The Role of Surface Hydroxyls in Dehydration and Dehydrogenationof Formic Acid on Fe₃O₄(001)

Understanding the role of surface structure and hydroxylation in catalytic reactions on metal oxide surfaces is important for developing a mechanistic insight into the complex interface processes. Here, we investigate the reactivity of formic acid on reconstructed Fe₃O₄(001) using a combination of X-ray photoelectron spectroscopy, infrared reflection absorption spectroscopy, temperature-programmed reaction spectroscopy, low energy electron diffraction, and electronic structure calculations. We find that formic acid initially dissociates at low temperatures (<80 K) into bidentate formate and a hydroxyl up to an initial dosed coverage of two HCOOH per Fe₃O₄(001) unit cell. At higher temperatures (>450 K), formate largely decomposes along the dehydration pathway, producing CO and H₂O, with dehydrogenation to CO₂ being a minority side reaction. As a first step, water formation leads to surface oxygen extraction via the Mars-van Krevelen mechanism. Computational studies reveal formate embedded in oxygen vacancies as a key intermediate in the CO formation mechanism. CO formation proceeds via two reaction pathways with desorption that peaks at 530 K on the hydroxyl-rich surface and 560 K on the hydroxyl-deficient surface. Atomic hydrogen coadsorption experiments and <i>ab initio</i> calculations reveal that the presence of surface hydroxyls reduces the CO formation barrier. These results highlight the complex interactions between substrate and intermediate species occurring during reactions on metal oxide surfaces.