ABSTRACT
To increase the conductivity of polyoxometalate-based metal-organic frameworks (POMOFs) and promote their applications in the field of energy storage, herein, a simple approach was employed to improve their overall electrochemical performances by introducing a functionalized single-walled carbon nanotubes (SWNT-COOH). A new POMOF compound, [Cu18 (trz)12 Cl3 (H2 O)2 ][PW12 O40 ] (CuPW), was successfully synthesized, then the size-matched functionalized SWNT-COOH was introduced to fabricate CuPW/SWNT-COOH composite (PMNT-COOH) by employing a simple sonication-driven periodic functionalization strategy. When the PMNT-COOH nanocomposite was used as the anode material for Lithium-ion batteries (LIBs), PMNT-COOH(3) (CuPWNC:SWNT-COOH=3:1) showed superior behavior of energy storage, a high reversible capacity of 885â mA h g-1 up to a cycle life of 170 cycles. The electrochemical results indicate that the uniform packing of SWNT-COOH provided a favored contact between the electrolyte and the electrode, resulting in enhanced specific capacity during lithium insertion/extraction process. This fabrication of PMNT-COOH nanocomposite opens new avenues for the design and synthesis of new generation electrode materials for LIBs.
ABSTRACT
In order to explore novel colorimetric biosensors with high sensibility and selectivity, two new Keggin polyoxometalates (POMs)-based Cu-trz (1,2,4-triazole) metal-organic frameworks (MOFs) with suitable specific surface areas and multiple active sites were favorably fabricated; then single-walled carbon nanotubes (SWNTs) were merged with new POMOFs to construct POMOF/SWNT nanocomposites. Herein, POMOF/SWNT nanocomposites as peroxidase mimics were explored for the first time, and the peroxidase-mimicking activity of the prepared POMOF/SWNT nanocomposites is heavily dependent on the mass ratio of POMOFs and SWNTs, in which the maximum activity is achieved at the mass ratio of 2.5:1 (named PMNT-2). More importantly, PMNT-2 exhibits the lowest limit of detection (0.103 µM) among all reported materials to date and the assumable selectivity toward l-cysteine (l-Cys) detection. With these findings, a convenient, sensitive, and effective "on-off switch" colorimetric platform for l-Cys detection has been successfully developed, providing a promising prospect in the biosensors and clinical diagnosis fields.
Subject(s)
Biosensing Techniques , Colorimetry/methods , Cysteine/isolation & purification , Nanotubes, Carbon/chemistry , Catalysis , Copper/chemistry , Cysteine/chemistry , Metal-Organic Frameworks/chemistry , Nanocomposites/chemistry , Oxidation-Reduction , Peroxidase/chemistry , Triazoles/chemistry , Tungsten Compounds/chemistryABSTRACT
Two new polyoxometalate (POM)-based three-dimensional metal organic carbene frameworks, [Ag10(trz)4(H2O)2][HPW12O40] (POMs@MCNCs-1) and [Ag10(trz)4(H2O)6][H2SiW12O40] (POMs@MCNCs-2), were hydrothermally synthesized, in which Keggin-type polyoxoanions as templates induce the formation of two different kinds of metal-carbene nanocages (MCNCs) for the first time. Combination of the reversible multielectron redox behavior and electron storage functions of POMs with the good electrical conductivity of the single-walled carbon nanotubes (SWNTs) renders the POMs@MCNCs-1/SWNT composite excellent electrochemical performance and good stability as anode materials of lithium-ion batteries, with up to 2000 mA h g-1 for the first discharge capacity and ca. 859 mA h g-1 for the second cycle at a current density of 100 mA g-1. The successful fabrication of unprecedented MCNCs into the POM-based three-dimensional metal-organic frameworks in the present work must initiate extensive research interests in diverse fields.
ABSTRACT
For exploring the multifold helical fabrication of polyoxometalate (POM)-based hybrid compounds, four POM-based crystalline compounds with different meso-helices, H3[Ag27(trz)16(H2O)6][SiW12O40]2·5H2O (1), H[Ag27(trz)16(H2O)4][PW12O40]2·2H2O (2), [Ag23(trz)14(H2O)2][HSiW12O40] (3), and [Ag23(trz)14(H2O)2][PW12O40] (4), were successfully isolated by using the delicate 1,2,3-triazole ligand and silver ions in this work. Crystal analysis reveals that compounds 1 and 2 and compounds 3 and 4 are isomorphous and display 2-/4-fold mixed meso-helices and simple 2-fold meso-helices, respectively. In addition, due to the reversible multielectron redox behavior and electron storage functions of POMs, compounds 1 and 3 were studied as anode materials in lithium-ion batteries (LIBs). Compounds 1 and 3 show very high lithiation capacities (1356 and 1140 mAh g-1, respectively) in the initial cycle, which are much higher than those of (NBu4)4[SiW12O40] and commercial graphite at the current density of 100 mA g-1. More importantly, both compounds also show good stable performance after 100 cycles.
ABSTRACT
Two extremely rare ß-cyclodextrin (ß-CD) supported metal-organic frameworks (MOFs), CD-MOF-1 and CD-MOF-2, were induced to crystallize for the first time through a template-induced approach. The targeted CD-MOFs were employed to perform controlled drug delivery and cytotoxicity assays that confirmed their favourable biological potential of being used as drug carriers.
Subject(s)
Biological Products/chemistry , Drug Delivery Systems , Metal-Organic Frameworks/chemistry , Biocompatible Materials/chemistry , Cell Survival/drug effects , Dose-Response Relationship, Drug , Drug Carriers/chemistry , Hep G2 Cells , Humans , Models, Molecular , Particle Size , Porosity , Structure-Activity Relationship , Surface Properties , beta-Cyclodextrins/chemistryABSTRACT
A series of remarkable crystalline compounds containing metallapillararene/metallacalixarene metal-organic frameworks (MOFs), [Ag5(pyttz)3·Cl·(H2O)][H3SiMo12O40]·3H2O (1), [Ag5(trz)6][H5SiMo12O40] (2), [Ag5(trz)6][H5GeMo12O40] (3), and [Ag5(trz)6][H4PW12O40] (4) (pyttz = 3-(pyrid-4-yl)-5-(1H-1,2,4-triazol-3-yl)-1,2,4-triazolyl, trz = 1,2,4-triazole), have been obtained by using a simple one-step hydrothermal reaction of silver nitrate, pyttz for 1 and trz for 2-4, and Keggin type polyoxometalates (POMs). Crystal analysis reveals that Keggin POMs have been successfully incorporated in the windows of the metallapillararene/metallacalixarene MOFs in compounds 1-4. In addition, the Keggin silicomolybdenate-based hybrid compounds 1 and 2 were used as anode materials in lithium ion batteries (LIBs), which exhibited promising electrochemical performance with the first discharge capacities of 1344 mAh g-1 for 1 and 1452 mAh g-1 for 2, and this stabilized at 520 mAh g-1 for 1 and 570 mAh g-1 for 2 after 100 cycles at a current density of 100 mA g-1. The performances are better than that of (NBu4)4[SiMo12O40] matrix and commercial graphite anodes.
