules can not only result in atomic-level differences in pore size but also significantly affect the binding forces between the host frameworks and vip molecules.Herein,we report a methyl-modified heptanuclear cluster-based MOF,Ni_(7)Me,constructed from inexpensive organic linkers under pure water conditions.Two vip-free materials,Ni_(7)Me-80(with coordinated water)and Ni_(7)Me-200(with OMSs),were synthesized to investigate the separation properties and mechanisms for C_(2)H_(2)/C_(2)H_(4) and C_(3)H_(6)/C_(3)H_(8) mixtures.Dynamic breakthrough tests showed that both Ni_(7)Me-80 and Ni_(7)Me-200 could achieve clean separation of binary C_(2)H_(2)/C_(2)H_(4) mixtures(5/95 v/v),yielding high-purity C_(2)H_(4)(>99.9%).Grand canonical Monte Carlo(GCMC)simulations revealed that the enhanced adsorption and separation performance of Ni_(7)Me-200,compared to Ni_(7)Me-80,is primarily due to differences in the interaction forces between C_(2) molecules and the framework,independent of the OMSs.Notably,Ni_(7)Me-80 exhibited thermodynamically driven adsorption for C_(3)H_(6),while showing kinetic behaviour for C_(3)H_(8) adsorption.This unique property enabled effective separation of C_(3)H_(6) and C_(3)H_(8),as demonstrated by dynamic permeation tests.Stability tests further showed that Ni_(7)Me has exceptional air and boiling water stability.展开更多
Sodium-ion batteries are promising for large-scale energy storage due to sodium's low cost and infinite abundance. The most popular cathodes for sodium-ion batteries, i.e., the layered sodium-containing oxides, us...Sodium-ion batteries are promising for large-scale energy storage due to sodium's low cost and infinite abundance. The most popular cathodes for sodium-ion batteries, i.e., the layered sodium-containing oxides, usually exhibit reversible host rearrangement between P-type and O-type stacking upon charge/discharge. Herein we demonstrate that such host rearrangement is unfavorable and can be suppressed by introducing transition-metal ions into sodium layers. The electrode with stabilized P3-type stacking delivers superior rate capability, high energy efficiency, and excellent cycling performance. Owing to the cation-mixing nature, it performs the lowest lattice strain among all reported cathodes for sodium-ion batteries. Our findings highlight the significance of a stable host for sodium-ion storage and moreover underline the fundamental distinction in material design strategy between lithium-and sodium-ion batteries.展开更多
基金Supported by the National Science Foundation (DMR-0600320)
文摘A new series of metal complex carboxylates（MCC）made of [Co（en）3]3＋（MC）and either 2,6-naphthalenedicarboxylic（NDC）or 4,4-biphenyldicarboxylic（BPDC）were synthesized and structurally characterized.The four new compounds have a general formula（MC）2（C）3·n（vip）with the vips of dimethylformamide（DMF）and dimethyl sulfoxide（DMSO）and water.All the structures represent a pillared-layer type,where the layer consists of MC cations,carboxylate anions or water molecules via a large number of hydrogen bonds.The layers are pillared by the organic residues of NDC or BPDC,resulting in the inclusion cavities where the vip molecules reside.Although their topological structures are similar,they crystallize in different crystal structures due to the rearrangement of pillars and hydrogen-bonded layers.
基金supported by the National Natural Science Foundation of China(Nos.21301024,21103017)the Fundamental Research Funds for the Central Universities(N120305003)
文摘Using the deep eutectic solvent formed of oxalic acid and choline chloride, a new charge-assisted hydrogen-bonded host framework [Co（en）312[Zr2（C2O4）7]·2H2O （1） has been obtained. The title complex crystallizes in the monoclinic, space group P21/n （No. 14） with a = 7.7448（10）, b = 14.5683（19）, c = 19.375（3） A, fl = 92.124（2）°, V= 2184.5（5） A3, Z = 4, Dc = 1.996 gcm-3, F（000） = 1332, μ = 1.328 mm＂1, R = 0.0353 and wR = 0.0718 （1 〉 2α（I））. Single-crystal structure analysis reveals that the title complex possesses a 3D network assembled through a multitude of charge-assisted hydrogen bonds between the in situ generated anionic coordination complexes [Zr2（C204）7]6- and metal complexes Co（en）33＋.
基金the Natural Science Foundation of Ningbo(2022J101)This work was carried out with the support of the Shanghai Synchrotron Radiation Facility,instrument BL17B.
文摘In cluster-based MOF materials,although clusters with open metal sites(OMSs)play a critical role in separation processes,excessively strong OMSs can lead to significant co-adsorption with the counterpart gases and result in reduced selectivity.Coordinated water molecules can not only result in atomic-level differences in pore size but also significantly affect the binding forces between the host frameworks and vip molecules.Herein,we report a methyl-modified heptanuclear cluster-based MOF,Ni_(7)Me,constructed from inexpensive organic linkers under pure water conditions.Two vip-free materials,Ni_(7)Me-80(with coordinated water)and Ni_(7)Me-200(with OMSs),were synthesized to investigate the separation properties and mechanisms for C_(2)H_(2)/C_(2)H_(4) and C_(3)H_(6)/C_(3)H_(8) mixtures.Dynamic breakthrough tests showed that both Ni_(7)Me-80 and Ni_(7)Me-200 could achieve clean separation of binary C_(2)H_(2)/C_(2)H_(4) mixtures(5/95 v/v),yielding high-purity C_(2)H_(4)(>99.9%).Grand canonical Monte Carlo(GCMC)simulations revealed that the enhanced adsorption and separation performance of Ni_(7)Me-200,compared to Ni_(7)Me-80,is primarily due to differences in the interaction forces between C_(2) molecules and the framework,independent of the OMSs.Notably,Ni_(7)Me-80 exhibited thermodynamically driven adsorption for C_(3)H_(6),while showing kinetic behaviour for C_(3)H_(8) adsorption.This unique property enabled effective separation of C_(3)H_(6) and C_(3)H_(8),as demonstrated by dynamic permeation tests.Stability tests further showed that Ni_(7)Me has exceptional air and boiling water stability.
基金The financial support from the National Basic Research Program of China(2014CB932300)Natural Science Foundation of Jiangsu Province of China(BK20170630)+1 种基金NSF of China(21633003 and 51602144)sponsored by the JST-CREST ‘‘Phase Interface Science for Highly Efficient Energy Utilization",JST(Japan)
文摘Sodium-ion batteries are promising for large-scale energy storage due to sodium's low cost and infinite abundance. The most popular cathodes for sodium-ion batteries, i.e., the layered sodium-containing oxides, usually exhibit reversible host rearrangement between P-type and O-type stacking upon charge/discharge. Herein we demonstrate that such host rearrangement is unfavorable and can be suppressed by introducing transition-metal ions into sodium layers. The electrode with stabilized P3-type stacking delivers superior rate capability, high energy efficiency, and excellent cycling performance. Owing to the cation-mixing nature, it performs the lowest lattice strain among all reported cathodes for sodium-ion batteries. Our findings highlight the significance of a stable host for sodium-ion storage and moreover underline the fundamental distinction in material design strategy between lithium-and sodium-ion batteries.
