Postsynthetic Functionalization of Three‐Dimensional Covalent Organic Frameworks for Selective Extraction of Lanthanide Ions

Chemical functionalization of covalent organic frameworks (COFs) is critical for tuning their properties and broadening their potential applications. However, the introduction of functional groups, especially to three‐dimensional (3D) COFs, still remains largely unexplored. Reported here is a general strategy for generating a 3D carboxy‐functionalized COF through postsynthetic modification of a hydroxy‐functionalized COF, and for the first time exploration of the 3D carboxy‐functionalized COF in the selective extraction of lanthanide ions. The obtained COF shows high crystallinity, good chemical stability, and large specific surface area. Furthermore, the carboxy‐functionalized COF displays high metal loading capacities together with excellent adsorption selectivity for Nd³⁺ over Sr²⁺ and Fe³⁺ as confirmed by the Langmuir adsorption isotherms and ideal adsorbed solution theory (IAST) calculations. This study not only provides a strategy for versatile functionalization of 3D COFs, but also opens a way to their use in environmentally related applications.     

Chiral acid selectivity displayed by PEDOT electropolymerised in the presence of chiral molecules

Chiral conducting polymers prepared by electropolymerising PEDOT in the presence of chiral anions such as hyaluronic acid and anionic collagen or in a chiral nematic phase (hydroxypropyl cellulose, HPC) show excellent chiral acid recognition. This paper demonstrates the enantioselective recognition and transfer of protonated mandelic acid and protons using chiral PEDOTs. Discrimination between (R)-(-)- and (S)-(+)-mandelic acid was observed using cyclic voltammetry and square-wave voltammetry.     

Impact of polyvinylpyrrolidone and quantity of silver nitrate on silver nanoparticles sizing via solvothermal method for dye-sensitized solar cells

The multiple sizing of silver nanoparticles (AgNPs) were synthesized from the miscible compound of ethylene glycol (EG), polyvinylpyrrolidone (PVP) and silver nitrate (AgNO3) via the solvothermal method. During the synthesis, the PVP-AgNO3 was contemplated as a paramount parameter. Using the simple method of solvothermal, the sizing of AgNPs was easily controlled in accord with the augmentation of PVP-AgNO3 at secured and moderate temperature. In regards to the sizing of AgNPs, the presence of minimum agglomeration, the absorption capability and chemical structures were highlighted through a series of verification includes ultraviolet–visible (UV–Vis) spectroscopy, Fourier-transform infrared (FTIR) spectroscopy and transmission electron microscopy (TEM) analysis. The effectiveness of the synthesized AgNPs was further investigated and compared with the commercial AgNPs by incorporating the AgNPs into titanium dioxide (TiO2) semiconductor film-based dye-sensitized solar cells (DSSCs). Results signified that the spherical AgNPs with produced sizing within the range of 19.6 to 45.2 nm were greatly impacting by tunable quantities of PVP-AgNO3, which was validated in the forms of linear equations. A larger size promotes a slower nucleation rate that conduces agglomeration. In opposition to this, the smallest size of AgNPs develops a faster formation rate of Ag ions into AgNPs, inducing the deterrent of agglomeration in light of notable particle dispersion. The power conversion efficiency (PCE) contributed by the incorporation of synthesized AgNPs into TiO2 is also 41.2% higher than that of the commercial AgNPs-TiO2. This is because the synthesized AgNPs provides less agglomeration which led to a better surface plasmonic effect towards the nanoparticles.     

Piezochromism in Dynamic Three-Dimensional Covalent Organic Frameworks

Piezochromic materials with pressure-dependent photoluminescence tuning properties are important in many fields, such as mechanical sensors, security papers, and storage devices. Covalent organic frameworks (COFs), as an emerging class of crystalline porous materials (CPMs) with structural dynamics and tunable photophysical properties, are suitable for designing piezochromic materials, but there are few related studies. Herein, we report two dynamic three-dimensional COFs based on aggregation-induced emission (AIE) or aggregation-caused quenching (ACQ) chromophores, termed JUC-635 and JUC-636 (JUC=Jilin University China), and for the first time, study their piezochromic behavior by diamond anvil cell technique. Due to the various luminescent groups, JUC-635 has completely different solvatochromism and molecular aggregation behavior in the solvents. More importantly, JUC-635 with AIE effect exhibits a sustained fluorescence upon pressure increase (≈3 GPa), and reversible sensitivity with high-contrast emission differences (Δλ_em=187 nm) up to 12 GPa, superior to other CPMs reported so far. Therefore, this study will open a new gate to expand the potential applications of COFs as exceptional piezochromic materials in pressure sensing, barcoding, and signal switching.