Solvent-Induced In(III)-MOFs with Controllable Interpenetration Degree Performing High-Efficiency Separation of CO2/N2 and CO2/CH4.

Herein, three In(III)-based metal-organic frameworks (In-MOFs) with different degrees of interpenetration (DOI), namely In-MOF-1, In-MOF-2, and In-MOF-3, constructed by In3+ and Y-shaped ligands 4,4',4″-s-triazine-2,4,6-triyltribenzoate (H3TATB), are successfully synthesized through the ionothermal/solvothermal method. Subsequently, three novel In-MOFs, including noninterpenetration polycatenation, 2-fold interpenetrated, and 4-fold interpenetrated structure, are employed as the platform for systematically investigating the separation efficiency of CO2/N2, CO2/CH4, and CO2/CH4/N2 mixture gas system. Among them, In-MOF-2 shows the highest CO2 uptake capacities at 298 K and simultaneously possesses the low adsorption enthalpy of CO2 (26.4 kJ/mol at low coverage), a feature desirable for low-energy-cost adsorbent regeneration. The CO2/N2 (v: v = 15/85) selectivity of In-MOF-2 reaches 37.6 (at 298 K and 1 bar), also revealing outstanding selective separation ability from flue gases and purifying natural gas, affording a unique robust separation material as it has moderate DOI and pore size. In-MOF-2 shows exceptional stability and feasibility to achieve reproducibility. Aperture adjustment makes In-MOF-2 a versatile platform for selectively capturing CO2 from flue gases or purifying natural gas.

Fabrication of Cu-MOF-Derived Cu/CuxO/C Bifunctional Materials for Light and Dark Catalytic Properties.

Metal-organic frameworks (MOFs) are self-assembled constitutive precursors and efficient self-sacrificial templates with metal ions/clusters and organic linkers from which multifunctional materials with carbon nanostructures can be derived. In this study, we synthesized a novel Cu-MOF with Cu(II) as the central metal ion through two ligands, N,N'-bis(pyridin-3-yl)terephthalamide (3-bpta) and fumaric acid (H2FA), which was used as a template for derivatizing carbon-based nanostructured materials of Cu and CuxO through doping with different materials (melamine, urea, and TiO2) in a simple and efficient one-step pyrolysis. The Cu/CuxO-1 catalyst possesses both dark-catalyzed degradation activity and photocatalytic reduction activity during water purification due to the hole-transfer ability between Cu+ and Cu2+ and its inhibition of electron-hole complexation. In the absence of light, force, and cocatalyst, it can also effectively remove azo dyes in water and effectively reduce Cr(VI) under the action of visible light; therefore, Cu/CuxO-1 can be used as a new type of bifunctional material for the removal of pollutants in water, which has a broad prospect.

Fabrication of carbon-based materials derived from a cobalt-based organic framework for enhancing photocatalytic degradation of dyes.

The pyrolysis of metal-organic frameworks (MOFs) has emerged as a promising route to synthesize carbon/metal oxide-based materials with diverse phase compositions, morphologies, sizes and surface areas. In this paper, 1,3,5-benzoic acid (BTC) and 2,4,6-tri(4-pyridinyl)-1-pyridine (TPP) were used as ligands to prepare a novel cobalt-based MOF (Co-MOF) which was used as a precursor to obtain five carbon-based materials at different temperatures (Co-C200/400/600/800/1000). Furthermore, five dyes were used as degradation targets to investigate the photocatalytic degradation performance of the title materials under UV light irradiation. Co-C1000 exhibited the best photocatalytic degradation performance for methyl orange (MO), and the degradation rate could reach 99.21%. The enhanced photocatalytic activity was attributed to narrower band-gaps and a synergistic effect originating from the well-aligned straddling band structures between Co/CoO/Co3O4 and C, also resulting in a faster interfacial charge transfer during the photocatalytic reaction. This study will aid in the development of photocatalysts generated from carbon-based materials via the pyrolysis transformation of MOFs, therefore greatly enhancing the photocatalytic performance.

Fabrication of Metal-Organic Framework-Based Mixed-Matrix Membranes by "Soft Spray" Technique.

