Ozone decomposition on transition-metal-atom anchored graphdiyne: Insights from computation and experiment.

Transition-metal-atom anchored graphdiynes (TM@GDY, TM = Mn, Fe, Co, Ni and Cu) have already been synthesized and found applications in hydrogen evolution, nitrogen fixation and etc. By means of first-principle predictions and test experiments, we propose here that Fe@GDY and Co@GDY are efficient catalysts for the sustainable conversion of O to O. These two catalysts can spontaneously chemisorb O with zero reaction barrier and have low O conversion barriers (0.31 eV and 0.19 eV, respectively). The O decomposition experiment in a continuous flow membrane reactor and electron paramagnetic resonance results verify that Fe@GDY and Co@GDY are efficient catalysts under humid conditions. Raman spectra prove the formation of the key Fe-O/Co-O and FeOO and CoOO intermediates. The hydrophobic nature of graphdiyne and the strongest chemisorption of O among tested ambient gases, make Fe@GDY and Co@GDY ideal catalysts under both dry and humid conditions. These findings would stimulate future explorations on metal anchored GDY-based catalysts for applications of toxic gas decomposition or fixation.