UC Davis

The reaction pathways on supported catalysts can be tuned by optimizing the catalyst structures, which helps the development of efficient catalysts. Such design is particularly desired for CO₂ hydrogenation, which is characterized by complex pathways and multiple products. Here, we report an investigation of supported cobalt, which is known for its hydrocarbon production and ability to turn into a selective catalyst for methanol synthesis in CO₂ hydrogenation which exhibits good activity and stability. The crucial technique is to use the silica, acting as a support and ligand, to modify the cobalt species via Co‒O‒SiO_n linkages, which favor the reactivity of spectroscopically identified *CH₃O intermediates, that more readily undergo hydrogenation to methanol than the C‒O dissociation associated with hydrocarbon formation. Cobalt catalysts in this class offer appealing opportunities for optimizing selectivity in CO₂ hydrogenation and producing high-grade methanol. By identifying this function of silica, we provide support for rationally controlling these reaction pathways.