Carbon nitride single-atom based catalysts: supporting the transition from the fossil past to the green future.

The recent findings on the fundamental understanding of the activity of carbon nitride-based materials in the hydrogen evolution reaction (HER) allow to design rationally the photocatalytic systems with improved activities....

C–H activation of hydrocarbons is extremely challenging, especially in short-chain hydrocarbons like propane. In industry, propane is first converted to propylene mostly by steam cracking, which is only oxidized to acetone in the cumene process, yielding acetone and phenol. In this work, we show that the simple FeCl3 salt in acetonitrile photocatalyzes the oxidation of propane to acetone at room temperature under aerobic conditions and visible-light irradiation. We achieved 100% conversion of propane with 67% selectivity in acetone after 4 h of irradiation and TON up to 600. Mechanistic studies, including electrospray ionization mass spectrometry, Mössbauer, and electroparamagnetic resonance spectroscopy, concluded that the reaction is driven by chlorine radicals generated by Fe–Cl bond photolysis. These results not only hold promise for the development of solar-based oxidation of hydrocarbons but more importantly also disclose deeper insights into the largely overlooked photochemistry of FeCl3.

We report on a new iron (iii)-cyamelurate-based coordination polymer. The new material based on a heptazine derivative was prepared in aqueous medium and characterized by a variety of techniques including TGA, FTIR, XRD, HRTEM, and STEM. Due to the high structural stability of the complex in aqueous media, its heterogeneous Fenton-like catalytic activity was evaluated using a model molecule. The results obtained showed a high catalytic activity in both in basic and acid media. The pseudo-first-order rate constants normalized by iron(III) concentrations was approximately 1000 times higher than the result obtained for traditional heterogeneous catalysts based on iron(III) oxyhydroxides. The best observed catalytic activities were attributed to the increase in the binding sites of Fe3+ ions, in parallel with the increased exposure of the catalytic sites, leading to a higher atomic efficiency of the reaction.

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