镧系元素-锌共掺杂Pd/CeO2单原子催化剂中晶格氧活化与表面再氧化的平衡及其对CO氧化性能的影响

doi:10.1016/S1872-2067(26)65256-4

摘要/Abstract

摘要：

氧化铈负载的Pd单原子催化剂在三效催化体系的低温CO氧化中具有良好的应用前景, 但其稳定性与活性之间的内在权衡关系仍缺乏深入认识. 本文结合密度泛函理论计算和微动力学模拟, 系统地研究了镧系元素(Ln)-Zn共掺杂对Pd₁/CeO₂(111)单原子催化剂结构与CO氧化性能的影响. 在该设计体系中, Zn稳定孤立的Pd原子并促进晶格氧活化, 而引入Ln旨在进一步提高晶格氧反应性并调控反应物吸附. 然而, 微观动力学模拟结果表明, 与锌掺杂参考体系相比, Ln-Zn共掺杂反而降低了CO氧化活性. 尽管Ln的引入增强了晶格氧反应性并促进了氧空位形成, 但同时也抑制了O₂的吸附与活化以及氧空位的再填充, 使催化循环的动力学限制由晶格氧参与转变为O₂活化, 最终导致转化率降低. 研究结果表明, 对于Mars-van Krevelen反应, 单纯增强晶格氧的反应性并不能提高整体催化活性; 催化性能的提升需要兼顾晶格氧活化和表面再氧化过程. 因此, 仅凭氧空位形成能等单一描述符难以准确预测催化性能. 本文强调, 有效的催化剂设计需要根据特定催化体系的动力学特性选择组合描述符, 而不是依赖于单一的通用描述符.

关键词: 密度泛函理论, CO氧化, 共掺杂, 镧系, 过渡金属, 微观动力学模拟, Pd, 单原子催化

Abstract:

Ceria-supported Pd single-atom catalysts are promising for low-temperature CO oxidation in three-way catalysis, yet the fundamental trade-off between stability and activity remains poorly understood. Here, we systematically investigate the effect of lanthanide (Ln)-Zn co-doping on Pd₁/CeO₂(111) using density functional theory and microkinetic simulations. In this design, Zn stabilizes isolated Pd atoms and promotes lattice-oxygen activation, while Ln dopants are introduced to further enhance lattice oxygen reactivity and tune reactant adsorption. Despite these intended benefits, microkinetic simulations reveal that Ln co-doping consistently decreases the CO oxidation activity compared to the Zn-doped reference. While Ln incorporation enhances lattice oxygen reactivity and facilitates vacancy formation, it simultaneously hinders O₂ adsorption, activation, and vacancy replenishment. As a result, the catalytic cycle becomes limited by O₂ activation rather than lattice oxygen participation, leading to a lower turnover frequency. These findings demonstrate that increasing lattice oxygen reactivity alone does not guarantee improved catalytic performance in systems operating via a Mars-van Krevelen mechanism. Instead, catalytic activity is governed by a delicate balance between lattice oxygen activation and reoxidation kinetics. Consequently, commonly used descriptors such as oxygen vacancy formation energy are insufficient to predict catalytic performance. This work highlights that effective catalyst design requires the selection of combined descriptors based on the kinetic characteristics of the specific catalytic system, rather than relying on a single universal descriptor.

Key words: Density functional theory, CO oxidation, Co-doping, Lanthanides, Transition metal, Microkinetic simulations, Pd, Single atom catalysis

Mengrong Li, Bram D. Bruininks, Ivo A. W. Filot, Emiel J. M. Hensen. 镧系元素-锌共掺杂Pd/CeO₂单原子催化剂中晶格氧活化与表面再氧化的平衡及其对CO氧化性能的影响[J]. 催化学报, 2026, 91: 396-411.

