Defect engineering of Fe-N-C single-atom catalysts for oxygen reduction reaction

doi:10.1016/S1872-2067(23)64419-5

Abstract

Abstract:

Fe-N-C single-atom catalysts (SACs) have been widely considered as a promising candidate for oxygen reduction reaction (ORR), and its intrinsic activity is closely related to electronic and geometric structure of graphene supports. The carbon defect is widely existed in graphene, of which the intrinsic effect on ORR activity of Fe-N-C is still unclear. Here, we investigate ORR activity of 43 models representing Fe-N-C SACs accompanying with defects, including 555777, 5775 and 585-defects in three shell distances around FeN₄ site. Both pre-adsorption of hydroxide radical during ORR and the distance between Fe SAC and defect are demonstrated to affect the orbital hybridizations between Fe SAC and *OH intermediate, including Fe(d_xz)-O(p_x), Fe(d_yz)-O(p_y) and Fe(d_z²)-O(p_z+s) orbitals, which can accordingly regulate ORR activity of defective Fe-N-C materials. Importantly, we establish a geometrical structure descriptor to quantitatively predict the ORR activity of defective Fe-N-C catalysts without any requirements of performing DFT calculations. With the assistance of the structure descriptor, we find that the 585 and 5775-defects of the large ring adjacent to the FeN₄ pentagonal in fourth shell significantly boost the ORR performance of Fe-N-C. This work reveals the ORR activity origin of defective Fe-N-C materials, which provides intuitive guidance to boost the ORR performance of Fe-N-C materials by defect engineering, and may be extended to other types of defects and other single-atom catalysts.

Key words: Single-atom catalyst, Oxygen reduction reaction, Defect engineering, Orbital hybridization theory, Pre-adsorption, Structure descriptor

Run Jiang, Zelong Qiao, Haoxiang Xu, Dapeng Cao. Defect engineering of Fe-N-C single-atom catalysts for oxygen reduction reaction[J]. Chinese Journal of Catalysis, 2023, 48: 224-234.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64419-5

https://www.cjcatal.com/EN/Y2023/V48/I5/224

Figures/Tables 5

Fig. 1. Structure models of different defects on Fe-N-C catalysts. (a) Illustration diagram of FeN4 site nearby shells. Brown, gray and gold balls represent carbon (C), nitrogen (N), and iron (Fe) respectively. (b) Schematic diagram of defects approaching FeN4 site gradually. (c) The stability of defective Fe-N-C. Black, red and blue symbols represent 555777, 5775 and 585-defect respectively. Square and triangle represent the nearest defect ring is larger and smaller than hexagon, respectively. Circle represents that the nearest neighbor has both large and small rings.

Fig. 2. ORR performance evaluation of defective Fe-N-C materials. (a) Mechanism scheme for ORR on clean slab and pre-adsorption slab. (b) Surface Pourbaix diagram of 585-FS5. (c) ORR Gibbs free energy diagram on clean slab and pre-adsorption slab of 585-FS5. (d) ORR onset potential (Uonset) of all the configurations (gray area for 555777-defects, red area for 5775-defects and blue area for 585-defects). Orange and green areas represent Uonset on clean slab and pre-adsorption slab. Brown and green vertical dotted lines represent Uonset on clean slab and pre-adsorption slab of pristine Fe-N-C respectively. (e) ORR activity volcano. Green area represents that ORR activity is better than pristine Fe-N-C. Blue and red circle represent the ΔGOH on clean slab and pre-adsorption slab of Fe-N-C respectively. Red and green points represent the defective Fe-N-C with and without pre-adsorption respectively. Purple points represent the ΔGOH of pristine Fe-N-C. (f) 2e- and 4e- ORR selectivity diagram based on ΔGO.

Fig. 3. The role of defect and pre-adsorption behavior in enhanced ORR performance of Fe-N-C materials. (a) (i) ORR onset potential, (ii) -ICOHP, (iii) Fe d-band center, (iv) Bader charge transfer from Fe to *OH and (v) Fe-OH bond length on pristine FeN4, 555777-FS4, 5775-FS3 and 585-FS5 configurations. (b,c) PDOS and PCOHP before and after adsorbing *OH on 585-FS5 defective Fe-N-C materials. The top panels in Figs. 3(b), 3(c) are PDOS of Fe center before adsorbing *OH, while middle and bottom panels are PDOS and PCOHP of Fe center after adsorbing *OH, respectively. Solid and dotted lines in bottom panel in Figs. 3(b), 3(c) represent bonding and anti-bonding orbitals, respectively. Orbital interactions between ORR intermediates and FeN4 site of clean slab (d) and pre-adsorption slab (e). Charge density difference after *OH adsorbed on clean slab (f) and pre-adsorption slab (g). (h) The correlation of Uonset vs. index P (relative with peak position of Fe dyz orbital) for defective Fe-N-C materials.

Fig. 4. The relationship between φ and defective Fe-N-C ORR activity. (a) Uonset vs. descriptor φ for training set. (b) Uonset vs. descriptor φ for training set (gray points) and validation set (red points) of defective Fe-N-C materials. Purple star represents pristine Fe-N-C materials. LFe-OH (c) and LFe-defect (d) of Fe-N-C materials with defects in varying locations. Black, red and blue symbols represent 555777, 5775 and 585-defects, respectively. Square and triangle representing the nearest defect ring is larger and smaller than hexagon, respectively. Circle represents the nearest neighbor with both large and small rings.

Fig. 5. Influence law of defects on Fe-N average bond length. Fe-N average bond length of FeN4 (a) and Fe(OH)N4 (b) vs. α.

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