Dual Activation of N2 and CO2 toward N–O Coupling by Single Copper Ions

Concurrent activation and conversion of N2 and CO2 are of significance yet face numerous obstacles due to the large dissociation energies of N≡N and C═O bonds. Utilizing a specifically developed reflectron time-of-flight mass spectrometer, we investigated the dual activation of N2 and CO2 mediated by copper and silver ions under ambient conditions. Isotope experiments identified that both N2 and CO2 can be effectively activated to generate a N–O coupling product (NO+), especially in the presence of copper ions, and the NO+ product attains the maximum intensity with an N2/CO2 ratio of 1:2, which validates a three-molecule reaction mechanism, namely, N2 + 2CO2 → 2NO + 2CO. Through detailed analyses of thermo-dynamics and reaction dynamics, we illustrate the Cu+-catalyzed three-molecule reaction mechanism for N–O coupling, validating the dual activation of N2 and CO2 simply by plasma-assisted single-ion catalysis.