Tuning Octahedron Sites of CoVO via Cationic Competition for Efficient Oxygen Evolution Reaction.

Doping transition metal oxide spinels with metal ions represents a significant strategy for optimizing the electronic structure of electrocatalysts. Herein, a bimetallic Fe and Ru doping strategy to fine-tune the crystal structure of CoVO spinel for highly enhanced oxygen evolution reaction (OER) is presented performance. The incorporation of Fe and Ru is observed at octahedral sites within the CoVO structure, effectively modulating the electronic configuration of Co.

Altering electronic structure of nickel foam supported CoNi-based oxide through Al ions modulation for efficient oxygen evolution reaction.

Developing highly active and durable non-precious metal-based electrocatalysts for the oxygen evolution reaction (OER) is crucial in achieving efficient energy conversion. Herein, we reported a CoNiAlO/NF nanofilament that exhibits higher OER activity than previously reported IrO-based catalysts in alkaline solution. The as-synthesized CoNiAlO/NF catalyst demonstrates a low overpotential of 230 mV at a current density of 100 mA cm, indicating its high catalytic efficiency.

Visible-Light-Driven Inactivation of Bacteria and H Generation Catalyzed by Oxygen-Vacancy-Rich One-Dimensional/Two-Dimensional WO/g-CN Z-Scheme Heterostructures.

Z-scheme heterostructure-based photocatalysts consist of a reduction photocatalyst and an oxidation photocatalyst, enabling them to possess a high capacity for both reduction and oxidation. However, the coupling reaction between photocatalytic H generation through water reduction and sterilization using Z-scheme systems has been rarely reported. Herein, 1D WO nanowires embedded over 2D g-CN nanosheets are well-constructed as an integrated Z-scheme heterojunction.

An efficient mixed-valence copper pyrazolate catalyst for the conversion of carbon dioxide and epoxides into cyclic carbonates.

In this paper, a cyclic (1) precursor and a mixed-valence pentanuclear complex I3 (2) have been synthesized and structurally characterized by single-crystal X-ray diffraction, where pzH = 4-chloro-3,5-diphenylpyrazole. The excellent catalytic activity of 2 has been demonstrated in the chemical fixation of CO into value-added cyclic carbonates, which can be carried out at ambient pressure and room temperature along with ultra-high yield and perfect steric hindrance tolerance. Based on density functional theory (DFT) calculations and comparison with the catalytic performance of 1, it is proposed that the coordinatively unsaturated Cu atoms of 2 are probably the active sites for this catalytic reaction.

Rational Design of Mixed Matrix Membranes Modulated by Trisilver Complex for Efficient Propylene/Propane Separation.

The application of membrane-based separation processes for propylene/propane (C H /C H ) is extremely promising and attractive as it is poised to reduce the high operation cost of the established low temperature distillation process, but major challenges remain in achieving high gas selectivity/permeability and long-term membrane stability. Herein, a C H facilitated transport membrane using trisilver pyrazolate (Ag pz ) as a carrier filler is reported, which is uniformly dispersed in a polymer of intrinsic microporosity (PIM-1) matrix at the molecular level (≈15 nm), verified by several analytical techniques, including 3D-reconstructed focused ion beam scanning electron microscropy (FIB-SEM) tomography. The π-acidic Ag pz combines preferentially with π-basic C H , which is confirmed by density functional theory calculations showing that the silver ions in Ag pz form a reversible π complex with C H , endowing the membranes with superior C H affinity.

Complexation of triangular silver(I) or copper(I) nitropyrazolates with dibenzothiophenes having potential use in adsorptive desulfurization.

Triangular silver(i) and copper(i) 3,5-diethyl-4-nitropyrazolates (abbreviated as [Ag(denpz)]3 or Ag3pz3, and [Cu(denpz)]3 or Cu3pz3), as well as their adducts with dibenzothiophene (DBT), 4,6-dimethyldibenzothiophene (DMDBT) and benzothiophene (BT), have been prepared and characterized by a series of techniques. X-ray analyses show that these adducts are stabilized by MS, MC contacts and ππ stacking interactions. NMR measurements and theoretical calculations indicate that the intensity of interaction between the metal complexes and dibenzothiophenes follows the trend: Ag3pz3-DMDBT > Ag3pz3-DBT > Cu3pz3-DMDBT > Cu3pz3-DBT, which can be understood on the basis of a weak interaction between π-acid (Ag3pz3 or Cu3pz3) and π-base (DBT/DMDBT).

Conversion of CO to Heterocyclohexenol Carboxylic Acids through a Metal-Organic Framework Sponge.

The conversion of CO into high value-added chemical products is the focus of current scientific research. We make use of the specific porous structure of nanosized metal-organic frameworks (MOFs) loading the highly active yet metastable nano CuO to catalyze the conversion of CO into a series of high value-added bioactive pyridone/pyrone-3-carboxylic acid products via heterocyclic 4-hydroxy-2-pyridones/pyrones, which exhibit high activity, selectivity, and reusability. Nano MOF sponge-covered metastable nanoparticles (NPs) converting CO into high value-added bioproducts provide a facile "dual-side surfactant" strategy, a highly efficient composite catalyst, and a practicable pathway not only for the sustainable use of CO but also for environment-friendly production of bioproducts.

