Metal-organic framework-mediated construction of confined ultrafine nickel phosphide immobilized in reduced graphene oxide with excellent cycle stability for asymmetric supercapacitors.

Transition metal phosphides (TMPs) with unique metalloid features have been promised great application potential in developing high-efficiency electrode materials for electrochemical energy storage. Nevertheless, sluggish ion transportation and poor cycling stability are the critical hurdles limiting their application prospects. Herein, we presented the metal-organic framework-mediated construction of ultrafine Ni2P immobilized in reduced graphene oxide (rGO). Nano-porous two-dimensional (2D) Ni-metal-organic framework (Ni-MOF) was grown on holey graphene oxide (Ni(BDC)-HGO), followed by MOF-mediated tandem pyrolysis (carbonization and phosphidation; Ni(BDC)-HGO-X-P, X denoted carbonization temperature and P represented phosphidation). Structural analysis revealed that the open-framework structure in Ni(BDC)-HGO-X-Ps had endowed them with excellent ion conductivity. The Ni2P wrapped by carbon shells and the PO bonds linking between Ni2P and rGO ensured the better structural stability of Ni(BDC)-HGO-X-Ps. The resulting Ni(BDC)-HGO-400-P delivered a capacitance of 2333.3 F g-1 at 1 A g-1 in a 6 M KOH aqueous electrolyte. More importantly, Ni(BDC)-HGO-400-P//activated carbon, the assembled asymmetric supercapacitor with an energy density of 64.5 Wh kg-1 and a power density of 31.7 kW kg-1, almost maintained its initial capacitance after 10,000 cycles. Furthermore, in situ electrochemical-Raman measurements were exploited to demonstrate the electrochemical changes of Ni(BDC)-HGO-400-P throughout the charging and discharging processes. This study has further shed light on the design rationality of TMPs for optimizing supercapacitor performance.

Template-directed synthesis of pomegranate-shaped zinc oxide@zeolitic imidazolate framework for visible light photocatalytic degradation of tetracycline.

The development of photocatalysts for efficient tetracycline (TC) degradation under visible light is urgently needed yet remains a great challenge. Most semiconductor photocatalysts with low specific surface area are easy to agglomerate in solution and unfavorable for enriching pollutants. Herein, we present the preparation of pomegranate-shaped zinc oxide@zeolitic imidazolate framework (ZnO@ZIF-8) by in situ growth of ZIF-8 on a petal-shaped ZnO template that enhances the adsorption and photocatalytic degradation of TC. ZnO@ZIF-8 exhibits an excellent photostability and a TC photodegradation efficiency of 91% under visible light (λ > 420 nm) in 50 min at room temperature, which can be recycled over five times without any loss of activity. Moreover, the plausible photocatalysis reaction mechanism and the degradation intermediates are elucidated with the aid of three-dimensional excitation-emission matrix spectra and liquid chromatography-mass spectrometry system. This study offers new insights into the design of antibiotic degradation photocatalysts and the development of photocatalysts with broad-spectrum responses for efficient TC elimination.

Hydrophilicity gradient in covalent organic frameworks for membrane distillation.

Desalination can help to alleviate the fresh-water crisis facing the world. Thermally driven membrane distillation is a promising way to purify water from a variety of saline and polluted sources by utilizing low-grade heat. However, membrane distillation membranes suffer from limited permeance and wetting owing to the lack of precise structural control. Here, we report a strategy to fabricate membrane distillation membranes composed of vertically aligned channels with a hydrophilicity gradient by engineering defects in covalent organic framework films by the removal of imine bonds. Such functional variation in individual channels enables a selective water transport pathway and a precise liquid-vapour phase change interface. In addition to having anti-fouling and anti-wetting capability, the covalent organic framework membrane on a supporting layer shows a flux of 600 l m-2 h-1 with 85 °C feed at 16 kPa absolute pressure, which is nearly triple that of the state-of-the-art membrane distillation membrane for desalination. Our results may promote the development of gradient membranes for molecular sieving.