Metal-organic framework (MOF)-based mixed-matrix membranes (MMMs) represent a class of composite membranes that seamlessly integrate the properties of MOF fillers and polymer matrix into a hybrid system and have been widely used in countless advanced technologies. However, there remains a need for scalable and simple manufacturing techniques that can fabricate a MOF-based MMM with uniform dispersion. Herein, a series of MMMs with well-dispersed MOFs are constructed by a soft spray technique. In brief, by uniformly spraying metal ions onto the surface of a mixed solution containing polyvinylpyrrolidone (PVP) and organic ligands, a free-standing MMM is synthesized at the miscible liquid-liquid interface, facilitated by the dual function of metal ions. Moreover, soft spray technology can also introduce multifunctional materials into the MMM to customize performance. We have successfully introduced carbon black into a MOF-based MMM by soft spray, resulting in MMMs with excellent photothermal effects. The resulted MOF-based MMM exhibits favorable catalytic performance in the condensation reaction of benzaldehyde with primary amines, and the MOF-based MMM modified with carbon black significantly boosts the endothermic CO2 conversion. The work opens a new avenue for the development of MOF-based MMMs with a promising future.

Fabrication of nanofibrous membranes decorated with metal-organic frameworks for detection of pollutants in water.

The environmental pollution caused by antibiotics, Fe3+ and MnO4- pollutants is becoming increasingly serious. Polyacrylonitrile (PAN) and polymethyl methacrylate (PMMA) were used and decorated with metal-organic frameworks (MOFs) to fabricated three kinds of nanofibrous membranes (NFMs) with different shapes and sizes were prepared by electrospinning technology using in situ growth method and mixed spinning method. The structures and properties of the above three kinds of NFMs were characterized. Among them, PAN@Co/Mn-MOF-74 NFM prepared by in-situ growth method based on PAN was a kind of nano-fluorescent NFM sensor with uniform structure and good fluorescence performance. It showed unique specificity and excellent sensitivity in the detection of ORN, Fe3+ and MnO4-. Compared with previously reported functionalized MOFs, PAN@Co/Mn-MOF-74 NFM has a lower limit of detection (LOD). This study provides a feasible technical route for the preparation of nano-fluorescent NFMs and the targeted detection of trace metal ions and antibiotics.

Fabrication of a Co-Mo-Based Metal-Organic Framework for Growth of Double-Walled Carbon Nanotubes.

Double-walled carbon nanotubes (DWCNTs) make up a unique class of carbon nanotubes (CNTs) that are particularly intriguing for scientific research and are promising candidates for technological applications. A more precise level of control and greater yields can be achieved via catalytic chemical vapor deposition (CCVD), which involves the breakdown of a carbonaceous gas over nanoparticles. The addition of molybdenum to the system can increase the selectivity with regard to the number of walls that exist in the obtained CNTs. As reported herein, we have designed and synthesized a novel Co-Mo-MOF, [Co(3-bpta)1.5(MoO4)]·H2O (where 3-bpta = N,N'-bis(3-pyridyl)terephthalamide), and employed the Co-Mo-MOF as a bimetallic catalyst precursor for the CCVD approach to prepare high-quality DWCNTs. The Co-Mo-MOF was employed after being calcined in N2 and H2 at 1100 °C and decomposing into CoO, CoMoO4, and MoO3. Existing CoMoO4 is unaltered after reduction in H2 at 1100 °C, while CoO and MoO3 are converted into Co0 and MoO2, and more CoMoO4 is created at the expense of Co0 and MoO2 without clearly defining agglomeration. Finally, the interaction between metallic Co particles and C2H4 is what initiates the formation of DWCNTs. In-depth discussion is provided in this paper regarding the mechanism underlying the high selectivity and activity of Co-Mo catalysts in regulating the development and structure of DWCNTs. The DWCNTs also offer excellence performance when they are used as water purification agents and as selective sorbents. This work opens a feasible way to use MOFs as a way to produce MWCNTs, thus blazing a new trail in the field of MOF-derived carbon-based materials.

Ultrafast and Scalable Fabrication of Coordination Polymer Films on Network Substrates via Thermal Current-Induced Dewetting.

Coordination polymers are among the most favored active materials by researchers due to their broad application prospects. However, most of them are usually difficult to directly process into applicable devices because of their unsatisfied processability. One process of great concern for researchers is the in situ preparation of the coordination polymer on the applicable substrate, especially for the favored network substrates with good mechanical properties and 3D porous structure, which could provide obvious convenience and facilitation in the application process. Herein, we present an ultrafast and scalable thermal current-induced dewetting strategy to obtain uniform coordination polymer film in situ on network substrates, which could enable unprecedented convenience to obtain directly usable coordination polymer composites such as practical catalytic electrodes with excellent electrocatalytic performance. The proposed thermal current-induced dewetting method provides a highly adaptable and efficient practical production approach to integrate coordination polymer materials with network substrates and also provides new inspiration for understanding and applying the dewetting process on complex 3D network substrates.