Mengrong Li, Bram D. Bruininks, Ivo A. W. Filot, Emiel J. M. Hensen. Balancing lattice oxygen activation and surface reoxidation in lanthanide-Zn co-doped Pd/CeO₂ single-atom catalysts for CO oxidation[J]. Chinese Journal of Catalysis, 2026, 91: 396-411.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(26)65256-4

https://www.cjcatal.com/CN/Y2026/V91/I12/396

图/表 11

Fig. 1. Configurations (left) and corresponding Ov formation energy heatmaps (right) for Ln-doped CeO2(111) (a) and Ln-Zn co-doped Pd1/CeO2(111) (b) (Ln=purple; Zn=yellow; Pd=blue).

Fig. 2. (a) Stabilization energies of a Pd atom on Zn-Ln co-doped CeO2(111), with Zn-doped CeO2(111) taken as the reference (Ref). (b) Energy profiles for migration of a Pd atom on Zn-Ln co-doped CeO2(111) surfaces. IM1, IM2, and IM3 denote the initial, transition, and final states, respectively. The values reported along the migration pathway represent the energy difference between the transition state (IM2) and the initial state (IM1). (c) Corresponding structures along the migration pathway for IM1, IM2, and IM3 in both Zn-Ln co-doped and Zn-doped CeO2(111).

Fig. 3. The partial density of states of Pd-4d and O-2p orbitals (O adjacent to the Pd and Ln) in Ln-Zn co-doped Pd1/CeO2(111) (Ln=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu). Energies are referenced to the Fermi level (EF=0). The value shown in each of the graphs corresponds to the integrated DOS (number of electrons) of the Pd-4d below the Fermi level. The corresponding pDOS of Zn-doped Pd1/CeO2(111) and pristine Pd1/CeO2(111), denoted as None, are included for comparison [65].

Fig. 4. The reaction pathways over Ln-Zn co-doped Pd1/CeO2(111) (Ln=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) (colour code: white=Ce; red=lattice O; yellow=Zn; light purple=Ln; blue=Pd; grey=C; pink=O involved in reaction). Pathway 1=P1 + P2, Pathway 2=P1 + P3.

Fig. 5. Potential energy diagrams of CO oxidation on Ln-Zn co-doped Pd1/CeO2(111), with Zn-doped Pd1/CeO2(111) as reference (Ref). (a) The common initial pathway (P1), followed by O2 dissociative pathway (P2). (b) The possible O2 non-dissociative pathway (P3) following P1.

Table 1 Calculated energies for the CO oxidation reaction of Ln-Zn co-doped and Zn-doped Pd1/CeO2(111), which also correspond to Figs. 4 and 5 (all energies in eV).

