CO reduction reaction on Sc-doped nanocages as catalysts.

CONTEXT

The catalytic ability of Sc-doped C and Sc-doped AlP as catalysts of CO-RR to create the CH and CHOH is investigated. The mechanisms of CO-RR are examined by theoretical methods and ΔG of reaction steps of CO-RR mechanisms are calculated. The overpotential of CH and CHOH production on Sc-doped C and Sc-doped AlP is calculated. The Sc atoms of Sc-doped C and Sc-doped AlP can adsorb the CO molecule as the first step of CO-RR. The CH is produced from hydrogenation of *CHO and the *CO → *CHO reaction step is the rate limiting step for CH production. The CHOH can be formed on Sc-doped C and Sc-doped AlP by *CO → *CHO → *CHO → *CHO → CHOH mechanism and HCOOH → *CHO → *CHO → *CHO → CHOH mechanism. The Sc-C and Sc-AlP can catalyze the CO-RR to produce the CH and CHOH 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 CO-RR are investigated by mentioned methods. The transition state of each reaction step of CO-RR is searched by Berny method to find the CO-RR intermediates. The ∆E of intermediates of CO-RR on surfaces of nanocages is calculated and the ∆G of reaction steps of CO-RR is calculated.