Metal-organic frameworks（MOFs） are a unique class of porous crystalline materials that have shown promise for a wide range of applications. MOFs have been explored as a new type of heterogeneous catalytic materials,...Metal-organic frameworks（MOFs） are a unique class of porous crystalline materials that have shown promise for a wide range of applications. MOFs have been explored as a new type of heterogeneous catalytic materials, because of their high surface area, uniform and tunable pores, facile functionalization and incorporation of catalytic active sites. The use of multi-functional sites MOF materials as catalysts for synergistic catalysis and tandem reactions has attracted increasing attention. In this review, we aim to introduce the construction of bi-or multi-functional MOF catalysts with cooperative or cascade functions via post-synthetic modification（PSM）.展开更多
Multivariate metal-organic frameworks（MTV-MOFs） with different ratios of terephthalate（BDC） linker and amino-benzenedicarboxylate（BDC-NH2） linker were synthesized through both direct synthesis from linker mixtur...Multivariate metal-organic frameworks（MTV-MOFs） with different ratios of terephthalate（BDC） linker and amino-benzenedicarboxylate（BDC-NH2） linker were synthesized through both direct synthesis from linker mixture and linker exchange of activated single-linker MOFs. Functionality proportion was impacted by the thermodynamics during the one-pot MOF construction, resulting in preference of BDC over BDC-NH2 in the MTV-MOF, in agreement with the quantum mechanics calculations. The functionality difference also affects the thermodynamics in the linker exchange process, as indicated by the more effective linker exchange in BDC-NH2-based IRMOF-3 than in BDC-based MOF-5. Furthermore,the thermal decomposition temperatures and chemical integrity upon ambient air exposure of these MOFs with variate functionalities were investigated, and it reveals that higher proportion of BDC in the MTV-MOF crystals contribute to both higher thermal and higher chemical stabilities.展开更多
Coordinated mission decision-making is one of the core steps to effectively exploit the capabilities of cooperative attack of multiple aircrafts. However, the situational assessment is an essential base to realize the...Coordinated mission decision-making is one of the core steps to effectively exploit the capabilities of cooperative attack of multiple aircrafts. However, the situational assessment is an essential base to realize the mission decision-making. Therefore, in this paper, we develop a mission decision-making method of multi-aircraft cooperatively attacking multi-target based on situational assessment. We have studied the situational assessment mathematical model based on the Dempster-Shafer(D-S) evidence theory and the mission decision-making mathematical model based on the game theory. The proposed mission decision-making method of antagonized airfight is validated by some simulation examples of a swarm of unmanned combat aerial vehicles(UCAVs)that carry out the mission of the suppressing of enemy air defenses(SEAD).展开更多
Hydrogen spillover mechanism of metal-supported covalent-organic frameworks COF-105 is investigated by means of the density functional theory, and the effects of metal catalysts M_4（Pt_4, Pd_4, and Ni_4） on the whol...Hydrogen spillover mechanism of metal-supported covalent-organic frameworks COF-105 is investigated by means of the density functional theory, and the effects of metal catalysts M_4（Pt_4, Pd_4, and Ni_4） on the whole spillover process are systematically analyzed. These three metal catalysts exhibit several similar phenomena：（i） they prefer to deposit on the tetra（_4-dihydroxyborylphenyl） silane（TBPS） cluster with surface-contacted configuration;（ii） only the H atoms at the bridge site can migrate to 2,3,6,7,10,11-hexahydroxy triphenylene（HHTP） and TBPS surfaces, and the migration process is an endothermic reaction and not stable;（iii） the introduction of M_4 catalyst can greatly reduce the diffusion energy barrier of H atoms, which makes it easier for the H atoms to diffuse on the substrate surface. Differently, all of the H2 molecules spontaneously dissociate into H atoms onto Pt_4 and Pd_4clusters. However, the adsorbed H2 molecules on Ni_4 cluster show two types of adsorption states： one activated state with stretched H–H bond length of 0.88 ？A via the Kubas interaction and five dissociated states with separated hydrogen atoms. Among all the M_4 catalysts, the orders of the binding energy of M_4 deposited on the substrate and average chemisorption energy per H2 molecule are Pt_4〉Ni_4〉Pd_4. On the contrary, the orders of the migration and diffusion barriers of H atoms are Pt_4展开更多
