The mechanism for CO2 reduction over Fe-modified Cu(100) surfaces with thermodynamics and kinetics: a DFT study

摘要

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.