We investigated the adsorption performance of five Fe-based MOFs(Fe-BTC,MIL-100(Fe),MIL-101(Fe),MIL-53(Fe)and MIL-88 C(Fe))for removal of antimonite(Sb(Ⅲ))and antimonate(Sb(Ⅴ))from water.Among these MOFs,MIL-101(Fe)...We investigated the adsorption performance of five Fe-based MOFs(Fe-BTC,MIL-100(Fe),MIL-101(Fe),MIL-53(Fe)and MIL-88 C(Fe))for removal of antimonite(Sb(Ⅲ))and antimonate(Sb(Ⅴ))from water.Among these MOFs,MIL-101(Fe)exhibited the best adsorption capacities for both Sb(Ⅲ)and Sb(Ⅴ)(151.8 and 472.8 mg/g,respectively)which were higher than those of most adsorbents previously reported.The effect of steric hindrance was evident during Sb removal using the Fe-based MOFs,and the proper diameter of the smallest cage windows/channels should be considered an important parameter during the evaluation and selection of MOFs.Additionally,the adsorption capacities of MIL-101(Fe)for Sb(Ⅴ)decreased with increasing initial p H values(from 3.0 to 8.0),while the opposite trend was observed for Sb(Ⅲ).Chloride,nitrate and sulfate ions had a negligible influence on Sb(Ⅴ)adsorption,while NO3-and SO42-improved Sb(Ⅲ)adsorption.This result implies that inner sphere complexes might form during both Sb(Ⅲ)and Sb(Ⅴ)adsorption.展开更多
Mesoporous carbons have been widely utilized as the sulfur host for lithium-sulfur （Li-S） batteries. The ability to engineer the porosity, wall thickness, and graphitization degree of the carbon host is essential fo...Mesoporous carbons have been widely utilized as the sulfur host for lithium-sulfur （Li-S） batteries. The ability to engineer the porosity, wall thickness, and graphitization degree of the carbon host is essential for addressing issues that hamper commercialization of Li-S batteries, such as fast capacity decay and poor high-rate performance. In this work, highly ordered, ultrathin mesoporous graphitic-carbon frameworks （MGFs） having unique cage-like mesoporosity, derived from self-assembled Fe304 nanoparticle superlattices, are demonstrated to be an excellent host for encapsulating sulfur. The resulting S@MGFs exhibit high specific capacity （1,446 mAh.g-1 at 0.15 C）, good rate capability （430 mAh.g-1 at 6 C）, and exceptional cycling stability （-0.049% capacity decay per cycle at 1 C） when used as Li-S cathodes. The superior electrochemical performance of the S@MGFs is attributed to the many unique and advantageous structural features of MGFs. In addition to the interconnected, ultrathin graphitic-carbon framework that ensures rapid electron and lithium-ion transport, the microporous openings between adjacent mesopores efficiently suppress the diffusion of polysulfides, leading to improved capacity retention even at high current densities.展开更多
Self-assembly of cadmium ions and the rigid bridging ligand 4,4′-methylenebis(3-hydroxy-2-naphthoic acid) (pamoic acid, H4PA) leads to a one-dimensional metal-organic framework with open cube-like M2(H2PA)2 cages wit...Self-assembly of cadmium ions and the rigid bridging ligand 4,4′-methylenebis(3-hydroxy-2-naphthoic acid) (pamoic acid, H4PA) leads to a one-dimensional metal-organic framework with open cube-like M2(H2PA)2 cages within its backbone, and exhibiting interesting yellow fluorescence.展开更多
A heterogeneous metal-organic cage based on Rh-Rh bonds [Rh4（pbeddb）4（H2O）2（DMAC）2] （MOC-18; pbeddb2- = 3,3＇-（1,3-phenylenebis（ethyne-2,1-diyl））dibenzoate） was applied to the N-- H insertion reactions wit...A heterogeneous metal-organic cage based on Rh-Rh bonds [Rh4（pbeddb）4（H2O）2（DMAC）2] （MOC-18; pbeddb2- = 3,3＇-（1,3-phenylenebis（ethyne-2,1-diyl））dibenzoate） was applied to the N-- H insertion reactions with diazo compounds. This method offered an environmentally friendly and highly efficient approach for C--N bond formation.展开更多
The design and synthesis of stable metal–organic frameworks(MOFs)have been a core obstacle in the widespread application of these functional crystalline porous materials,because of the stability limitations of MOFs u...The design and synthesis of stable metal–organic frameworks(MOFs)have been a core obstacle in the widespread application of these functional crystalline porous materials,because of the stability limitations of MOFs under harsh operating conditions.Herein,a highly stable microporous MOF based on the Fe_(3)O cluster(PCN-678)has been synthesized using a tetracarboxylate ligand.Utilizing symmetry reduced tetratopic carboxylate ligand,a mesoporous MOF(PCN-668)could be obtained in which nanoscale cage-like building units and one-dimensional(1D)channels coexist.The neighboring cages were mutual diastereomers in PCN-668 due to the further reduction of the Cs symmetry of the free ligand to C1 symmetry after self-assembly.Furthermore,the acid stability of this mesoporous MOF was improved via postsynthetic metal exchange to chromium(PCN-668-Cr).The PCN-668-Cr exhibited very high stability in both acidic and basic aqueous solutions(pH=1–11).Additionally,the mesoporous MOF showed a high total gravimetric methane uptake(∼500 cm^(3) g^(−1) at 100 bar),while the microporous MOF showed a high volumetric methane storage capacity of 147 cm3 cm−3 at room temperature.展开更多
基金supported by the National Natural Science Foundation of China (No. 41201302)the Natural Science Foundation of Shanghai (No. 17ZR1407000)the Fundamental Research Funds for the Central Universities (No. 222201514337)
文摘We investigated the adsorption performance of five Fe-based MOFs(Fe-BTC,MIL-100(Fe),MIL-101(Fe),MIL-53(Fe)and MIL-88 C(Fe))for removal of antimonite(Sb(Ⅲ))and antimonate(Sb(Ⅴ))from water.Among these MOFs,MIL-101(Fe)exhibited the best adsorption capacities for both Sb(Ⅲ)and Sb(Ⅴ)(151.8 and 472.8 mg/g,respectively)which were higher than those of most adsorbents previously reported.The effect of steric hindrance was evident during Sb removal using the Fe-based MOFs,and the proper diameter of the smallest cage windows/channels should be considered an important parameter during the evaluation and selection of MOFs.Additionally,the adsorption capacities of MIL-101(Fe)for Sb(Ⅴ)decreased with increasing initial p H values(from 3.0 to 8.0),while the opposite trend was observed for Sb(Ⅲ).Chloride,nitrate and sulfate ions had a negligible influence on Sb(Ⅴ)adsorption,while NO3-and SO42-improved Sb(Ⅲ)adsorption.This result implies that inner sphere complexes might form during both Sb(Ⅲ)and Sb(Ⅴ)adsorption.