A sequential improvement strategy has been devised and implemented on a 3D open framework In-BQ showing 2D intersected channels filled by dimethylamine and its protonated cation constructed by-COOCH_(3)-functionalized...A sequential improvement strategy has been devised and implemented on a 3D open framework In-BQ showing 2D intersected channels filled by dimethylamine and its protonated cation constructed by-COOCH_(3)-functionalized anilicate linkers.In situ aliovalent metal substitution and post-synthetic ligand esterolysis led to Cd-BQ-COOH with a doubling of Me_(2)NH_(2)^(+)carriers and a great number of residual-COOH groups,resulting in maximum proton concentration and frequent jumping sites.As a result,the modified Cd-BQ-COOH exhibits a 300-fold enhanced value of proton conductivity compared with that of pristine In-BQ,reaching 6.06×10^(-2) S cm^(-1).MD calculations reveal that the entire process of proton transportation in Cd-BQ-COOH is achieved by the vehicle mechanism.展开更多
The high porosity,excellent water stability and optimized supramolecular host–vip interactions of MOFs are the three key factors for their potential practical applications in many important areas including gas stor...The high porosity,excellent water stability and optimized supramolecular host–vip interactions of MOFs are the three key factors for their potential practical applications in many important areas including gas storage/separation,catalysis and so on.In this study,we designed and constructed a highly porous(3,36)-connected txt-type acylamide-functionalized metal–organic framework(HNUST-8)from a pyridine-based acylamide-linking diisophthalate and dicopper(II)-paddlewheel clusters.展开更多
Two Co(II)-MOFs with different structures were successfully synthesized under the premise of designing two ligands containing alkynyl functional groups. Complexes 1 ([Co(TEPA)(TPT)2/3]·2DMF·H2O) and 2 ([Co(E...Two Co(II)-MOFs with different structures were successfully synthesized under the premise of designing two ligands containing alkynyl functional groups. Complexes 1 ([Co(TEPA)(TPT)2/3]·2DMF·H2O) and 2 ([Co(EPA)(TPT)]·1.5DMF·1.5H2O) show excellent luminescence properties. Meanwhile, as fluorescent sensors, complexes 1 and 2 exhibit selectivity and sensitivity for Fe3+ with the Ksv of 1.520 ×104 L/mol and 3.543 ×104 L/mol, which can rapidly detect nitroaromatic compounds in methanol and ethanol, especially for 2,4-NPH through fluorescence quenching with high quenching efficiency. In particular, the Ksv value of complexes 1 and 2 towards 2,4-NPH can reach up to 1.627 ×105 L/mol and 9.600 ×104 L/mol, demonstrating that complexes 1 and 2 are good candidates for the identification and detection of Fe3+and nitroaromatic compounds.展开更多
基金supported by the National Natural Science Foundation of China (Nos. 21371069 and 21621001)
文摘Metal-organic frameworks（MOFs） are a unique class of porous crystalline materials that have shown promise for a wide range of applications. MOFs have been explored as a new type of heterogeneous catalytic materials, because of their high surface area, uniform and tunable pores, facile functionalization and incorporation of catalytic active sites. The use of multi-functional sites MOF materials as catalysts for synergistic catalysis and tandem reactions has attracted increasing attention. In this review, we aim to introduce the construction of bi-or multi-functional MOF catalysts with cooperative or cascade functions via post-synthetic modification（PSM）.
基金supported by the "Top-Notch Students Training in Basic Disciplines" undergraduate program of Ministry of Education of China
文摘Multivariate metal-organic frameworks（MTV-MOFs） with different ratios of terephthalate（BDC） linker and amino-benzenedicarboxylate（BDC-NH2） linker were synthesized through both direct synthesis from linker mixture and linker exchange of activated single-linker MOFs. Functionality proportion was impacted by the thermodynamics during the one-pot MOF construction, resulting in preference of BDC over BDC-NH2 in the MTV-MOF, in agreement with the quantum mechanics calculations. The functionality difference also affects the thermodynamics in the linker exchange process, as indicated by the more effective linker exchange in BDC-NH2-based IRMOF-3 than in BDC-based MOF-5. Furthermore,the thermal decomposition temperatures and chemical integrity upon ambient air exposure of these MOFs with variate functionalities were investigated, and it reveals that higher proportion of BDC in the MTV-MOF crystals contribute to both higher thermal and higher chemical stabilities.
基金supported by the Aeronautical Science Foundation of China (No. 05D01002)
文摘Coordinated mission decision-making is one of the core steps to effectively exploit the capabilities of cooperative attack of multiple aircrafts. However, the situational assessment is an essential base to realize the mission decision-making. Therefore, in this paper, we develop a mission decision-making method of multi-aircraft cooperatively attacking multi-target based on situational assessment. We have studied the situational assessment mathematical model based on the Dempster-Shafer(D-S) evidence theory and the mission decision-making mathematical model based on the game theory. The proposed mission decision-making method of antagonized airfight is validated by some simulation examples of a swarm of unmanned combat aerial vehicles(UCAVs)that carry out the mission of the suppressing of enemy air defenses(SEAD).
