CO2 reduction reaction on Sc-doped nanocages as catalysts.

CONTEXT: The catalytic ability of Sc-doped C46 and Sc-doped Al23P23 as catalysts of CO2-RR to create the CH4 and CH3OH is investigated. The mechanisms of CO2-RR are examined by theoretical methods and ΔGreaction of reaction steps of CO2-RR mechanisms are calculated. The overpotential of CH4 and CH3OH production on Sc-doped C46 and Sc-doped Al23P23 is calculated. The Sc atoms of Sc-doped C46 and Sc-doped Al23P23 can adsorb the CO2 molecule as the first step of CO2-RR. The CH4 is produced from hydrogenation of *CH3O and the *CO → *CHO reaction step is the rate limiting step for CH4 production. The CH3OH can be formed on Sc-doped C46 and Sc-doped Al23P23 by *CO → *CHO → *CH2O → *CH3O → CH3OH mechanism and HCOOH → *CHO → *CH2O → *CH3O → CH3OH mechanism. The Sc-C46 and Sc-Al23P23 can catalyze the CO2-RR to produce the CH4 and CH3OH by acceptable mechanisms. METHODS: Here, the structures are optimized by PW91PW91/6-311+G (2d, 2p) and M06-2X/cc-pVQZ methods in GAMESS software. The frequencies of nanocages and their complexes with species of CO2-RR are investigated by mentioned methods. The transition state of each reaction step of CO2-RR is searched by Berny method to find the CO2-RR intermediates. The ∆Eadsorption of intermediates of CO2-RR on surfaces of nanocages is calculated and the ∆Greaction of reaction steps of CO2-RR is calculated.