Abstract
We investigated the catalytic NH(3) decomposition on Ru and Ir metal surfaces using density functional theory. The reaction mechanisms were unraveled on both metals, considering that, on the nano-scale, Ru particles may also present an fcc structure, hence, leading to three energy profiles. We implemented thermodynamic and kinetic parameters obtained from DFT into microkinetic simulations. Batch reactor simulations suggest that hydrogen generation starts at 400 K, 425 K and 600 K on Ru(111), Ru(0001) and Ir(111) surfaces, respectively, in excellent agreement with experiments. During the reaction, the main surface species on Ru are NH, N and H, whereas on Ir(111), it is mainly NH. The rate-determining step for all surfaces is the formation of molecular nitrogen. We also performed temperature-programmed reaction simulations and inspected the desorption spectra of N(2) and H(2) as a function of temperature, which highlighted the importance of N coverage on the desorption rate.