The mechanism for CO 2 reduction over Fe-modified Cu(100) surfaces with thermodynamics and kinetics: a DFT study.

The adsorption, activation and reduction of CO 2 over Fe x /Cu(100) ( x = 1-9) surfaces were examined by density functional theory. The most stable structure of CO 2 adsorption on the Fe x /Cu(100) surface was realized. The electronic structure analysis showed that the doped Fe improved the adsorption, activation and reduction of CO 2 on the pure Cu(100) surface. From the perspective of thermodynamics and kinetics, the Fe 4 /Cu(100) surface acted as a potential catalyst to decompose CO 2 into CO with a barrier of 32.8 kJ mol -1 . Meanwhile, the first principle molecular dynamics (FPMD) analysis indicated that the decomposition of the C-O1 bond of CO 2 on the Fe 4 /Cu(100) surface was only observed from 350 K to 450 K under a CO 2 partial pressure from 0 atm to 10 atm. Furthermore, the results of FPMD analysis revealed that CO 2 would rather decompose than hydrogenate when CO 2 and H co-adsorbed on the Fe 4 /Cu(100) surface.