On the Structural Transformation of Ni/BaH 2 During a N 2 -H 2 Chemical Looping Process for Ammonia Synthesis: A Joint In Situ Inelastic Neutron Scattering and First-Principles Simulation Study
The demand for decarbonizing the ammonia industry by using renewable energy has invoked increasing research interests into catalyst development for effective N 2 reduction under mild conditions. Hydride-based materials are among some of the emerging catalysts for ammonia synthesis at ambient pressure and low temperatures (< 673 K). A recent chemical looping process based on Ni/BaH 2 showed the most promise as it can realize ammonia production at a temperature as low as 373 K and under ambient pressure. However, the chemical transformation of the hydride catalyst at the molecular level remains unclear in this process. Here, we report detailed in situ neutron spectroscopy and diffraction investigations along with first-principles simulations on the structural transformation of Ni/BaH 2 during the nitridation and hydrogenation steps in the chemical looping process for ammonia synthesis. It was shown that a ball-milling process of the starting Ni/BaH 2 could significantly decrease the size of BaH 2 and increase the density of defects, thus potentially enhancing the reactivity of the hydride. The evolution from BaH 2 to barium imide (BaNH) was evidenced in the inelastic neutron scattering (INS) and neutron diffraction results during the N 2 reaction step. During the hydrogenation study, in addition to the recovery of BaH 2 , a possible intermediate species, N-deficient barium imide, was also detected. In comparing the N 2 and H 2 reaction steps, the neutron results indicate that the hydrogenation step appears more difficult than the nitridation step, confirming the facile N 2 fixation property of Ni/BaH 2 catalyst in ammonia synthesis.