DFT Investigation of Ammonia Formation via a Langmuir–Hinshelwood Mechanism on Mo-Terminated δ-MoN(0001)

Sajid, Muhammad; Kaden, William E.; Kara, Abdelkader

doi:10.1021/acsomega.1c05967

DFT Investigation of Ammonia Formation via a Langmuir–Hinshelwood Mechanism on Mo-Terminated δ-MoN(0001)

Journal Article · Mon Jan 24 23:00:00 EST 2022 · ACS Omega

DOI:https://doi.org/10.1021/acsomega.1c05967· OSTI ID:1904024

^[1]; Kaden, William E. ^[2]; ^[2]

University of Central Florida, Orlando, FL (United States); OSTI
University of Central Florida, Orlando, FL (United States)

In this work, we employed density functional theory to elucidate the energetics associated with elementary steps along a Langmuir-Hinshelwood mechanism for the Haber-Bosch synthesis of ammonia from N₂ and H₂ on a hexagonal, Mo-terminated molybdenum nitride surface. Using nudged elastic band calculations, we determined the energy barriers involved in the reaction processes. An active site consisting of four nearest-neighbor Mo atoms, previously identified as an active site on similar surfaces, was chosen to investigate the reaction processes. Using this approach, we calculate a barrier of ~0.5 eV for the dissociation of N₂. The superior activity of the dissociation of the strong N₂ bonds is rationalized based on the unique geometric and electronic configurations present at these active sites. Despite the favorable energetics for nitrogen dissociation, the energy cost for hydrogenation of NH_x (0 ≤ x ≤ 2) species is shown to be energetically limiting for the formation of ammonia through the Langmuir-Hinshelwood mechanism at these sites, with elementary step activation barriers calculated to be as large as ~2 eV. A comparison to Haber-Bosch results derived from a similar γ-Mo₂N model system suggests the relative independence of surface chemistry and bulk stoichiometry for rhombic Mo₄ active sites present on molybdenum nitrides.

View Accepted Manuscript (DOE)

Research Organization:: University of Central Florida, Orlando, FL (United States)

Sponsoring Organization:: USDOE Office of Science (SC); American Chemical Society Petroleum Research Fund

OSTI ID:: 1904024

Journal Information:: ACS Omega, Journal Name: ACS Omega Journal Issue: 5 Vol. 7; ISSN 2470-1343

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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