Synthesis of water-soluble Ni(II) complexes and their role in photo-induced electron transfer with MPA-CdTe quantum dots.

Photocatalytic water splitting using solar energy for hydrogen production offers a promising alternative form of storable and clean energy for the future. To design an artificial photosynthesis system that is cost-effective and scalable, earth abundant elements must be used to develop each of the components of the assembly. To develop artificial photosynthetic systems, we need to couple a catalyst for proton reduction to a photosensitizer and understand the mechanism of photo-induced electron transfer from the photosensitizer to the catalyst that serves as the fundamental step for photocatalysis. Therefore, our work is focused on the study of light driven electron transfer kinetics from the quantum dot systems made with inorganic chalcogenides in the presence of Ni-based reduction catalysts. Herein, we report the synthesis and characterization of four Ni(II) complexes of tetradentate ligands with amine and pyridine functionalities (N2/Py2) and their interactions with CdTe quantum dots stabilized by 3-mercaptopropionic acid. The lifetime of the quantum dots was investigated in the presence of the Ni complexes and absorbance, emission and electrochemical measurements were performed to gain a deeper understanding of the photo-induced electron transfer process.

Reactivity of bio-inspired Cu(II) (N2/Py2) complexes with peroxide at room temperature.

Developing coordination complexes of earth abundant metals that can perform substrate oxidations under benign conditions is an ongoing challenge. Herein, the reactivity of two mononuclear Cu-complexes toward the oxidant H2O2 is reported. Both complexes displayed ligand oxidation upon reaction with the oxidant. Analysis of spectroscopic data established that the respective product complexes contained mononuclear Cu(II) centers. Moreover, treatment of these Cu-complexes with oxidant in the presence of substrate resulted in the interception of ligand oxidation with preferential oxidation of the substrate. Computational studies identified plausible mechanistic pathways, suggesting a copper-oxyl intermediate as the likely reactive intermediate responsible for substrate and ligand oxidation. To our knowledge, this is the first Cu-mediated system that showed ligand oxidation, oxo-transfer capability, and external hydrocarbon oxidation under stoichiometric conditions.

Ups and Downs of Water Photodecolorization by Nanocomposite Polymer Nanofibers.

Given the exponentially expanding water pollution causing water scarcity, there is an urgent need for operative nanotechnological systems that can purify water, with insignificant energy consumption, and rapidly. Here, we introduce a nanocomposite system based on TiO2 nanoparticles (NPs) and PES nanofibers (NFs) that can adsorb and then photodecompose organic water pollutants such as dye molecules. We evaluate pros and cons of this system with respect to its purification efficiency and structural properties that can be impacted by the photocatalytic activity of the nanofillers. While the material is superhydrophilic and able to remove 95% methylene blue (MB) from water via adsorption/photodecomposition, its thermomechanical properties decline upon UV irradiation. However, these properties still remain at the level of the neat NFs. The removal behavior is modeled by the first- and second-order kinetic models from the kinetic point of view. The nanocomposite NFs' removal behavior complies much better with the second-order kinetic model. Overall, such feedbacks implied that the nanocomposite can be effectively applied for water treatment and the structural properties are still as reliable as those of the neat counterpart.