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Abstract Photoredox catalysis has proven to be a powerful tool in synthetic organic chemistry. The rational design of photosensitizers with improved photocatalytic performance constitutes a major advancement in photoredox organic transformations. This review summarizes the fundamental ground-state and excited-state photophysical and electrochemical attributes of molecular photosensitizers, which are important determinants of their photocatalytic reactivity. 

A cobalt porphyrin molecule, namely CoTcPP (TcPP = the dianion of meso -tetra(4-carboxyphenyl)porphyrin), is intercalated into zirconium phosphate (ZrP) layers as an effective way to heterogenize a porphyrin-based molecular electrocatalyst. Fourier-transform infrared (FT-IR) spectroscopy, X-ray powder diffraction (XRPD) measurements, UV-Vis spectroscopy, elemental mapping, energy dispersive X-ray (EDX) analysis, inductively coupled plasma mass spectrometry (ICP-MS) and X-ray photoelectron spectroscopy (XPS) were utilized to determine the successful intercalation of CoTcPP into ZrP. While the CoTcPP molecule is not amendable to be used as a heterogeneous catalyst in basic environment due to the carboxylic groups, the intercalated species (CoTcPP/ZrP) is effective towards water oxidation from KOH aqueous solution when utilized as a heterogeneous electrocatalyst and shows remarkable catalytic durability. Electrochemical results show that CoTcPP/ZrP requires an overpotential of 0.467 V to achieve a current density of 10 mA cm −2 while the pristine α-ZrP shows negligible electrocatalytic OER behavior. 

In this work, we describe bis-cyclometalated iridium complexes with efficient deep-red luminescence. Two different cyclometalating (C^N) ligands-1-phenylisoquinoline (piq) and 2-(2-pyridyl)benzothiophene (btp)-are used with five strong π-donating ancillary ligands (L^X) to furnish a suite of nine new complexes with the general formula Ir(C^N) 2 (L^X). Improvements in deep-red photoluminescence quantum yields were accomplished by the incorporation of sterically encumbering substituents onto the ancillary ligand, which can enhance the radiative rate constant ( k r ) and/or reduce the non-radiative rate constant ( k nr ). Five of the complexes were characterized by X-ray crystallography, and all of them were investigated by in-depth spectroscopic and electrochemical measurements. 

The conversion of solar energy into chemical fuel is one of the “Holy Grails” of 21st century chemistry. Solar energy can be used to split water into oxygen and protons, which are then used to make hydrogen fuel. Nature is able to catalyze both the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER) required for the conversion of solar energy into chemical fuel through the employment of enzymes that are composed of inexpensive transition metals Instead of using expensive catalysts such as platinum, cheaper alternatives (such as cobalt, iron, or nickel) would provide the opportunity to make solar energy competitive with fossil fuels. However, obtaining efficient catalysts based on earth abundant materials is still a daunting task. Progress in finding an ideal catalyst for the OER has been challenging as it appears that the overpotential for these catalysts have plateaued. Recent theory has shown that nanoscopic confinement of catalysts into 3D frameworks increases stability and efficiency of catalysts for OER. We are studying the use of the layered inorganic nanomaterial zirconium phosphate (ZrP) for water splitting. In this chapter we review the advancements made with ZrP as a support for transition metals for the OER. Our studies have found that ZrP is a suitable support for transition metals as it provides an accessible surface where the OER can occur. Further findings have also show that exfoliation of ZrP increases the availability of sites where active species can be adsorbed and performance is improved with this strategy.