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11304079,11304140,11404094,and 11504088)the China National Scholarship Foundation(Grant No.201508410255)+4 种基金the Foundation for Young Core Teachers of Higher Education Institutions of Henan Province of Chinathe Foundation for Young Core Teachers of Henan University of Technology in Chinathe Korea Institute of Science and Technology(KIST)Institutional Program(Grant No.2E26291)Flag Program(Grant No.2E26300)the Research Grants of NRF funded by the National Research Foundation under the Ministry of Science,ICT&Future,Korea(Grant No.NRF-2015H1D3A1036078)
文摘Hydrogen spillover mechanism of metal-supported covalent-organic frameworks COF-105 is investigated by means of the density functional theory, and the effects of metal catalysts M_4（Pt_4, Pd_4, and Ni_4） on the whole spillover process are systematically analyzed. These three metal catalysts exhibit several similar phenomena：（i） they prefer to deposit on the tetra（_4-dihydroxyborylphenyl） silane（TBPS） cluster with surface-contacted configuration;（ii） only the H atoms at the bridge site can migrate to 2,3,6,7,10,11-hexahydroxy triphenylene（HHTP） and TBPS surfaces, and the migration process is an endothermic reaction and not stable;（iii） the introduction of M_4 catalyst can greatly reduce the diffusion energy barrier of H atoms, which makes it easier for the H atoms to diffuse on the substrate surface. Differently, all of the H2 molecules spontaneously dissociate into H atoms onto Pt_4 and Pd_4clusters. However, the adsorbed H2 molecules on Ni_4 cluster show two types of adsorption states： one activated state with stretched H–H bond length of 0.88 ？A via the Kubas interaction and five dissociated states with separated hydrogen atoms. Among all the M_4 catalysts, the orders of the binding energy of M_4 deposited on the substrate and average chemisorption energy per H2 molecule are Pt_4〉Ni_4〉Pd_4. On the contrary, the orders of the migration and diffusion barriers of H atoms are Pt_4
基金support of NSFC(21871167)1331 Project of Shanxi,Shanxi Province Science Foundation for Youths(201901D211391)+1 种基金research project supported by Shanxi Scholarship Council of China(2020-088)the Technology Innovation Team(CX201904).
文摘A sequential improvement strategy has been devised and implemented on a 3D open framework In-BQ showing 2D intersected channels filled by dimethylamine and its protonated cation constructed by-COOCH_(3)-functionalized anilicate linkers.In situ aliovalent metal substitution and post-synthetic ligand esterolysis led to Cd-BQ-COOH with a doubling of Me_(2)NH_(2)^(+)carriers and a great number of residual-COOH groups,resulting in maximum proton concentration and frequent jumping sites.As a result,the modified Cd-BQ-COOH exhibits a 300-fold enhanced value of proton conductivity compared with that of pristine In-BQ,reaching 6.06×10^(-2) S cm^(-1).MD calculations reveal that the entire process of proton transportation in Cd-BQ-COOH is achieved by the vehicle mechanism.
基金supported by the National Natural Science Foundation of China(Grant No.21401055,21371150 and 21201062)Hunan Provincial Natural Science Foundation of China(Grant No.2018JJ2113 and 2017JJ2095)State Key Laboratory of Coordination Chemistry(Grant No.SKLCC1417).
文摘The high porosity,excellent water stability and optimized supramolecular host–vip interactions of MOFs are the three key factors for their potential practical applications in many important areas including gas storage/separation,catalysis and so on.In this study,we designed and constructed a highly porous(3,36)-connected txt-type acylamide-functionalized metal–organic framework(HNUST-8)from a pyridine-based acylamide-linking diisophthalate and dicopper(II)-paddlewheel clusters.
基金supported by the National Natural Science Foundation of China(NSFC, No. 21771191)the Taishan Scholar Foundation(No. ts201511019)+1 种基金the Shandong Natural Science Fund (No.ZR2017QB012)the Fundamental Research Funds for the Central Universities(Nos.16CX05015A,18CX06003A,YCX2018071)
文摘Two Co(II)-MOFs with different structures were successfully synthesized under the premise of designing two ligands containing alkynyl functional groups. Complexes 1 ([Co(TEPA)(TPT)2/3]·2DMF·H2O) and 2 ([Co(EPA)(TPT)]·1.5DMF·1.5H2O) show excellent luminescence properties. Meanwhile, as fluorescent sensors, complexes 1 and 2 exhibit selectivity and sensitivity for Fe3+ with the Ksv of 1.520 ×104 L/mol and 3.543 ×104 L/mol, which can rapidly detect nitroaromatic compounds in methanol and ethanol, especially for 2,4-NPH through fluorescence quenching with high quenching efficiency. In particular, the Ksv value of complexes 1 and 2 towards 2,4-NPH can reach up to 1.627 ×105 L/mol and 9.600 ×104 L/mol, demonstrating that complexes 1 and 2 are good candidates for the identification and detection of Fe3+and nitroaromatic compounds.