Blue luminescent N,S-doped carbon dots encapsulated in red emissive Eu-MOF to form dually emissive composite for reversible anti-counterfeit ink.

Lanthanide metal-organic frameworks (Ln-MOFs) have demonstrated great potential in luminescence sensing and optical anti-counterfeiting. High-security anti-counterfeiting technology is of great importance and requires the development of universal luminescent materials with multiple modes of emission and adjustable photoluminescence. Herein, a 3D red light emission microporous europium(iii) metal-organic framework [Eu3(OH)(1,3-db)2(H2O)4]·3H2O (1) (1,3-db = 1,3-di(3',5'-dicarboxylpheny) benzene) was constructed from a zigzag [Eu3(COO)8] chain and π-electron-rich terphenyl-tetracarboxylate. Notably, the quenched fluorescence of 1 under hydrogen chloride vapor could be recovered upon fuming by a vapor of Et3N. Most strikingly, the strong blue light emission by nitrogen and sulfur co-doped carbon dots (N,S-CDs) could be encapsulated in 1 to generate a dual-emission composite, namely, N,S-CDs@Eu-MOF, which shows solvent-dependent photoluminescence: N,S-CD-related blue luminescence in water and Eu-MOF-related red emission in organic solvents. Taking advantage of the above unique reversible fluorescent behavior, Eu-MOF and N,S-CDs@Eu-MOF are prepared as fluorescent high-security inks to achieve data encryption and decryption on specific flower patterns.

Molecular-Sieving Membrane by Partitioning the Channels in Ultrafiltration Membrane by In†Situ Polymerization.

Commercial ultrafiltration membranes have proliferated globally for water treatment. However, their pore sizes are too large to sieve gases. Conjugated microporous polymers (CMPs) feature well-developed microporosity yet are difficult to be fabricated into membranes. Herein, we report a strategy to prepare molecular-sieving membranes by partitioning the mesoscopic channels in water ultrafiltration membrane (PSU) into ultra-micropores by space-confined polymerization of multi-functionalized rigid building units. Nine CMP@PSU membranes were obtained, and their separation performance for H2 /CO2 , H2 /N2 , and H2 /CH4 pairs surpass the Robeson upper bound and rival against the best of those reported membranes. Furthermore, highly crosslinked skeletons inside the channels result in the structural robustness and transfer into the excellent aging resistance of the CMP@PSU. This strategy may shed light on the design and fabrication of high-performance polymeric gas separation membranes.

Copper(II) 1,4-naphthalenedicarboxylate on copper foam nanowire arrays for electrochemical immunosensing of the prostate specific antigen.

Nanowires of copper(II)-based metal-organic frameworks (Cu-MOFs) of type Cu(II)(1,4-naphthalenedicarboxylic acid) (1,4-NDC) were deposited on the surface of a copper foam by immersion of Cu(OH)2 nanowires in a solution of 1,4-NDC. An electrochemical immunosensor for the prostate specific antigen (PSA) is obtained by using the nanowire arrays as a redox signal probe. The signal is generated by the conversion of Cu(I) and Cu(II) of Cu-MOFs nanowires. Cu(1,4-NDC) nanowires contain many uncoordinated carboxyl groups which can bind to the amino groups of the PSA antibody. When PSA antibody binds to PSA antigen during an immune response, the current signal will decrease due to the electrical insulation of PSA antigen. The decrease of current is directly proportional to the increase of PSA concentration. The immunosensor, best operated at a voltage of typically -0.08 V (vs. Ag/AgCl), has a low limit of detection (4.4 fg·mL-1) and a wide linear range (0.1 pg·mL-1 to 20 ng·mL-1). This meets the demands of clinical diagnosis (with values <4 ng·mL-1) in serum. The method was applied to the determination of PSA in spiked serum. Graphical abstractSchematic representation of the in-situ growth of ordered Cu-MOFs wrapped with Cu(OH)2 nanowires, building the core-shell structure as the 3D electrode. A novel electrochemical immunosensor for PSA detection has been exploited, using the Cu-MOFs nanowire arrays on Cu foam as a redox signal probe for the first time.

