Mechanism of photocatalytic CO 2 methanation on ultrafine Rh nanoparticles.

Selective hydrogenation of CO 2 to yield CH 4 relies on the appropriate catalysts that can facilitate the cleavage of CO bonds and dissociative adsorption of H 2 . Ultrafine Rh nanoparticles loaded on silica nanospheres were used as a class of photocatalysts to significantly improve the selectivity and reaction rate of producing CH 4 from the mixture of CO 2 and H 2 under the illumination of a broadband visible light source. The intense light scattering resonances in the silica nanospheres generate strong electric fields near the silica surface to enhance the light absorption power in the supported ultrafine Rh nanoparticles, promoting the efficiency of hot electron generation in the Rh nanoparticles. The interaction of the hot electrons with the adsorbate species on the Rh nanoparticle surface weakens the C-O bond to facilitate the deoxygenation of CO 2 , favoring the production of CH 4 with a unity selectivity at a faster rate in the presence of surface adsorbed hydrogen (H*). The systematic studies on reaction kinetics and diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy under different conditions, including various temperatures, illumination powers, and feeding gas compositions, reveal the reaction mechanism responsible for CO 2 methanation and the role of photoillumination.