基金A. G. D. acknowledges the financial support from the National Basic Research Program of China （No. 2014CB845602）, Natural National Science Foundation of China （No. 21373052）, and Shanghai International Science and Technology Cooperation Project （No. 15520720100）. D. Y. is grateful for financial support from Natural National Science Foundation of China （Nos. 51373035, 51373040, 51573030, and 51573028）, and International Science and Technology Cooperation Program of China （No. 2014DFE40130）.
文摘Mesoporous carbons have been widely utilized as the sulfur host for lithium-sulfur （Li-S） batteries. The ability to engineer the porosity, wall thickness, and graphitization degree of the carbon host is essential for addressing issues that hamper commercialization of Li-S batteries, such as fast capacity decay and poor high-rate performance. In this work, highly ordered, ultrathin mesoporous graphitic-carbon frameworks （MGFs） having unique cage-like mesoporosity, derived from self-assembled Fe304 nanoparticle superlattices, are demonstrated to be an excellent host for encapsulating sulfur. The resulting S@MGFs exhibit high specific capacity （1,446 mAh.g-1 at 0.15 C）, good rate capability （430 mAh.g-1 at 6 C）, and exceptional cycling stability （-0.049% capacity decay per cycle at 1 C） when used as Li-S cathodes. The superior electrochemical performance of the S@MGFs is attributed to the many unique and advantageous structural features of MGFs. In addition to the interconnected, ultrathin graphitic-carbon framework that ensures rapid electron and lithium-ion transport, the microporous openings between adjacent mesopores efficiently suppress the diffusion of polysulfides, leading to improved capacity retention even at high current densities.
基金supported by the National Natural Science Foundation of China (20772019)NSF of Shanghai (08dj1400100)the Doctoral Program of National Education Ministry of China
文摘Self-assembly of cadmium ions and the rigid bridging ligand 4,4′-methylenebis(3-hydroxy-2-naphthoic acid) (pamoic acid, H4PA) leads to a one-dimensional metal-organic framework with open cube-like M2(H2PA)2 cages within its backbone, and exhibiting interesting yellow fluorescence.
文摘A heterogeneous metal-organic cage based on Rh-Rh bonds [Rh4（pbeddb）4（H2O）2（DMAC）2] （MOC-18; pbeddb2- = 3,3＇-（1,3-phenylenebis（ethyne-2,1-diyl））dibenzoate） was applied to the N-- H insertion reactions with diazo compounds. This method offered an environmentally friendly and highly efficient approach for C--N bond formation.
基金supported by the Center for Gas Separations,an Energy Frontier Research Center funded by the U.S.Department of Energy,Office of Science,Office of Basic Energy Sciences(no.DESC0001015)Structural analyses were supported by the Robert A.Welch Foundation through a Welch Endowed Chair to H.-C.Z.(A-0030)+3 种基金The National Science Foundation Graduate Research Fellowship(DGE:1252521)is gratefully acknowledged.The authors also acknowledge the financial support of the U.S.Department of Energy Office of Fossil Energy,National Energy Technology Laboratory(no.DE-FE0026472)and National Science Foundation Small Business Innovation Research(NSFSBIR)under grant no.(1632486)the financial support of the Strategic Priority Research Program of the Chinese Academy of Sciences(no.XDB20000000)National Nature Science Foundation of China(no.21871266),CAS(no.QYZDY-SSWSLH025),and Youth Innovation Promotion Association CAS.
文摘The design and synthesis of stable metal–organic frameworks(MOFs)have been a core obstacle in the widespread application of these functional crystalline porous materials,because of the stability limitations of MOFs under harsh operating conditions.Herein,a highly stable microporous MOF based on the Fe_(3)O cluster(PCN-678)has been synthesized using a tetracarboxylate ligand.Utilizing symmetry reduced tetratopic carboxylate ligand,a mesoporous MOF(PCN-668)could be obtained in which nanoscale cage-like building units and one-dimensional(1D)channels coexist.The neighboring cages were mutual diastereomers in PCN-668 due to the further reduction of the Cs symmetry of the free ligand to C1 symmetry after self-assembly.Furthermore,the acid stability of this mesoporous MOF was improved via postsynthetic metal exchange to chromium(PCN-668-Cr).The PCN-668-Cr exhibited very high stability in both acidic and basic aqueous solutions(pH=1–11).Additionally,the mesoporous MOF showed a high total gravimetric methane uptake(∼500 cm^(3) g^(−1) at 100 bar),while the microporous MOF showed a high volumetric methane storage capacity of 147 cm3 cm−3 at room temperature.
