The catalytic conversion of carbon dioxide to synthetic fuels and other valuable chemicals is an issue of global environmental and economic impact. In this report we show by means of X-ray photoelectron spectroscopy in the millibar range that, on a Ni surface, the reduction of carbon dioxide is indirectly governed by the CO chemistry. While the growth of graphene and the carbide-graphene conversion can be controlled by selecting the reaction temperature, oxygen is mainly removed by CO, since oxygen reduction by hydrogen is a slow process on Ni. Even though there is still a consistent pressure gap with respect to industrial reaction conditions, the observed phenomena provide a plausible interpretation of the behavior of Ni/Cu based catalysts for CO2 conversion and account for a possible role of CO in the methanol synthesis process.
Keywords: carbon dioxide; carbon monoxide; graphene; hydrogen; nickel; reduction.