MXene-supported transition metal single-atom catalysts for nitrogen dissociation

• Published in: Molecular catalysis 2023-08, Vol.547, p.113373, Article 113373
• Main Authors: Gouveia, José D., Rocha, Henrique, Gomes, José R.B.
• Format: Article
• Language: English
• Subjects: Adsorption; Density functional theory; MXenes; Nitrogen dissociation; Single-atom catalysts
• ISSN: 2468-8231; 2468-8231
• DOI: 10.1016/j.mcat.2023.113373

•MXene-supported transition metal atoms are stable following N2 adsorption.•All Ti2C MXene-supported single transition metal atoms exothermically adsorb N2.•N2 binds preferably to transition metal atoms of groups 3 to 6 of the periodic table deposited over the Ti2C MXene, rather than on pristine regions of the MXene.•Doping the Ti2C MXene with atoms of transition metal elements significantly reduces the activation energy for N2 dissociation.•Single-atom catalysts based on the Ti2C MXene can be combined with other catalysts to complete N2 conversion to ammonia. 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 two-dimensional 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. [Display omitted]