H2‐free synthesis of aromatic, cyclic and linear oxygenates from CO2

The synthesis of oxygenate products, including cyclic ketones and phenol, from CO2 and water in the absence of gas‐phase H2 has been demonstrated. The reaction takes place in sub‐critical conditions at 300 °C and pressure at room temperature of 25 barg. This is the first observation of the production of cyclic ketones by this route, and represents a step towards the synthesis of chemical products including methanol, without relying on fossil sources or H2 ‐ which carries a high carbon footprint in its production by conventional methods. Inspiration for these studies is taken directly from natural processes occurring in hydrothermal environments around ocean vents. Reactions over Al2O3 and zeolite‐based catalysts have, for the first time, demonstrated the ability to use catalyst properties such as acidity and pore size to direct the reaction towards specific products. These catalysts enhance the production of longer‐chained species (up to C8) with respect to conventional Fe catalysts due to the role of acid sites in catalysing rapid oligomerisation reactions. Notably, zeolite‐based catalysts promoted the formation of cyclic ketones. These proof‐of‐concept studies show the potential of this process to contribute sustainable development through either targeting methanol production, as part of ‘methanol economy’ or longer‐chained species including aromatics phenol and cyclic ketones.