Highly Efficient Ambient Temperature CO 2 Photomethanation Catalyzed by Nanostructured RuO 2 on Silicon Photonic Crystal Support

Abstract Sunlight‐driven catalytic hydrogenation of CO 2 is an important reaction that generates useful chemicals and fuels and if operated at industrial scales can decrease greenhouse gas CO 2 emissions into the atmosphere. In this work, the photomethanation of CO 2 over highly dispersed nanostructured RuO 2 catalysts on 3D silicon photonic crystal supports, achieving impressive conversion rates as high as 4.4 mmol g cat −1 h −1 at ambient temperatures under high‐intensity solar simulated irradiation, is reported. This performance is an order of magnitude greater than photomethanation rates achieved over control samples made of nanostructured RuO 2 on silicon wafers. The high absorption and unique light‐harvesting properties of the silicon photonic crystal across the entire solar spectral wavelength range coupled with its large surface area are proposed to be responsible for the high methanation rates of the RuO 2 photocatalyst. A density functional theory study on the reaction of CO 2 with H 2 revealed that H 2 splits on the surface of the RuO 2 to form hydroxyl groups that participate in the overall photomethanation process.