Membrane adsorbers with ultrahigh metal-organic framework loading for high flux separations.

Metal-organic frameworks (MOFs) with high porosity and designable functionality make it possible to access the merits of high permeability and selectivity. However, scalable fabrication methods to produce mixed matrix membranes (MMMs) with good flexibility and ultrahigh MOF loading are urgently needed yet largely unmet. Herein, we report a thermally induced phase separation-hot pressing (TIPS-HoP) strategy to roll-to-roll produce 10 distinct MOF-membranes (loadings up to 86 wt%). Ultrahigh-molecular-weight polyethylene interweaving the MOF particles contributes to their mechanical strength. Rejections (99%) of organic dyes with a water flux of 125.7 L m-2 h-1 bar-1 under cross-flow filtration mode. The micron-sized channels between the MOF particles translate into fast water permeation, while the porous MOFs reject solutes through rapid adsorption. This strategy paves ways for developing high-performance membrane adsorbers for crucial separation processes. As a proof-of-concept, the abilities of the membrane adsorbers for separating racemates and proteins have been demonstrated.

Unveiling the relative stability and proton binding of non-classical Wells-Dawson isomers of [(NaF6)W18O54(OH)2]7- and [(SbO6)W18O54(OH)2]9-: a DFT study.

Density functional theory calculations combined with the energy and building-block decomposition analyses have been carried out to investigate the structures, stability orders, redox potentials and proton binding of the six Baker-Figgis isomers (α, ß, γ, α*, ß* and γ*) of [(SbO6)W18O54(OH)2]9- {H2SbW18} and [(NaF6)W18O54(OH)2]7- {H2NaW18} anions at the level of PBEsol-D3/TZP. Both bonding energy and Gibbs free energy analyses exhibit that the two non-classical Wells-Dawson (WD) species behave quite differently from each other. The pyroanimonate {H2SbW18}, with a stability order of γ* > ß* > α > α* > ß > γ, is a non-classical WD species, while the hexafluoride {H2NaW18} (α > ß > γ > γ* > ß* > α*) is a transition intermediate between classical and non-classical WD types, possessing both non-classical ([XW18O60(OH)2]n-, X = I, Te and W) and classical [Si2W18O62]8- properties. Energy decomposition analyses (EDA) reveal that spatial arrangement (Ehost), host-guest fragment interaction energy (FIE), and structural distortion energy (DE) are three key factors governing the relative stability of isomers; among these, DE is always dominant, while FIE and Ehost are subordinated but are still important. Building-block decomposition analyses (BDA) disclose that the octahedral {MO6} units of the equatorial belt, particularly the staggered belt, are always more distorted than those of the two polar caps inside each structure. The theoretical redox potentials demonstrate that the oxidizing power increases with a trend of α < ß < γ and α* < ß* < γ* for both species, and the first redox potential is closely related to the energy level of the LUMO of each anion. Evaluation of the proton inclusion energies suggests that {H2NaW18} can only embed two protons, while {H2SbW18} may encapsulate four; the number of embedded protons is controlled by both the charge of the heteroatom X and the volume of the tetrahedral {O4}/{OF3} cavity.

Fourfold-Interpenetrated MOF [Ni(pybz)2] as Coating Material in Gas Chromatographic Capillary Column for Separation.

A fourfold interpenetrated diamond-like topological metal-organic framework (MOF), Ni(pybz)2 [pybz = 4-(4-pyridyl)benzoate] was successfully synthesized and fully characterized. This MOF can serve as coating material in gas chromatographic capillary column for the separation of some low boiling point essential oils. The prepared columns have good recognition ability and excellent selectivity toward a series of organic compounds, including alcohols, aldehydes, ketones, carboxylic acid, ethers, ester, and amines. It is found that the strained metal sites, van der Waals interactions, C-H···π attraction, and weak nonclassical hydrogen bond contribute to the recognition and selectivity of prepared columns. The grand canonical Monte Carlo technique is used to simulate the interactions of the adsorbates with MOF. The calculated van der Waals energies agree with the results of gas chromatographic separation.

