Abstract
Converting CO(2) directly from the air to fuel under ambient conditions is a huge challenge. Thus, there is an urgent need for CO(2) conversion protocols working at room temperature and atmospheric pressure, preferentially without any external energy input. Herein, we employ magnesium (nanoparticles and bulk), an inexpensive and the eighth-most abundant element, to convert CO(2) to methane, methanol and formic acid, using water as the sole hydrogen source. The conversion of CO(2) (pure, as well as directly from the air) took place within a few minutes at 300 K and 1 bar, and no external (thermal, photo, or electric) energy was required. Hydrogen was, however, the predominant product as the reaction of water with magnesium was favored over the reaction of CO(2) and water with magnesium. A unique cooperative action of Mg, basic magnesium carbonate, CO(2), and water enabled this CO(2) transformation. If any of the four components was missing, no CO(2) conversion took place. The reaction intermediates and the reaction pathway were identified by (13)CO(2) isotopic labeling, powder X-ray diffraction (PXRD), nuclear magnetic resonance (NMR) and in situ attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), and rationalized by density-functional theory (DFT) calculations. During CO(2) conversion, Mg was converted to magnesium hydroxide and carbonate, which may be regenerated. Our low-temperature experiments also indicate the future prospect of using this CO(2)-to-fuel conversion process on the surface of Mars, where CO(2), water (ice), and magnesium are abundant. Thus, even though the overall process is non-catalytic, it could serve as a step towards a sustainable CO(2) utilization strategy as well as potentially being a first step towards a magnesium-driven civilization on Mars.