Electrocatalytic water oxidation performance in an extended porous organic framework with a covalent alliance of distinct Ru sites.

The rational synthesis of durable, earth-abundant efficient electrocatalysts for the oxygen evolution reaction (OER) from water is one of the most important routes for storing renewable energy and minimizing fossil fuel combustion. The prime hurdles for effectively utilizing commercial RuO2 as (OER) electrocatalysts are its very low stability, catalyst deactivation, and high cost. In this work, we explored a Ru-integrated porous organic polymer (Ru@Bpy-POP) by a facile one-pot Friedel-Crafts alkylation strategy between redox-active (Ru(demob)3Cl2) and a carbazole unit, which is composed of unique features including an extended framework unit, isolated active sites, and tunable electrode kinetics. Ru@Bpy-POP can serve as a bridge between a Metal-Organic Framework (MOF) and POP-based catalytic systems with a balanced combination of covalent bonds (structural stability) and open metal sites (single site catalysis). Ru@Bpy-POP, deposited on a three-dimensional nickel foam electrode support, exhibits a promising electrocatalytic OER activity with an ultra-low ruthenium loading compared to a benchmark RuO2 catalyst, providing an overpotential of about 270 mV to reach 10 mA cm-2 in an alkaline medium. Moreover, a high current density of 248 mA cm-2 was achieved for the Ru@Bpy-POP catalyst at only 1.6 V (vs. RHE), which is much higher than 91 mA cm-2 for commercial RuO2. The robust, albeit highly conjugated, POP framework not only triggered facile electro-kinetics but also suppressed aggregation and metallic corrosion during electrolysis. In particular, the benefits of covalent integration of distinct Ru sites into the framework can modulate intermediate adsorption and charge density, which contributes to its exceptional OER activity. All of the critical steps involved in OER are complemented by Density Functional Theory (DFT) calculations, which suggest that electrocatalytic water oxidation proceeds from a closed-shell configuration to open-shell electronic configurations with high-spin states. These open-shell configurations are more stable than their closed-shell counterparts by 1 eV, improving the overall catalytic activity.

A simple chemical method for the synthesis of Cu2+ engrafted MgAl2O4 nanoparticles: Efficient fluoride adsorbents, photocatalyst and latent fingerprint detection.

An adaptable, energy efficient chemical process is employed to synthesize Cu2+ engrafted MgAl2O4 nanoparticles (Mg1-xCuxAl2O4, x=0, 0.1, 0.3, 0.5 abbreviated as MCA0, MCA1, MCA3, and MCA5 respectively), using chelating ligand and the calcination temperature was determined by the thermogravimetric analysis of the precursor mass. They acted as good fluoride adsorbent in the presence of co-ions, different pH (2-11) via chemisorption revealed from Fourier-transform infrared spectroscopy (FTIR) and photodegraded Methylene Blue (MB). The satisfactory results were for MCA1 (specific surface area 25.05m2/g) with 97% fluoride removal at pH7.0 for the 10mg/L initial fluoride concentration for 1.5g/L adsorbent dose with 45min contact time obeying the Langmuir isotherm model with negative thermodynamic parameters and 4mmol of MCA3 with 98.51% photodegradation for 10-5mol/LMB solution obeying pseudo-second-order and pseudo-first-order kinetics respectively. The proposed photodegradation mechanism of MB was established by the FTIR and high-performance liquid chromatography (HPLC) analysis. The nanoparticles are cubic, estimated through X-ray diffraction (XRD) and transmission electron microscopy (TEM) analysis. The band gap energies, grain size, and the effective working pH were estimated by diffuse reflectance spectra (DRS), scanning electron microscope (SEM), and zero-point potential analysis respectively. A soil candle with MCA1 also fabricated for the household purpose and tested with some fluorinated field samples. The MCA3 was able to enhance the latent fingerprint on smooth surfaces.

Efficient Fluoride Removal and Dye Degradation of Contaminated Water Using Fe/Al/Ti Oxide Nanocomposite.

The trimetallic Fe/Al/Ti (1:1:1) nanocomposite (FAT), synthesized by an adaptable tuned chemical route, offers a new approach for water treatment, for example, the de-fluoridation and photodegradation soluble dye methylene blue (MB) at pH 7. FAT acted as a good fluoride scavenger in the presence of other co-ions and within a widespread pH range (pH 2-11). The photodegradation efficiencies were >90% for different concentrations of MB solutions. The characterization of FAT includes thermogravimetric analysis, X-ray diffraction, Fourier transform-infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, and ζ-potential analysis. Furthermore, the regeneration efficiencies of both the water treatments were checked, where the removal efficiency was not hampered significantly even after five batches. Spectroscopic techniques were adopted to perform the kinetic studies and to propose the probable mechanistic paths.