A Fluorescent Anionic MOF with Zn4(trz)2 Chain for Highly Selective Visual Sensing of Contaminants: Cr(III) Ion and TNP.

Heavy-metal ions and nitroaromatic substances are highly toxic and harmful to human health and the ecological environment. It is an urgent issue to selectively detect and capture these toxic substances. By introducing the triazole ligand to the π-conjugated aromatic carboxylate system and borrowing the organic template open framework idea, a stable fluorescent framework [Me2NH2]4[Zn6(qptc)3(trz)4]·6H2O (1) (H4qptc = terphenyl-2,5,2'5'-tetracarboxylic acid, trz = 1,2,4-triazole) has been successfully synthesized, which features Zn4(trz)2 chain-based 3D anionic structure with channels filled by [Me2NH2]+ cations. It is worth noting that the material exhibits selective adsorption and recyclable detection of heavy-metal Cr3+ ion in aqueous solutions, which may be the synergy from the metal charge, bond ability of metal ions to carboxylate oxygen atom, and soft-hard acid-base properties. Furthermore, it can selectively sense of 2,4,6-trinitrophenol with a large quenching coefficient Ksv of 2.08 × 106 M-1.

A Luminescent Zinc(II) Metal-Organic Framework (MOF) with Conjugated π-Electron Ligand for High Iodine Capture and Nitro-Explosive Detection.

A porous luminescent zinc(II) metal-organic framework (MOF) with a NbO net [Zn2(tptc)(apy)2-x(H2O)x]·H2O (1) (where x ≈ 1, apy = aminopyridine, H4tptc = terphenyl-3,3″,5,5″-tetracarboxylic acid), constructed using paddlewheel [Zn2(COO)4] clusters and π-electron-rich terphenyl-tetracarboxylic acid, has been solvothermally synthesized and characterized. Interestingly, the material displays efficient, reversible adsorption of radioactive I2 in vapor and in solution (up to 216 wt %). The strong affinity for I2 is mainly due to it having large porosity, a conjugated π-electron aromatic system, halogen bonds, and electron-donating aminos. Furthermore, luminescent study indicated that 1 exhibits high sensitivity to electron-deficient nitrobenzene explosives via fluorescence quenching.

Enhanced Catalysis Activity in a Coordinatively Unsaturated Cobalt-MOF Generated via Single-Crystal-to-Single-Crystal Dehydration.

Hydrothermal reaction of Co(NO3)2 and terphenyl-3,2",5",3'-tetracarboxyate (H4tpta) generated Co3(OH)2 chains based 3D coordination framework Co3(OH)2(tpta)(H2O)4 (1) that suffered from single-crystal-to-single-crystal dehydration by heating at 160 °C and was transformed into dehydrated Co3(OH)2(tpta) (1a). During the dehydration course, the local coordination environment of part of the Co atoms was transformed from saturated octahedron to coordinatively unsaturated tetrahedron. Heterogenous catalytic experiments on allylic oxidation of cyclohexene show that dehydrated 1a has 6 times enhanced catalytic activity than as-synthesized 1 by using tert-butyl hydroperoxide (t-BuOOH) as oxidant. The activation energy for the oxidation of cylcohexene with 1a catalyst was 67.3 kJ/mol, far below the value with 1 catalysts, which clearly suggested that coordinatively unsaturated Co(II) sites in 1a have played a significant role in decreasing the activation energy. It is interestingly found that heterogeneous catalytic oxidation of cyclohexene in 1a not only gives the higher conversion of 73.6% but also shows very high selectivity toward 2-cyclohexene-1-one (ca. 64.9%), as evidenced in high turnover numbers (ca. 161) based on the open Co(II) sites of 1a catalyst. Further experiments with a radical trap indicate a radical chain mechanism. This work demonstrates that creativity of coordinatively unsaturated metal sites in MOFs could significantly enhance heterogeneous catalytic activity and selectivity.

