Regulating the frontier orbital of iron phthalocyanine with nitrogen doped carbon nanosheets for improving oxygen reduction activity.

Iron phthalocyanine (FePc) has attracted widespread attention for its tunable electronic structure. However, the Fe-N sites suffer from undesirable oxygen reduction activity due to the symmetric geometries. A suitable substrate was thus needed to induce electron redistribution around Fe-N to improve the activity. Herein, ultrathin nitrogen-doped carbon nanosheets (N-CNSs) were prepared by a simple high temperature pyrolysis. Then iron phthalocyanine was loaded on the ultrathin nitrogen-doped carbon nanosheets (FePc@N-CNSs) by a low-cost and simple solution method. This composite catalyst shows an excellent ORR activity with a half potential of 0.88 V, an onset potential of 0.99 V and durability superior to commercial Pt/C. When used as an air cathode catalyst for rechargeable zinc-air batteries, FePc@N-CNS modified batteries outperform Pt/C + RuO2 modified batteries with higher power density and superior constant current charge-discharge cycling stability of 37 hours. The regulated electronic structure of FePc by the N-CNS substrate was revealed further by DFT calculations, which explained the enhanced adsorption of the active center to the intermediates and the increased ORR performance.

An electronic perturbation in TiC supported platinum monolayer catalyst for enhancing water-gas shift performance: DFT study.

The water-gas shift (WGS) reaction behaviors over the TiC(0 0 1) supported Pt monolayer catalyst (PtML/TiC(0 0 1)) are investigated by using the spin-unrestricted density functional theory calculations. Importantly, we find that the PtML/TiC(0 0 1) system exhibits a much lower density of Pt-5d states nearby the Fermi level compared with that for Pt(1 1 1), and the monolayer Pt atoms undergo an electronic perturbation when in contact with TiC(0 0 1) support that would strongly improve the WGS activity of supported Pt atoms. Our calculations clearly indicate that the dominant reaction path follows a carboxyl mechanism involving a key COOH intermediate, rather than the common redox mechanism. Furthermore, through the detailed comparisons, the results demonstrate that the strong interactions between the monolayer Pt atoms and TiC(0 0 1) support make PtML/TiC(0 0 1) a highly active catalyst for the low-temperature WGS reaction. Following the route presented by Bruix et al (2012 J. Am. Chem. Soc. 134 8968-74), the positive effect derived from strong metal-support interaction in the metal/carbide system is revealed.