Titelaufnahme

Hydrated singly charged metal ions doped with carbon dioxide, Mg2+(CO2)-(H2O)n, in the gas phase are valuable model systems for the electrochemical activation of CO2. Here, we study these systems by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry combined with ab initio calculations. We show that the exchange reaction of CO2 with O2 proceeds fast with bare Mg+(CO2), with a rate coefficient kabs = 1.2 × 10-10 cm3 s-1, while hydrated species exhibit a lower rate in the range of kabs = (1.2-2.4) × 10-11 cm3 s-1 for this strongly exothermic reaction. Water makes the exchange reaction more exothermic but, at the same time, considerably slower. The results are rationalized with a need for proper orientation of the reactants in the hydrated system, with formation of a Mg2+(CO4)-(H2O)n intermediate while the activation energy is negligible. According to our nanocalorimetric analysis, the exchange reaction of the hydrated ion is exothermic by -1.7 +/- 0.5 eV, in agreement with quantum chemical calculations.