CO oxidation with O₂ direct dissociation (P1 + P2)
Ln	CO_ads	TS1	CO_2rea	CO_2des	O_2ads	TS2	O_2rea	CO_ads	CO_2des
La	‒1.65	0.34	‒1.00	0.41	‒1.44	1.17	0.85	‒5.01	1.53
Pr	‒1.70	0.37	‒1.00	0.42	‒1.45	1.16	0.77	‒4.93	1.52
Nd	‒1.65	0.36	‒0.88	0.35	‒1.48	1.15	0.76	‒4.92	1.51
Sm	‒1.64	0.34	‒0.97	0.44	‒1.47	1.14	0.74	‒4.91	1.50
Eu	‒1.64	0.34	‒0.96	0.44	‒1.48	1.14	0.74	‒4.92	1.50
Gd	‒1.64	0.33	‒0.95	0.63	‒1.67	1.13	0.75	‒4.92	1.48
Tb	‒1.58	0.26	‒1.00	0.46	‒1.50	1.12	0.72	‒4.90	1.47
Dy	‒1.64	0.33	‒0.92	0.46	‒1.50	1.12	0.72	‒4.89	1.46
Ho	‒1.64	0.33	‒0.69	0.25	‒1.51	1.12	0.71	‒4.90	1.46
Er	‒1.63	0.32	‒0.91	0.49	‒1.53	1.11	0.73	‒4.90	1.44
Tm	‒1.80	0.33	‒0.94	0.82	‒1.65	1.11	0.73	‒4.92	1.43
Yb	‒1.62	0.32	‒0.89	0.49	‒1.53	1.10	0.68	‒4.88	1.44
Lu	‒1.63	0.33	‒0.86	0.48	‒1.51	1.09	0.65	‒4.86	1.42
Ref	‒1.93	0.53	‒0.06	0.63	‒1.51	0.43	‒0.33	‒4.46	1.34
CO oxidation with O₂ non-direct dissociation (P1 +P3)
Ln	CO_ads	TS1	CO_2rea	CO_2des	CO_ads	O_2ads	TS3	CO_2rea	CO_2des
La	—	—	—	—	‒1.88	‒1.15	0.70	‒1.58	0.55
Pr	—	—	—	—	‒1.85	‒1.19	0.70	‒1.59	0.55
Nd	—	—	—	—	‒1.90	‒1.88	0.70	‒1.61	0.55
Sm	—	—	—	—	‒1.88	‒1.18	0.69	‒1.64	0.55
Eu	—	—	—	—	‒1.88	‒1.88	0.68	‒1.66	0.55
Gd	—	—	—	—	‒2.05	‒1.19	0.68	‒1.67	0.55
Tb	—	—	—	—	‒1.90	‒1.17	0.68	‒1.63	0.49
Dy	—	—	—	—	‒1.88	‒1.18	0.67	‒1.70	0.55
Ho	—	—	—	—	‒1.90	‒1.16	0.61	‒1.71	0.55
Er	—	—	—	—	‒1.90	‒1.19	0.66	‒1.73	0.55
Tm	—	—	—	—	‒2.05	‒1.16	0.66	‒1.74	0.55
Yb	—	—	—	—	‒1.91	‒1.18	0.60	‒1.75	0.55
Lu	—	—	—	—	‒1.88	‒1.19	0.65	‒1.77	0.55
Ref	—	—	—	—	‒1.90	‒1.57	0.39	‒0.05	0.43

Table 1 Calculated energies for the CO oxidation reaction of Ln-Zn co-doped and Zn-doped Pd1/CeO2(111), which also correspond to Figs. 4 and 5 (all energies in eV).

CO oxidation with O₂ direct dissociation (P1 + P2)
Ln	CO_ads	TS1	CO_2rea	CO_2des	O_2ads	TS2	O_2rea	CO_ads	CO_2des
La	‒1.65	0.34	‒1.00	0.41	‒1.44	1.17	0.85	‒5.01	1.53
Pr	‒1.70	0.37	‒1.00	0.42	‒1.45	1.16	0.77	‒4.93	1.52
Nd	‒1.65	0.36	‒0.88	0.35	‒1.48	1.15	0.76	‒4.92	1.51
Sm	‒1.64	0.34	‒0.97	0.44	‒1.47	1.14	0.74	‒4.91	1.50
Eu	‒1.64	0.34	‒0.96	0.44	‒1.48	1.14	0.74	‒4.92	1.50
Gd	‒1.64	0.33	‒0.95	0.63	‒1.67	1.13	0.75	‒4.92	1.48
Tb	‒1.58	0.26	‒1.00	0.46	‒1.50	1.12	0.72	‒4.90	1.47
Dy	‒1.64	0.33	‒0.92	0.46	‒1.50	1.12	0.72	‒4.89	1.46
Ho	‒1.64	0.33	‒0.69	0.25	‒1.51	1.12	0.71	‒4.90	1.46
Er	‒1.63	0.32	‒0.91	0.49	‒1.53	1.11	0.73	‒4.90	1.44
Tm	‒1.80	0.33	‒0.94	0.82	‒1.65	1.11	0.73	‒4.92	1.43
Yb	‒1.62	0.32	‒0.89	0.49	‒1.53	1.10	0.68	‒4.88	1.44
Lu	‒1.63	0.33	‒0.86	0.48	‒1.51	1.09	0.65	‒4.86	1.42
Ref	‒1.93	0.53	‒0.06	0.63	‒1.51	0.43	‒0.33	‒4.46	1.34
CO oxidation with O₂ non-direct dissociation (P1 +P3)
Ln	CO_ads	TS1	CO_2rea	CO_2des	CO_ads	O_2ads	TS3	CO_2rea	CO_2des
La	—	—	—	—	‒1.88	‒1.15	0.70	‒1.58	0.55
Pr	—	—	—	—	‒1.85	‒1.19	0.70	‒1.59	0.55
Nd	—	—	—	—	‒1.90	‒1.88	0.70	‒1.61	0.55
Sm	—	—	—	—	‒1.88	‒1.18	0.69	‒1.64	0.55
Eu	—	—	—	—	‒1.88	‒1.88	0.68	‒1.66	0.55
Gd	—	—	—	—	‒2.05	‒1.19	0.68	‒1.67	0.55
Tb	—	—	—	—	‒1.90	‒1.17	0.68	‒1.63	0.49
Dy	—	—	—	—	‒1.88	‒1.18	0.67	‒1.70	0.55
Ho	—	—	—	—	‒1.90	‒1.16	0.61	‒1.71	0.55
Er	—	—	—	—	‒1.90	‒1.19	0.66	‒1.73	0.55
Tm	—	—	—	—	‒2.05	‒1.16	0.66	‒1.74	0.55
Yb	—	—	—	—	‒1.91	‒1.18	0.60	‒1.75	0.55
Lu	—	—	—	—	‒1.88	‒1.19	0.65	‒1.77	0.55
Ref	—	—	—	—	‒1.90	‒1.57	0.39	‒0.05	0.43

