[Cu2O]2+ active site formation in Cu-ZSM-5: geometric and electronic structure requirements for N2O activation.

Understanding the formation mechanism of the [Cu2O](2+) active site in Cu-ZSM-5 is important for the design of efficient catalysts to selectively convert methane to methanol and related value-added chemicals and for N2O decomposition. Spectroscopically validated DFT calculations are used here to evaluate the thermodynamic and kinetic requirements for formation of [Cu2O](2+) active sites from the reaction between binuclear Cu(I) sites and N2O in the 10-membered rings Cu-ZSM-5. Thermodynamically, the most stable Cu(I) center prefers bidentate coordination with a close to linear bite angle. This binuclear Cu(I) site reacts with N2O to generate the experimentally observed [Cu2O](2+) site. Kinetically, the reaction coordinate was evaluated for two representative binuclear Cu(I) sites. When the Cu-Cu distance is sufficiently short (<4.2 Å), N2O can bind in a "bridged" μ-1,1-O fashion and the oxo-transfer reaction is calculated to proceed with a low activation energy barrier (2 kcal/mol). This is in good agreement with the experimental Ea for N2O activation (2.5 ± 0.5 kcal/mol). However, when the Cu-Cu distance is long (>5.0 Å), N2O binds in a "terminal" η(1)-O fashion to a single Cu(I) site of the dimer and the resulting E(a) for N2O activation is significantly higher (16 kcal/mol). Therefore, bridging N2O between two Cu(I) centers is necessary for its efficient two-electron activation in [Cu2O](2+) active site formation. In nature, this N2O reduction reaction is catalyzed by a tetranuclear CuZ cluster that has a higher E(a). The lower E(a) for Cu-ZSM-5 is attributed to the larger thermodynamic driving force resulting from formation of strong Cu(II)-oxo bonds in the ZSM-5 framework.