Solvent-free heterogeneous catalysis for cyanosilylation in a dynamic cobalt-MOF.

The butterfly-like tetranuclear cobalt cluster based 3D MOF [Me2NH2][Co2(bptc)(µ3-OH)(H2O)2] (1) underwent a reversible thermally triggered single-crystal-to-single-crystal transformation via Co-Owater weakened intermediate 1a to produce a partly dehydrated phase [Me2NH2][Co2(bptc)(µ3-OH)(H2O)] (2), which was confirmed by single-crystal X-ray diffraction, powder X-ray diffraction, thermogravimetric analysis, and IR spectroscopy. During the dehydration course, the local coordination environment of one Co(2+) ion was changed from the saturated octahedron to a coordinately unsaturated square-pyramid, accompanied by a crystal color change from red to purple. Compared with pristine hydrated 1, dehydrated 2 exhibits highly efficient and recyclable catalytic activity for cyanosilylation of carbonyl compounds with a low catalyst loading of 0.1 mol% Co at room temperature under solvent-free conditions, which due to the open Co(2+) sites as catalytically activated sites played a significant role in the heterogeneous catalytic process.

Planar Mn4O cluster homochiral metal-organic framework for HPLC separation of pharmaceutically important (±)-ibuprofen racemate.

A planar tetracoordinated oxygen containing a homochiral metal-organic framework (MOF) has been synthesized and characterized that can be used as a new chiral stationary phase in high-performance liquid chromatography to efficiently separate racemates such as pharmaceutically important (±)-ibuprofen and (±)-1-phenyl-1,2-ethanediol.

A homochiral magnet based on D3 symmetric [(NaO3)Co3] clusters: from spontaneous resolution to absolute chiral induction.

A pair of novel enantiomeric 3D magnetic complexes [NaCo3(IA)6](NO3)·H2O (1Δ and 1Λ) have been synthesized using an achiral ligand HIA via spontaneous resolution, which crystallize in the hexagonal crystal system with a chiral P63 space group, and diamagnetic sodium cations are located at the center of D3 symmetric clusters. This kind of spontaneous resolution is uncontrollable and dependent on batches. By utilizing cheap enantiopure mandelic acid as a chiral inducing agent, they are driven to controllable homochiral crystallization of the desired enantiomorph, confirmed by circular dichroism spectra.

A perfectly aligned 63 helical tubular cuprous bromide single crystal for selective photo-catalysis, luminescence and sensing of nitro-explosives.

A perfectly aligned 63 helical tubular cuprous bromide single crystal has been synthesized and characterized, which can selectively decompose negatively charged dyes of Methyl Orange (MO) and Kermes Red (KR), and the photocatalytic efficiency is higher than that of nanosized (∼25 nm) TiO2 and ZnO. The direction and magnitude of the dipole moments as well as the band structure were calculated to reveal high photocatalytic efficiency. Moreover, luminescence studies indicate that the CuBr tube materials show very strong yellowish green emissions in the solid state and emulsion even at room temperature, and exhibit extremely high detection sensitivity towards nitro-explosives via fluorescence quenching. Detectable luminescence responses were observed at a very low concentration of 20 ppm with a high quenching efficiency of 94.90%. The results suggest that they may be promising multifunctional materials for photo-catalysis, luminescence and sensing of nitro-explosives.

Heterometallic mixed-valence copper(I,II) cyanides that were tuned by using the chelate effect: discovery of famous Cairo pentagonal tiling and unprecedented (3,4)-connected {8(3)}2{8(6)} topological 3D net.