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.

Fabrication of metal-organic salts with heterogeneous conformations of a ligand as dual-functional urease and nitrification inhibitors.

Urease inhibitors (UIs) and nitrification inhibitors (NIs) can greatly reduce nitrogen loss in agriculture soil. However, design and synthesis of an efficient and environmentally friendly dual-functional inhibitor is still a great challenge. Herein, four metal-organic salts (MOSs) based on heterogeneous conformations of the ligand N1,N1,N2,N2-tetrakis(2-fluorobenzyl)ethane-1,2-diamine (L), namely, [2HL]2+·[MCl4]2- (M = Cu, Zn, Cd, and Co), have been synthesized by the "second sphere" coordination method and structurally characterized in detail. Single crystal X-ray diffraction (SCXRD) analyses reveal that the four MOSs are 0D supramolecular structures containing [2HL]2+ and [MCl4]2-, which are connected through non-covalent bonds. Furthermore, the urease and nitrification inhibitory activities of MOSs are evaluated, showing excellent nitrification inhibitory activity with the nitrification inhibitory rate as high as 70.57% on the 28th day in soil cultivation experiment. In particular, MOS 1 shows significant urease inhibitory activity with half maximal inhibitory concentration (IC50) values of 0.89 ± 0.01 µM (0.5 h) and 1.87 ± 0.01 µM (3 h), which can serve as a dual-functional inhibitor.

Controllable synthesis of copper-organic frameworks via ligand adjustment for enhanced photo-Fenton-like catalysis.

The efficient heterogeneous photo-Fenton-like catalysts based on two secondary ligand-induced Cu(II) metal-organic frameworks (Cu-MOF-1 and Cu-MOF-2) were constructed for the first time and investigated for the degradation of multiple antibiotics. Herein, two novel Cu-MOFs were prepared using mixed ligands by a facile hydrothermal method. The one-dimensional (1D) nanotube-like structure could be obtained by using V-shaped, long and rigid 4,4'-bis(3-pyridylformamide)diphenylether (3-padpe) ligand in Cu-MOF-1, while polynuclear Cu cluster could be prepared more easily by using short and small isonicotinic acid (HIA) ligand in Cu-MOF-2. Their photocatalytic performances were measured by degradation of multiple antibiotics in Fenton-like system. Comparatively, Cu-MOF-2 exhibited superior photo-Fenton-like performance under visible light irradiation. The outstanding catalytic performance of Cu-MOF-2 was ascribed to the tetranuclear Cu cluster configuration and excellent ability of photoinduced charge transfer and hole separation thus improved the photo-Fenton activity. In addition, Cu-MOF-2 showed high photo-Fenton activity in wide pH working range 3-10 and maintained wonderful stability after five cyclic experiments. The degradation intermediates and pathways were deeply studied. The main active species h+, O2- and OH worked together in photo-Fenton-like system and possible degradation mechanism was proposed. This study provided a new approach to design the Cu-based MOFs Fenton-like catalysts.

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 .

Ligand-induced synthesis of two Cu-based coordination polymers and derivation of carbon-coated metal oxide heterojunctions for enhanced photocatalytic degradation.

Photocatalytic degradation of dyes is an extremely difficult but very important issue in the field of environmental protection. Two coordination polymers (CPs) [Cu(3-bpah)(HD)]n (1) and [Cu(3-dpye)0.5(HD)]n (2) [3-bpah = N,N'-bis(3-pyridinecarboxamide)-1,2-cyclohexane, 3-dpye = N,N'-bis(3-pyridinecarboxamide)-1,2-ethane, H2HD = hexanedioic acid] were successfully synthesized by tuning the auxiliary ligands under hydrothermal conditions. CPs 1 and 2 exhibited different compositions because of the different N-donor ligands, and were used as precursors for the preparation of metal oxide heterojunctions. Doping foreign elements into intrinsic CP-based materials is an effective way to enhance their photocatalytic activity, and thus we designed a facile method to synthesize a series of carbon-coated metal oxide heterojunctions which were derived from the two Cu-based CPs (Cu@V-1, Cu@V-2, Cu@Mo-1, Cu@Mo-2, Cu@W-1 and Cu@W-2) in this work for the first time. Benefiting from the formation of a carbon shell and regulation of the electronic structure through doping molybdenum and generating the Mo2C phase, the photocatalytic degradation rates were 94.84% for MB, 76.02% for RhB, 52.29% for MO, and 86.18% for CR after 4 h.

