Synergistic enhancement of methane combustion over Pd/CeO2 via single-atom Ni doping: Boosting Pd4+ and oxygen vacancies

doi:10.1016/S1872-2067(26)64965-0

Abstract

Abstract:

Single-atom catalysts possess the ability to effectively modulate the chemical environment of active sites, thereby synergistically enhancing catalytic reaction activity due to their unique electronic properties. In this study, single-atom Ni-doped CeO₂-supported Pd catalysts were designed and synthesized. The introduction of single-atom Ni induced lattice distortion in the CeO₂ support, resulting in an increased concentration of oxygen vacancies on the surface. This increase in oxygen vacancies enhances the strong metal-support interactions between Pd and the support. Under the intensified metal-support interaction effect, Pd species tend to transfer more electrons to Ni atoms and adjacent O atoms, leading to a higher proportion of high oxidation states (Pd⁴⁺) in PdO_x species. The presence of high-valent Pd⁴⁺ and oxygen vacancies synergically enhances the activation of C-H bonds in methane and the adsorption and dissociation of oxygen, significantly improving the overall catalytic activity of methane combustion. This study provides a critical theoretical foundation and practical guidance for the design and optimization of clean energy catalysts.

Key words: Single-atom Ni, CeO₂, Strong metal-support interaction, Pd⁴⁺, CH₄ combustion

Cheng Rao, Mengyu Qian, Songyun Tao, Huaiyuan Wang, Dan He, Jun Ye, Hai Liu, Xiangguang Yang, Yibo Zhang. Synergistic enhancement of methane combustion over Pd/CeO₂ via single-atom Ni doping: Boosting Pd⁴⁺ and oxygen vacancies[J]. Chinese Journal of Catalysis, 2026, 83: 419-431.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)64965-0

https://www.cjcatal.com/EN/Y2026/V83/I4/419

Figures/Tables 9

Fig. 1. XRD patterns (a,b) and Raman patterns (c) of Pd/Ni1-CeO2 and related catalysts. High-resolution transmission electron microscope and spherical aberration electron microscopy images of CeO2 (d?f) and Ni1-CeO2 (g?i) catalysts.

Fig. 2. Spherical aberration electron microscopy images and the EDS mapping of Pd, Ni, Ce and O for Pd/CeO2 (a?f) and Pd/Ni1-CeO2 (g?l) catalysts and correspondingly mapping images.

Fig. 3. (a) Normalized Ni K-edge XANES spectra. (b) Fourier transforms of k3-weighted Ni K-edge EXAFS spectra for Pd/Ni1-CeO2, Ni foil, and NiO. (c) EXAFS spectrum fitting result of Pd/Ni1-CeO2 in R space. EXAFS wavelets transform images of Ni foil (d), NiO (e), and Pd/Ni1-CeO2 (f).

Table 1 EXAFS fitting parameters at the Ni K-edge for various samples.

Sample	Shell	CN^a	R ^b (Å)	σ²^c (Å²)	ΔE₀ ^d (eV)	R factor
Ni-foil	Ni-Ni	12.0	2.485 ± 0.002	0.0062	7.7	0.0010
NiO	Ni-O	6.0±0.8	2.097 ± 0.014	0.0076	5.1	0.0057
NiO	Ni-Ni	12.5±1.0	2.948 ± 0.006	0.0076	1.1	0.0057
Pd/Ni₁-CeO₂	Ni-O	3.5±0.1	2.049 ± 0.002	0.0044	‒2.4	0.0046
Pd/Ni₁-CeO₂	Ni-Ce	1.1±0.1	3.046 ± 0.008	0.0022	0.3	0.0046

Fig. 4. Catalytic activities of CeO2, Pd/CeO2 and Pd/Ni1-CeO2 catalysts. The conversion rate of methane at different temperatures (a), the activation energy (b), the reaction order of methane (c) and oxygen for catalytic methane combustion (d).

Fig. 5. (a) Methane oxidation activity under cyclic testing of Pd/Ni1-CeO2 catalyst. Stability test at 400 °C for 130 h (b), stability test against 5 vol% H2O (c) and stability test against 5 × 10-6 SO2 (d).

Fig. 6. Ni 2p (a), Pd 3d (b), O 1s (c) and Ce 3d (d) XPS spectra of CeO2, Ni1-CeO2, Pd/CeO2 and Pd/Ni1-CeO2 catalysts. The optimized computational models (e) and the differential charge density of Pd/Ni1-CeO2 (f) are illustrated. Color scheme: Pd, grey; Ce, chartreuse; Ni, purple; O, red; C, brown and H, white. The yellow and cyan areas represent the regions of electron gain and loss, respectively.

Fig. 7. H2-TPR (a) and CH4-TPD (b) spectra of CeO2, Ni1-CeO2, Pd/CeO2 and Pd/Ni1-CeO2 catalysts.

Fig. 8. In-situ DRIFTS study of CH4 adsorption and oxidation at 350 °C for different durations. Pd/CeO2 (1% CH4/Ar) (a), Pd/CeO2 (1% CH4/Air) (b), Pd/Ni1-CeO2 (1% CH4/Ar) (c) and Pd/Ni1-CeO2 (1% CH4/Air) (d). (e) DFT simulations of methane activation and the energy barriers over Pd/CeO2 and Pd/Ni1-CeO2. (initial state (IS), adsorbed state (*CH4), transition state (TS), and final state (*CH3+H). Color scheme: Pd, grey; Ce, chartreuse; Ni, purple; O, red; C, brown and H, white.

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Synergistic enhancement of methane combustion over Pd/CeO₂ via single-atom Ni doping: Boosting Pd⁴⁺ and oxygen vacancies

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