By using environmentally friendly [Ni(CN)4](2-) as a cyanide source, three new heterometallic cyano-bridged mixed-valence Cu(I)/Cu(II) coordination polymers with three different electronic configurations (d(8)-d(10)), that is, [Cu2Ni(CN)5(H2O)3] (1), [Cu2Ni(CN)5(pn)H2O] (2), and [Cu3Ni(CN)6(pn)2] (3, pn = 1,2-propane diamine) have been synthesized by gradually increasing the amount of pn. Compound 1, which was hydrothermally synthesized in the absence of pn ligand, exhibits the famous 2D Cairo pentagonal tiling, in which the Cu(I), Cu(II), and Ni(II) atoms act as trigonal, T-shaped, and square-planar nodes, respectively. Notably, there are three water molecules located at the meridianal positions of the octahedrally coordinated Cu(II) atom in compound 1. A similar reaction, except for the addition of a small amount of pn, generated a similar Cairo pentagonal tiling layer in which two of the water molecules that were located at the meridianal positions of the octahedrally coordinated Cu(II) atom were replaced by a chelating pn group. Another similar hydrothermal reaction, with the addition of a larger amount of pn, yielded compound 3, which showed a related two-fold-interpenetrated (3,4)-connected 3D framework with an unprecedented {8(3)}2{8(6)} topology in which the Cu(II) atom was chelated by two pn groups. These structural changes between compounds 1-3 can be explained by the chelating effect of the pn group. The replacement of two meridianally coordinated water molecules on the octahedral Cu(II) atom in compound 1 by a pn group gives compound 2, which shows similar Cairo tiling, and a further increase in the amount of pn results in the formation of the [Cu(NC)2(pn)2] unit and the two-fold-interpenetrated 3D framework of compound 3. The mixed-valence properties of compounds 1, 2, and 3 were confirmed by variable-temperature magnetic-susceptibility measurements.

Triangle, square and delta-chain based cobalt tetrazolate magnets.

Three novel tetrazole-based frustrated magnets, namely, Co3(OH)2(3-ptz)2(SO4)(H2O)4 (1), Co2(OH)(tzba)(H2O)4 (2) and [Co(OH)(tta)] (3) (3-ptz = 5-(3-pyridyl) tetrazole, H2tzba = 4-(1H-tetrazol-5-yl) benzoic acid, Htta = 1H-tetrazole) were hydrothermal synthesized and magnetically characterized. Compound 1 is a 2D (4,4) layered structure assembled by sulfate capped triangular [Co3(µ3-OH)(µ3-SO4)] clusters and in situ synthesized µ3-3-ptz ligands. Compound 2 features Co3(µ3-OH) triangle based magnetic Δ-chains linked with in situ generated µ5-tzba ligands to form a 2D layer. Compound 3 is a uninodal eight-connected body-centered-cubic (bcu) 3D network with square Co4O4 clusters as nodes and µ4-tta ligands as linkers. Interestingly, spin frustration was observed in these complexes due to inherent spin competition in triangle, Δ-chain and square. Magnetic studies show that 1 behaves as antiferromagnet, while 2 and 3 exhibits spin canting and long-range magnetic ordering.

[Direct determination of four components in compound paracetamol and diphenhydramine tablets by wide bore capillary gas chromatography].

A gas chromatographic method for the simultaneous determination of paracetamol (PAR), caffeine (CAF), diphenhydramine hydrochloride (DPH) and ephedrine hydrochloride (EPD) in Compound Paracetamol and Diphenhydramine Tablets has been developed. The separation of several components was achieved on a wide bore capillary column HP-1 (10 m x 0. 53 mm, 2. 65 microm) with flame ionization detector (FID), and with pentadecane as internal standard, at a column temperature of 190 degrees C. The linear ranges of detection for PAR, CAF, DPH and EPD were found to be 50 - 2 400, 10 - 500, 10 - 500 and 10 - 500 mg/L, respectively. The detection limits were 1 - 30 microg/L, the average recoveries were 98. 5% - 101. 1%. For intra-day assay, the relative standard deviations were less than 2. 2%. The method has been applied successfully to the determination of fourfold mixture of PAR, CAF, DPH and EPD in pharmaceutical preparations. The developed method is rapid and sensitive and therefore provides a scientific, basis for the quality control of Compound Paracetamol and Diphenhydramine Tablets.