Exploring the catalytic activity of metal‐fullerene C ₅₈ M (M = Mn, Fe, Co, Ni, and Cu) toward oxygen reduction and CO oxidation by density functional theory

Abstract

Summary In the present work, the catalytic activity of metal‐fullerene C58M (M = Mn, Fe, Co, Ni, and Cu) toward oxygen reduction reaction (ORR) and CO oxidation has been explored by detailed density functional theory calculations. Firstly, the binding energy of various ORR species (OOH, O, and OH) on C58M and the corresponding adsorption structures are calculated. The results show that the adsorption strength of any ORR species on C58M follows the order of C58Mn > C58Fe > C58Co > C58Ni > C58Cu and C58Co shows the closest binding energy compared with the Pt(111) surface. Further analysis of the free energy change of ORR indicates that C58Co, C58Ni, and C58Fe have different degrees of catalytic activities, with the calculated free energy change of rate‐determining step of −0.70, −0.32, and −0.04 eV, respectively. On the basis of the above results, the C58Co obviously has the highest ORR activity, with a relatively small overpotential of 0.53 V. In addition, the adsorption free energy of OH can be used as a good descriptor for ORR activity due to the nearly linear relationships between ∆G*OOH, ∆G*O, and ∆G*OH. At last, the catalytic property of C58Co toward CO oxidation reaction is also explored. The calculated results show that CO oxidation on C58Co follows LH mechanism and the rate‐determining step is recognized as *CO + *O2 → *OOCO, with the energy change of −0.13 eV.

Cobalt‐based coordination polymer as high activity electrocatalyst for oxygen reduction reaction: Catalysis by novel active site CoO 4 N 2

“…It should be noted that, if the relative energy change of every ORR process is converted to the Gibbs free energy profiles based on above theory, the ORR overpotential ( η ORR ) can be obtained. The η ORR is estimated as η ORR = Δ G min /e + 1.23, in which ∆ G min is the smallest variation in Gibbs free energy during the entire ORR process . The calculated free energy changes of each electron transfer step for Pathway I and II are shown in Table .…”

“…The η ORR is estimated as η ORR = ΔG min /e + 1.23, in which ΔG min is the smallest variation in Gibbs free energy during the entire ORR process. 45 The calculated free energy changes of each electron transfer step for Pathway I and II are shown in Table 3. Therefore, the η ORR of Pathway I is 0.43 V, which is consistent with experimental observation (0.42 V).…”

Theoretical Study on the Structures of Single-Atom M (M=Fe, Co and Ni) Adsorption Outside and Inside the Defect Carbon Nanotubes

“…Moreover, once the defects formed, it is generally di cult to removed, eg., the recovery of the CNTs from the SW defect needs to overcome a very high barrier to ca 6eV [9]. We all know that Fe, Co and Ni nanocrystals have been used for organic pollutant removal due to their low cost and high catalytic activity [10][11][12][13][14][15][16][17][18][19][20][21][22][23]. Liu and coworkers report that the defect-rich Pt-M (M = Fe, Co, Ni) ultrathin nanowires can be used as electrode to enhance methanol electrooxidation.Fu et al study that PtM (M = Fe, Co, Ni) bimetallic nanoclusterscan be used as active and methanol-tolerant to enhance catalytic performances for the reactions of oxygen reduction.…”

The study of oxygen reduction reaction on Ge‐doped MoS 2 monolayer based on first principle

“…11,12 Carbon-based materials have been regarded as the most possible alternatives to Pt-based material due to their abundance, low cost, and excellent stability. [13][14][15] As a 2D carbon-based materials, graphene has been demonstrated to be an effective ORR catalyst, especially heteroatoms-doped graphene. 16,17 The introduction of heteroatoms, such as nitrogen, sulfur, phosphorus, or boron atom, into graphene lattice has shown an improved ORR catalytic activity.…”