用于氧还原反应的Fe-N-C单原子催化剂的缺陷工程

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

摘要/Abstract

摘要：

过渡金属M-N-C单原子催化剂(SACs), 特别是Fe-N-C催化剂, 已被认为是替代铂族金属进行氧还原反应(ORR)的最佳候选材料之一. 实验研究和理论计算均表明, FeN₄配位结构是Fe-N-C材料的活性中心, 但实验合成不可避免的构型缺陷明显影响了FeN₄中心的物理性质和催化活性. 目前有些技术能可控地产生缺陷, 这为原子级调控Fe-N-C催化剂局部结构提供可能. 目前关于缺陷对Fe-N-C材料ORR活性影响的计算研究仍存在一些不足, 如未考虑Fe位点的预吸附行为, 没有系统考察各种缺陷结构对FeN₄中心的ORR活性的影响. 因此, 探索不同缺陷类型及其位置对ORR活性的影响, 揭示缺陷Fe-N-C催化剂的结构-性能关系, 对于进一步指导实验调控局部结构以获得高性能的Fe-N-C氧还原催化剂具有极其重要的意义.
本文在FeN₄位点周围的二、三、四壳层内构建了13种含555777缺陷的Fe-N-C模型、16种含5775缺陷的Fe-N-C模型和14种含585缺陷的Fe-N-C模型, 研究了缺陷对Fe-N-C材料ORR活性的影响, 以及缺陷种类和位置对FeN₄位点ORR活性的影响. 首先通过DFT计算确定了缺陷Fe-N-C材料在ORR过程中真正的活性位点结构, 即当Fe-N键长 > 2.10 Å时, Fe位点不会预吸附任何中间体, 其活性中心为FeN₄, 速率决定步骤(PDS)为*OH质子化为H₂O (*OH + H⁺ + e^- → * + H₂O); 而当Fe-N键长 < 2.10 Å时, Fe位点会预吸附*OH物种形成Fe(OH)N₄活性中心, 其PDS为O₂质子化为*OOH (* + O₂ + H⁺ + e^- → *OOH). 预吸附的*OH会通过调节Fe(OH)N₄位点(特别是Fe-d_z2和d_yz轨道之间)和再吸附的*OH中间体之间的电子分布, 降低Fe中心的吸附能力, 从而提高ORR活性. 也进一步揭示了Fe(d_xz)-O(p_x)、Fe(d_yz)-O(p_y)和Fe(d_z2)-O(p_z+s)轨道的杂化是缺陷Fe-N-C材料ORR活性的来源. 为了在不进行DFT计算的情况下实现结构-性能关系的预测, 基于Fe(OH)N₄位点的L_Fe-OH(Fe-OH的键长)和L_Fe-defect (Fe原子和缺陷的距离), 建立了一个通用的仅与材料本征性能相关的结构描述符φ, 该描述符可以准确和定量地预测缺陷Fe-N-C催化剂的ORR活性. 研究发现, 5775和585缺陷的大环毗邻Fe-N-C五边形环时通常会增加L_Fe-OH和L_Fe-defect, 这显著调节了Fe-d_yz轨道在费米能级上方的峰值位置, 以接近最佳能级, 从而提高了ORR性能. 此外, 提出了与Fe-N键长相关的指数α, 以确认实验中是否形成主动设计的缺陷. 综上, 本文揭示了缺陷Fe-N-C材料的ORR活性来源, 建立了一个内在的结构描述符φ, 可以无需DFT计算准确预测ORR活性, 为通过缺陷工程提高Fe-N-C的ORR性能提供了新思路.

关键词: 单原子催化剂, 氧还原反应, 缺陷工程, 轨道杂化理论, 预吸附, 结构描述符

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

姜润, 乔泽龙, 许昊翔, 曹达鹏. 用于氧还原反应的Fe-N-C单原子催化剂的缺陷工程[J]. 催化学报, 2023, 48: 224-234.

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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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(23)64419-5

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

图/表 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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