Small Au, Cu, and Ni particles in contact with TiC(001) display a very high activity for the catalytic hydrogenation of CO2. The major product over these catalysts is CO which is produced by the reverse water gas shift reaction (RWGS, CO2 + H-2 -> CO + H2O). In the cases of Au/TiC(001) and Cu/TiC(001), a substantial amount of methanol is also produced, but no methane is detected. Ni/TiC(001) produces a mixture of CO, methanol, and methane. The highest catalytic activity is found for small two-dimensional particles or clusters of the admetals in close contact with TiC(001). The catalytic activity of the supported metals can be orders of magnitude higher than those-of Au(100), Cu(100), or Ni(100). Density functional calculations point to HOCO as a key intermediate for the generation of CO through the RWGS, with the production of methanol probably involving the hydrogenation of a HCOO intermediate or the CO generated by the RWGS. (C) 2013 Elsevier Inc. All rights reserved.