Exponential interest in the field of covalent organic frameworks (COFs) stems from the direct correlation between their modular design principle and various interesting properties. However, existing synthetic approaches to realize this goal mainly result in insoluble and unprocessable powders, which severely restrict their widespread applicability. Therefore, developing a methodology for easy fabrication of these materials remains an alluring goal and a much desired objective. Herein, we have demonstrated a bottom-up interfacial crystallization strategy to fabricate these microcrystalline powders as large-scale thin films under ambient conditions. This unique design principle exploits liquid-liquid interface as a platform, allowing simultaneous control over crystallization and morphology of the framework structure. The thin films are grown without any support in free-standing form and can be transferred onto any desirable substrate. The porous (with Tp-Bpy showing highest S of 1 151 m g) and crystalline thin films, having high chemical as well as thermal stability, also hold the merit to tune the thickness as low as sub-100 nm. These nanostructured thin COF films demonstrate remarkable solvent-permeance and solute-rejection performance. A prominent instance is the Tp-Bpy thin film, which displays an unprecedented acetonitrile permeance of 339 L m h bar.

Membrane separation technologies are of great interest in industrial processes such as water purification, gas separation, and materials synthesis. However, commercial filtration membranes have broad pore size distributions, leading to poor size cutoff properties. In this work, mesoporous silica thin membranes with uniform and large vertical mesochannels are synthesized via a simple biphase stratification growth method, which possess an intact structure over centimeter size, ultrathin thickness (≤50 nm), high surface areas (up to 1420 m g ), and tunable pore sizes from ≈2.8 to 11.8 nm by adjusting the micelle parameters. The nanofilter devices based on the free-standing mesoporous silica thin membranes show excellent performances in separating differently sized gold nanoparticles (>91.8%) and proteins (>93.1%) due to the uniform pore channels. This work paves a promising way to develop new membranes with well-defined pore diameters for highly efficient nanosize-based separation at the macroscale.

Mercaptopropyl functionalized ordered mesoporous silica spheres were prepared (MPS). Ag or Au nanoparticles (NPs) were anchored onto the MPS materials (Ag-MPS or Au-MPS). Further, zinc phthalocyanine (ZnPc) was adsorbed into the channels and surface (MPS-ZnPc, Ag-MPS-ZnPc, Au-MPS-ZnPc). Diffuse reflectance studies revealed the successful incorporation of Ag or Au NPs inside the silica spheres with and without ZnPc. TEM images showed the uniform distribution of Ag or Au NPs in the silica spheres of different size ranging from 4 to 22 nm or 6 to 31 nm, respectively. XRD pattern showed average crystallite particle size of 18 or 28 nm for Ag or Au NPs respectively which were reduced to 14 or 16 nm on introduction of ZnPc which oxidizes the metal NPs partially. Chemically modified electrodes were prepared by coating the colloidal solutions of the silica materials on the glassy carbon (GC) electrodes. Electrocatalytic reductions of O(2) and CO(2) at the modified electrodes were studied. The presence of Ag or Au NPs was found to increase the electrocatalytic efficiency of ZnPc toward O(2) reduction by 290% or 70% based on the current density measured at -0.35 V and toward CO(2) reduction by 150% or 120% based on the current density measured at -0.60 V respectively. Catalytic rate constants were increased 2-fold for O(2) reduction and 8-fold for CO(2) reduction due to Ag or Au NPs, respectively, which act as nanoelectrode ensembles. The synergic effect of ZnPc and metal NPs on the electrocatalytic reduction of O(2) is presented.

In this work, we report the fabrication and characterization of silver nanoelectrode ensembles (Ag-NEEs) on a glassy carbon electrode. For this purpose, Ag nanoparticles (NPs) were anchored to the mercaptopropyl functionalized MCM-41 type silica spheres utilizing the chemisorption property of Ag NPs by -SH groups. The successful anchoring of Ag NPs into the silica matrix is characterized by several techniques including UV-vis diffuse reflectance and X-ray powder diffraction methods. The surface morphology of the Ag-NEEs was assessed by scanning and transmission electron microscopy (SEM and TEM respectively). Further, nitrite (NO(2)(-)) is electrocatalytically oxidized at Ag-NEEs, which leads to a sensitive determination of NO(2)(-). The fabrication, characterization, and efficient sensing of NO(2)(-) at the Ag-NEEs are presented.