Vibrational study of CO, O₂, and H₂ Adsorbed on the CoCrFeNi (110) High Entropy Alloy Surface

The vibrational properties of CO, O₂, and H₂ molecularly or dissociatively adsorbed on a CoCrFeNi(110) surface have been probed using high-resolution energy loss spectroscopy (HREELS) and modeled using density functional theory (DFT) calculations. Large (∼20 mm³) single-crystal, quaternary face-centered cubic CoCrFeNi was synthesized via a modified Czochralski technique. We show strong evidence that CO adsorbs primarily on bridge and on-top sites in compositionally varied local environments, which reflect the random, multielemental surface composition inherent in a high entropy alloy. A variation of adsorption sites is also found with oxygen, which exhibits two broad groups of modes. Comparison to previous photoemission and theoretical studies suggests that the higher energy modes consist primarily of local CrO species, while the lower energy modes are due to oxygen atoms adsorbed on other metal sites. Unlike CO and O₂, HREELS upon H₂ adsorption shows only two much narrower modes and is consistent with atomic adsorption on 3-fold hollow sites. The hypothesized adsorption sites for all three species are directly corroborated by our DFT calculations.