Synthesis of a 2D Cu@TiO2 composite via the design of a 1D Cu-based coordination polymer precursor for efficient and selective photodegradation of dyes.

A 2D Cu@TiO2 composite with a porous and crystalline structure was successfully synthesized via one-step and low-temperature calcination of a 1D Cu-based coordination polymer (Cu-CP), namely [Cu2(3-dpha)(1,4-NDC)2(H2O)3] n (3-dpha = N,N'-bis(3-pyridyl)adipamide and 1,4-H2NDC = 1,4-naphthalenedicarboxylic acid). Moreover, the Cu@TiO2 membrane was fabricated by a simple filtration of the as-grown Cu@TiO2 composite. Compared with the benchmark TiO2 photocatalyst, the Cu@TiO2 composite material with high specific surface area and reduced photogenerated electron-hole ratio exhibited good photodegradation activity and durability for gentian violet (GV), which could be attributed to the combined effect of co-doping of Cu and TiO2 structure. Furthermore, the ˙OH and ˙O2 - radicals were predicted to dominate the photocatalytic process. Therefore, this new efficient photocatalyst is a promising candidate for efficient and selective photodegradation of organic pollutants.

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.

Preparation of diameter-controlled free-standing MWCNT membranes and their application for dye adsorption.

The synthesis of multi-walled carbon nanotubes (MWCNTs) was carried out over different Ni-loaded metallic oxide catalyst nanoparticles and under different reduction times to control the outside diameter of the nanotubes. Moreover, high-purity, free-standing membranes were fabricated by a simple filtration of the as-grown MWCNTs. Furthermore, the dye-adsorption properties of the nanotubes depended on the diameter of the carbon nanotubes (CNTs). The adsorption isotherms and kinetics of anionic dyes could be described by Freundlich and pseudo-second-order models, respectively. Thermodynamic studies suggested that the adsorption processes were spontaneous and exothermic. This work provides new insights into the synthesis and application of MWCNTs with the selective adsorption properties of carbon-based materials for the removal of organic dyes.

Organocatalytic sulfa-Michael/aldol cascade: constructing functionalized 2,5-dihydrothiophenes bearing a quaternary carbon stereocenter.

A practical sulfa-Michael/aldol cascade reaction of 1,4-dithiane-2,5-diol and α-aryl-ß-nitroacrylates has been developed, which allows efficient access to functionalized 2,5-dihydrothiophenes bearing a quaternary carbon stereocenter in moderate to good yields with high enantioselectivities.

Fabrication of Monodisperse Flower-Like Coordination Polymers (CP) Microparticles by Spray Technique.

In this manuscript, we have developed an efficient spraying method to successfully fabricate a series of flower-like coordination polymers (CP) microparticles, including Co/BDC (1,4-benzenedicarboxylate) metal organic frameworks (MOF) and infinite coordination polymers (ICP) microparticles, as well as Ni-Co/BDC MOF and Zn/DOBDC (2,5-dioxido-1,4-benzenedicarboxylate) MOF. The spraying method has shown high efficiency and universality in synthesizing the flower-like CP. The crystalline structure can be adjusted by varying the solvent composition in the spraying process. SEM observation demonstrated the MOF and ICP microparticles possess the similar flower-like structure, which is composed of nanoflakes with smooth surface, and the flower-like microparticles could be monodisperse with as low as 5% polydispersity. Moreover, the fabrication of the flower-like CP microparticles by spraying has a wide operation window, because there is no need to precisely control the experiment conditions, like solvents, concentration, and spray order. Due to the practicality of spray technique, this work would pave the way for the manufacture of the flower-like materials and have great potential in applications of catalysis, sensor, energy storage, and so on.

Stirring-assisted assembly of nanowires at liquid-solid interfaces.

The assembly of Ag nanowires on quartz substrates from suspensions of water and ethylene glycol under stirring has been investigated. The introduction of stirring makes a remarkable difference to the assembly morphology. Firstly, the surface coverage of Ag nanowires is increased by a factor of 4 (in water) and 8 (in ethylene glycol) with stirring. Secondly, the Ag nanowires assembled in the stirred ethylene glycol dispersion were highly aligned. The influence of the surface of substrates, solvents and profile of the nanowires on the alignment has been explored, which indicates that stirring is an efficient way to generate nanowire arrays. This study has revealed the great potential of the stirring-assisted assembly technique in producing structurally controlled nanoarchitectures, opening up new opportunities for manufacturing ordered nanomaterials.