Fig. 6. (a) CO2 formation rate and (b) apparent activation energies ($E_{\text {act }}^{a p p}$) as a function of temperature for Zn-Ln co-doped Pd1/CeO2(111) systems, with Zn-doped Pd1/CeO2(111) system as reference (Ref).

Fig. 7. (a)-(n) Surface coverages of key intermediates as a function of temperature during the CO oxidation reaction on co-doped Zn-Ln Pd1/CeO2(111) systems, where Ln=La (a), Pr (b), Nd (c), Sm (d), Eu (e), Gd (f), Tb (g), Dy (h), Ho (i), Er (j), Tm (k), Yb (l), and Lu (m). (n) The corresponding results for the Zn-doped are shown in panel (n) as the reference system (Ref).

Fig. 8. Degree of rate-control coefficients for elementary steps in CO oxidation over Ln-Zn co-doped Pd1/CeO2(111) systems, where Ln=La (a), Pr (b), Nd (c), Sm (d), Eu (e), Gd (f), Tb (g), Dy (h), Ho (i), Er (j), Tm (k), Yb (l), and Lu (m), together with Zn-doped Pd1/CeO2(111) as the reference system (n).

Fig. 9. (a)‒(n) Normalized contributions of each CO2-forming flux to the overall reaction of CO2 production as a function of temperature. (o) Schematic representation of the CO oxidation reaction network based on CO2 as a key intermediate.

Fig. 10. Statistical assessment of the applicability and transferability of EOv as an activity descriptor. Pearson correlation matrices among EOv, TS2, TS3, TOF, and log10(TOF) for (a) Ln-Zn co-doped systems and (b) Ln-Zn co-doped systems together with Zn-doped reference. (c) Parity plot of the calculated and in-sample fitted log10(TOF) values for the Zn-Ln co-doped systems using a single-parameter linear regression based on EOv. (d) Parity plot of the calculated and in-sample fitted log10(TOF) values for the complete dataset using a multiple linear regression containing EOv, TS2, and TS3. The Zn-doped reference is highlighted by the red square, and the dashed lines in (c) and (d) represent perfect agreement between the calculated and fitted values (y=x). The detailed p-values, confidence intervals, adjusted R2, leave-one-out cross-validation metrics, variance inflation factors, and influence diagnostics have been added to Table S3 and Table S4, respectively.

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镧系元素-锌共掺杂Pd/CeO₂单原子催化剂中晶格氧活化与表面再氧化的平衡及其对CO氧化性能的影响

Balancing lattice oxygen activation and surface reoxidation in lanthanide-Zn co-doped Pd/CeO₂ single-atom catalysts for CO oxidation

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