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Abstract

Developing high-performance Fe-based ammonia catalysts through simple and cost-efficient methods has received an increased level of attention. Herein, we report for the first time, the synthesis of two-dimensional (2D) FeOOH nanoflakes encapsulated by mesoporous SiO₂ (mSiO₂) via a simple solution-based method for ammonia synthesis. Due to the sticking of the mSiO₂ coating layers and the limited spaces in between, the Fe after reduction retains the 2D morphology, showing high resistance against the sintering in the harsh Haber–Bosch process. Compared to supported Fe particles dispersed on mSiO₂ spheres, the coated catalyst shows a significantly improved catalytic activity by 50% at 425 °C. Thermal desorption spectroscopy (TDS) reveals the existence of a higher density of reactive sites for N₂ activation in the 2D Fe catalyst, which is possibly coupled to a larger density of surface defect sites (kinks, steps, point defects) that are generally considered as active centers in ammonia synthesis. Besides the structural impact of the coating on the 2D Fe, the electronic one is elucidated by partially substituting Si with Al in the coating, confirmed by ²⁹Si and ²⁷Al magic-angle spinning nuclear magnetic resonance (MAS NMR). An increased apparent activation energy (E_a) of the Al-containing catalyst evidences an influence on the nature of the active site. The herein-developed stable 2D Fe nanostructures can serve as an example of a 2D material applied in catalysis, offering the chance of a rational catalyst design based on a stepwise introduction of various promoters, in the coating and on the metal, maintaining the spatial control of the active centers.