Gas-phase CO2 activation with single electrons, metal atoms, clusters, and molecules

In this review, the history and outlook of gas-phase CO2 activation using single electrons, metal atoms, clusters (mainly metal hydride clusters), and molecules are discussed on both of the experimental and theoretical fronts. Although the development of bulk solid-state materials for the activation and conversion of CO2 into value-added products have enjoyed great success in the past several decades, this review focuses only on gas-phase studies, because isolated, well-defined gas-phase systems are ideally suited for high-resolution experiments using state-of-the-art spectrometric and spectroscopic techniques, and for simulations employing modern quantum theoretical methods. The unmatched high complementarity and comparability of experiment and theory in the case of gas-phase investigations bear an enormous potential in providing insights in the reactions of CO2 activation at the atomic level. In all of these examples, the reduction and bending of the inert neutral CO2 molecule is the critical step determined by the frontier orbitals of reaction participants. Based on the results and outlook summarized in this review, we anticipate that studies of gas-phase CO2 activations will be an avenue rich with opportunities for the rational design of novel catalysts based on the knowledge obtained on the atomic level.