Effect of non-boron element with the different electronegativity of binary boride on oxidative dehydrogenation of propane.

[Display omitted] • The content of the active sites over borides can be quantified by the temperature-programmed desorption of ammonia. • The TOF of catalysts, except for BP, exhibit negative linear regularity with the electronegativity of non-boron elements. • The non-boron elements affect the ability of B–OH groups to activate oxygen or propane and further change the relative energies of the rate-determining step. Boron-based catalysts are active and selective in the oxidative dehydrogenation reaction of propane (ODHP) to propylene. Herein, the binary boron-based compounds (boron nitride, boron phosphide, boron carbide, and silicon boride) composed of boron elements and one type of other non-boron elements, and the elemental boron were systematically compared to elucidate how the non-boron elements of binary borides influence their catalytic activity in ODHP. By combined experimental and computational studies, we demonstrated that the non-boron elements can modulate the performance of catalysts by altering the ability of the B-OH site to activate dioxygen and the subsequent activation of propane. In particular, the turnover frequency (TOF) of the catalyst exhibited a high negative linear correlation with the electronegativity of the non-boron element, except for the boron phosphide. This study highlights the importance of the chemical environment around the active boron sites and provides insight into the design of efficient ODHP catalysts. [ABSTRACT FROM AUTHOR]