Fabrication of bimetallic-doped materials derived from a Cu-based complex for enhanced dye adsorption and iodine capture.

In this work, we used Cu(II) ions, a bis-pyridyl-bis-amide ligand [N,N'-bis(4-pyridinecarboxamide)-1,2-cyclohexane (4-bpah)], and an aromatic dicarboxylic acid [1,4-cyclohexanedicarboxylic acid (H2CHDA)] to construct a 1D binuclear Cu-based complex, namely {[Cu3(4-bpah)(CHDA)3(H2O)]·2H2O}n (1). Moreover, we also developed a facile method to synthesize two monometallic/bimetallic-doped materials which were derived from the Cu complex (C-N-1 and C-V-1, which were doped with nitrogen and vanadium, respectively). The as-synthesized derived materials were fully characterized and the iodine sorption/release capabilities were investigated in detail. We performed iodine adsorption experiments on the two monometallic/bimetallic-doped materials and found that C-N-1 and C-V-1 possess highly efficient adsorption activities for the adsorption of iodine from solution. The C-N-1 and C-V-1 complexes exhibited remarkable adsorption capacities of 1141.60 and 1170.70 mg g-1, respectively, for iodine from a cyclohexane solution. Moreover, the dye adsorption properties of C-N-1 and C-V-1 were also investigated in detail. The obtained C-N-1 and C-V-1 exhibit effective dye uptake performances in water solution. The adsorption of Congo red (CR) on a single metal carbon material C-N-1 doped with heteroatoms reached equilibrium within 240 min and reached an adsorption capacity of 1357.00 mg g-1 and the adsorption capacities of C-V-1 for methylene blue (MB), gentian violet (GV), rhodamine B (RhB), and CR at room temperature were found to be 187.60, 190.60 and 108.10 and 1501.00 mg g-1 in 180 min, respectively. By comparison, we found that doping vanadium could play an important role in the adsorption processes. The adsorption capacity of C-V-1 (containing the vanadium in its structure) was relatively higher than that of C-N-1, which indicated that the introduction of non-noble metals may effectively tune the adsorption kinetics activity and the introduction of noble metals can change the surface electronegativity of porous carbon materials, thus leading to significantly improved adsorption capabilities.

A Novel Azo-Linked Polymer Bearing Trifluoromethyl Groups for I2 Capture.

In this work, a novel three nitro-group-bearing monomer 3,6-dinitro-9-(2-trifluoromethyl-4-nitrophenyl)-carbazole (Car-3NO2 -CF3 ) via a CN coupling reaction between 3,6-dinitro-9H-carbazole (Car-2NO2 ) and 2-chloro-5-nitrobenzotrifluoride is synthesized, and obtained single crystal and single crystal analysis data for this compound. The crystal system of Car-3NO2 -CF3 is monoclinic and it has a P 21/c space group. This new monomer (Car-3NO2 -CF3 ) is also utilized to synthesize a novel azo-linked polymer (Azo-Car-CF3 ). The trifluoromethyl group has polar CF bonds, and thus it is an effective functional group for the capture of iodine. Azo-Car-CF3 has great thermal stability with a mass loss of only 10% at 414 °C, as well as good chemical stability as is demonstrated by its low solubility in common organic solvents such as tetrahydrofuran (THF), acetone, methanol, ethanol, and N,N-dimethylformamide (DMF). The specific surface area of Azo-Car-CF3 can reach as high as 335 m2  g-1 . Azo-Car-CF3 exhibits an excellent capacity for iodine adsorption and can reach up to 1198 mg g-1 in cyclohexane solution, and its adsorption capacity for iodine vapor can get to 2100 mg g-1 . In addition, ethanol can be used to trigger the release of the captured iodine to be easily released from Azo-Car-CF3 .

Cu-Organic framework-derived V-doped carbon nanostructures for organic dye removal.

Metal-organic frameworks (MOFs) have recently emerged as a type of uniformly and periodically atom-distributed precursor and efficient self-sacrificial template to fabricate hierarchical porous-carbon-related nanostructured functional materials. In this work, we used Cu(II) ions and aromatic dicarboxylic acid to construct [Cu3(4,4'-oba)2(µ2-OH)2(H2O)2]n (4,4'-H2oba = 4,4'-oxybisbenzoic acid) as a precursor for the preparation of carbon nanostructures. Doping foreign elements into intrinsic MOF-based nanomaterials is an effective way to enhance the adsorption property and photocatalytic activity; thus, we designed a facile method to synthesize a vanadium-doped mixture of Cu2O and Cu nanoparticles encapsulated in a Cu-MOF-derived carbon nanostructure (C-V-1) in this work for the first time. Benefiting from the protection of the carbon shell and regulation of the electronic structure by doping vanadium and phase-mixing Cu2O and Cu, the adsorption capacities of C-V-1 for MB, RhB, MO, CR and GV at room temperature are 174.13, 147.06, 179.92, 275.90 and 611.81 mg g-1 in 240 min, respectively, while the photocatalytic degradation rates are 88.14% for MB, 79.80% for RhB, 71.31% for MO, and 71.19% for CR after 4 h. In addition, the degradation rate is larger than 99.01% for GV after only 30 min of UV irradiation. This strategy of using a diverse MOF as a structural and compositional material to create a multifunctional composite/hybrid may expand the opportunities to explore highly efficient, fast and robust adsorbents and photocatalysts for water treatment.

A novel 3D Zn-coordination polymer based on a multiresponsive fluorescent sensor demonstrating outstanding sensitivities and selectivities for the efficient detection of multiple analytes.

A novel and unusual 3D luminescent coordination polymer (CP) [Zn2(3-bpah)(bpta)(H2O)]·3H2O (1), where 3-bpah denotes N,N'-bis(3-pyridinecarboxamide)-1,2-cyclohexane and H4bpta denotes 2,2',4,4'-biphenyltetracarboxylic acid, was successfully synthesized via hydrothermal methods from Zn(II) ions and 3-bpah and bpta ligands. The structure of this CP was investigated via powder X-ray diffraction (PXRD) analysis along with single crystal X-ray diffraction. Notably, 1 exhibits remarkable fluorescence behavior and stability over a wide pH range and in various pure organic solvents. More importantly, 1 can become an outstanding candidate for the selective and sensitive sensing of Fe3+, Mg2+, Cr2O72-, MnO4-, nitrobenzene (NB) and nitromethane (NM), at an extremely low detection limit. The changes in the fluorescence intensity exhibited by these six analytes in the presence of 1 over a wide pH range indicate that this polymer can be an excellent luminescent sensor. To the best of our knowledge, 1 is a rare example of a CP-based multiresponsive fluorescent sensor for metal cations, anions, and toxic organic solvents.

Efficient and selective removal of Congo red by a C@Mo composite nanomaterial using a citrate-based coordination polymer as the precursor.

To research the effect of structural diversity on citrate-based coordination polymers (CPs), citric acid (H4cit) was selected to combine with Cu(ii) under hydrothermal conditions. A new CP [Cu2(cit)(H2O)2] (1) was synthesized and structurally characterized. The title complex shows a 3D 2,4,6-connected topology with the point symbol of {43·63}{44·66·85}{4}. Inspired by the decomposition and functional molybdenum component, 1 was used as a catalyst precursor to synthesize a carbon-based material (C-1) and a C@Mo material (C-Mo-1) by the chemical vapor deposition (CVD) method and characterized in detail. The selective removal of a contaminant (Congo red) by complex 1, C-1 and C-Mo-1 in the aqueous phase was also comparatively investigated.