In this work, we studied the reaction mechanisms for CO2 reduction reaction (CRR) on the iron-doped graphene and its coordinating sulfur (S) and nitrogen (N) variants, FeNn S4-n (n=1-4), using density functional theory calculations. Our results revealed that the electronic property and catalytic reactivity of the surfaces can be tuned by varying the N and S atoms ratio. The CRR activities of the mixed surfaces, FeN3 S1 , FeN2 S2 , and FeN1 S3 , were better than FeN4 and FeS4 , where the absolute value of the limiting potential of the mixed surface decreased by 0.3 V. Considering the stability, we suggest FeN3 S surface to be favorable for CRR. For the bare surfaces, we found a positive linear correlation between the magnetic moment and the charge of Fe metal. For these surfaces, the reduction of CO (*CO+(H+ +e- )→*CHO) was important in deciding the limiting potential. We found that the adsorption energy of CO displayed a volcano relationship with the magnetic moment of the Fe atom. The study showed that the change of local coordinating structure around the Fe atom could modify the electronic and magnetic properties of the active Fe center and improve the CRR activity performance.
Keywords: CO2 reduction; density functional theory; electrocatalysis; iron doped graphene; magnetic moment.
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