abstract
Industrial ammonia production follows the Haber-Bosch process, whose rate-limiting step is the dissociation of the nitrogen molecule (N2), hence requiring suitable catalysts to break its triple bond. MXenes, a class of twodimensional transition metal carbides and nitrides, have been proposed as very efficient catalysts for N2 dissociation. Here, by employing density functional theory-based calculations, we assess whether the deposition of one atom of a transition metal element (TM) on the Ti2C MXene surface further improves the catalytic potential of the MXene, serving as a single-atom catalyst. The results show that, for 21 of the 30 TMs considered, N2 can exothermically bind to the TM adatom, this bonding being favourable with respect to adsorption on the pristine Ti2C MXene surface for TMs of groups 3 to 6 of the Periodic Table. All the 21 TMs that successfully bind to N2 effectively reduce the N2 dissociation energy barrier when compared to the bulk Ti2C MXene by 18 to 84 %. Our results strongly indicate that doping the Ti2C MXene with atoms of transition metal elements significantly reduces the energy required to break the triple bond in N2, which may impact the nitrogen-to-ammonia process.
keywords
AMMONIA-SYNTHESIS; STABILITY; COMPLEXES; SURFACE; POINTS; IRON
subject category
Chemistry
authors
Gouveia, JD; Rocha, H; Gomes, JRB
our authors
José Daniel Lago da Silva Neves Gouveia
Assistant Researcher
José R. B. Gomes
Principal ResearcherProjects
CICECO - Aveiro Institute of Materials (UIDB/50011/2020)
CICECO - Aveiro Institute of Materials (UIDP/50011/2020)
Associated Laboratory CICECO-Aveiro Institute of Materials (LA/P/0006/2020)
Collaboratory for Emerging Technologies, CoLab (EMERGING TECHNOLOGIES)
acknowledgements
This work was developed within the scope of the project CICECO-Aveiro Institute of Materials, Refs. UIDB/50011/2020, UIDP/50011/2020 and LA/P/0006/2020, financed by national funds through the FCT/MCTES (PIDDAC). JDG thanks the Portuguese Foundation for Science and Technology (FCT) through the grant Ref. 2022.00719. CEECIND, in the scope of the Individual Call to Scientific Employment Stimulus - 5th Edition. We are also thankful to FCT I.P. for the computational resources granted in the framework of projectRef. 2021.09799.CPCA by the FCT/CPCA/2021/01 Call for Advanced Computing Projects.