A systematic investigation of structural transformation in a copper pyrazolato system: a case study.

Dissolution-recrystallization structural transformation (DRST) is a powerful tool to unravel unequivocally the mechanism of dynamic conversion processes, based on the structures of the initial reactants, final products and sometimes intermediates isolated from the reaction mixture. Herein, we illustrate the details of the conversion processes of (CuIpz)3 into [CuII(OH)pz]6 (pzH = 4-chloro-3,5-diphenylpyrazole) through DRSTs. Based on crystal structure determination and spectroscopic methods, the most encountered species, (CuIpz)3, is in equilibrium with (CuIpz)4 in solution with the tetramer becoming dominant at low temperature, indicating an entropy-controlled conversion between these two structural isomers.

Adducts of triangular silver(i) 3,5-bis(trifluoromethyl)pyrazolate with thiophene derivatives: a weak interaction model of desulfurization.

π-Acidic triangular silver(i) 3,5-bis(trifluoromethyl)pyrazolate (Agpz) can form 1 : 1 adducts with dibenzothiophene (DBT), 4,6-dimethyldibenzothiophene (DMDBT), benzothiophene (BT), and 2,5-dimethylthiophene (DMT), which are stabilized by weak AgS and AgC contacts and sometimes by π-π stacking and, therefore, may represent a weak interaction model for some adsorptive desulfurization processes.

A general strategy for synthesis of cyclophane-braced peptide macrocycles via palladium-catalysed intramolecular sp C-H arylation.

New methods capable of effecting cyclization, and forming novel three-dimensional structures while maintaining favourable physicochemical properties are needed to facilitate the development of cyclic peptide-based drugs that can engage challenging biological targets, such as protein-protein interactions. Here, we report a highly efficient and generally applicable strategy for constructing new types of peptide macrocycles using palladium-catalysed intramolecular C(sp)-H arylation reactions. Easily accessible linear peptide precursors of simple and versatile design can be selectively cyclized at the side chains of either aromatic or modified non-aromatic amino acid units to form various cyclophane-braced peptide cycles.

Research on Controllable Degradation of Novel Sulfonylurea Herbicides in Acidic and Alkaline Soils.

The degradation issue of sulfonylurea (SU) has become one of the biggest challenges that hamper the development and application of this class of herbicides, especially in the alkaline soils of northern China. On the basis of the previous discovery that some substituents on the fifth position of the benzene ring in Chlorsulfuron could hasten its degradation rate, apparently in acidic soil, this work on Metsulfuron-methyl showed more convincing results. Two novel compounds (I-1 and I-2) were designed and synthesized, and they still retained potent herbicidal activity in tests against both dicotyledons and monocotyledons.

The electrochemical discrimination of pinene enantiomers by a cyclodextrin metal-organic framework.

Pinene is a family of bicyclic monoterpenes found in nature, which exhibits important applications in chemical industry and biomedicine; however, the discrimination methods used for pinene enantiomers are still rare. The alpha- and beta-pinene enantiomers were recognized and discriminated via an electrochemical method for the first time based on a cyclodextrin metal-organic framework (CD-MOF) as an electrochemical chiral sensor.

A multi-responsive luminescent sensor for organic small-molecule pollutants and metal ions based on a 4d-4f metal-organic framework.

Two silver(i)-lanthanide(iii) heterometallic-organic frameworks (HMOFs) {[LnAg(BPDC)(OX)(HO)]·7HO} (Ln = Tb (1), Gd (2)) have been synthesized via a mixed ligand approach using 2,2'-bipyridine-3,3'-dicarboxylic acid (HBPDC) and oxalic acid (HOX) under hydrothermal conditions. Single crystal X-ray diffraction studies showed a (3,4,5)-connected new topology of {3·4·5·6}{3·4·5·6·7}{3·5·6·9·10}{4·5·6}{4·5}{4·6}{4·5·6}{4·6}{4·6·8·10}. Luminescence studies showed that the characteristic emissions of Tb ions are observed in HMOF 1 which can be capable of sensing organic small-molecule pollutants and metal ions.

Trigonal prismatic Cu(I) and Ag(I) pyrazolato nanocage hosts: encapsulation of S8 and hydrocarbon guests.

Two neutral hexanuclear trigonal prismatic cage molecules have been synthesized by coupling two planar triangular M3pz3-panels, M = Cu(I) and Ag(I), in eclipsed geometry. The ~230 Å(3) cage volume can be either vacant or occupied by neutral guests. The crystal structures of the M6-cyclohexane and Ag6-S8 host-guest species have been determined.

Bis(3,5-di-tert-butyl-4H-1,2,4-triazol-4-amine-κN(1))(nitrato-κO)silver(I) ethanol monosolvate monohydrate.

The Ag(I) atom in the title compound, [Ag(NO(3))(C(10)H(20)N(4))(2)]·C(2)H(5)OH·H(2)O, is coordinated by the N atoms of two N-heterocycles [N-Ag-N = 151.5 (1)°]; the approximately linear coordination geometry is distorted into a T-shaped geometry owing to a long Ag⋯O(nitrate) bond [2.717 (4) Å].