This pathway is notable because CH2O* desorption is kinetically preferred to hydrogenation to CH3OH, promoting the presence of methanal in the gas phase for subsequent coupling. Second, the facile coupling between CH2* and CO2 leading to CH2COO* aligns with recent observations of carboxylic acid formation in CO2 hydrogenation. To the best of our knowledge, this facile direct coupling of CO2 with CH2* on metallic Cu is reported for the first time, whereas CO2-CHx couplings on Fe-Zn, Ni-Zn, and Co-Mn catalysts, as well as on non-metallic Cu-zeolite centers, 50 are well-known.