Efficient methane combustion by engineering surface oxygen vacancies on MOF-derived multi-shell Pd@Co3O4

doi:10.1016/S1872-2067(26)65134-0

Abstract

Abstract:

ABSTRACT: Implementing low-temperature catalytic methane combustion is imperative for curbing the release of greenhouse gases. However, this process is fundamentally limited by the high energy barrier for C-H bond activation and the slow migration of lattice oxygen species. In this work, we introduced a topology-directed defect engineering strategy to synthesize a series of Pd@Co₃O₄ nanocages with adjustable shell numbers by precisely controlling the pyrolysis kinetics of ZIF-67. Among the synthesized catalysts, the quadruple-shell 1%Pd@Co₃O₄-Q system exhibits the best catalytic performance (T₅₀ = 305 °C), marking a 2.8-fold enhancement in reaction rate relative to the pristine Co₃O₄-Q catalyst, along with outstanding stability. Results of multidimensional characterizations (electron paramagnetic resonance, O₂-temperature programmed desorption, X-ray photoelectron spectroscopy) confirm that the unique multi-shell topology not only induces a high density of surface oxygen vacancies, but also optimizes the electronic configuration of Pd through strong electron-metal-support interactions. Kinetic analysis and in-situ diffuse reflectance Fourier transform infrared spectroscopy experiments verify that the reaction proceeds via the Mars-van Krevelen mechanism. The Pd sites significantly lower the activation barrier associated with C-H bond rupturing during the rate-determining step (with E_a decreasing to 66.6 kJ·mol^-1), and the abundant oxygen vacancies boost the transport efficiency of lattice oxygen species. Furthermore, density functional theory calculations unveil that electron donation from Pd to Co₃O₄ weakens the Co-O bond, thereby simultaneously depressing the energy required for oxygen vacancy formation and the barrier for methane dissociation. This work not only introduces an efficient catalyst for methane combustion, but also proposes a universal mechanism for regulating the chemistry of surface defects through the topological structure of MOF derivatives.

Key words: Metal-organic frameworks-derived materials, Methane catalytic combustion, Multi-shelled structure, Oxygen vacancy construction, Catalyst

Chunlei Zhang, Hanyu Tan, Chaoyang Sui, Ying Feng, Xinyu Chen, Xiaoqiang Fan, Xuehua Yu, Zhen Zhao. Efficient methane combustion by engineering surface oxygen vacancies on MOF-derived multi-shell Pd@Co₃O₄[J]. Chinese Journal of Catalysis, 2026, 88: 492-505.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65134-0

https://www.cjcatal.com/EN/Y2026/V88/I9/492

Figures/Tables 8

Fig. 1. XRD patterns (A), N2 adsorption-desorption isotherms (B), and pore size distributions (C) of prepared catalysts. (a) Co3O4-Q; (b) 1%Pd@Co3O4-Z; (c) 1%Pd@Co3O4-S; (d) 1%Pd@Co3O4-T; (e) 1%Pd@Co3O4-Q).

Fig. 2. TEM images of as-prepared catalysts (A1-D1); SAED patterns of as-prepared catalysts (A2-D2); EDS elemental mapping images (A3-D5). (A: 1%Pd@Co3O4-Q, B: 1%Pd@Co3O4-T, C: 1%Pd@Co3O4-S, D: 1%Pd@Co3O4-Z).

Fig. 3. XPS spectra of Pd 3d (A), O 1s (B), and Co 2p (C). (D) EPR spectra of as prepared catalysts. O2-TPD (E) and H2-TPR (F) curves of as-prepared catalysts. (a) Co3O4-Q; (b) 1%Pd@Co3O4-Z; (c) 1%Pd@Co3O4-S; (d) 1%Pd@Co3O4-T; (e) 1%Pd@Co3O4-Q.

Table 1 Parameters of the fitted components on surface from Pd 3d, Co 2p and O 1s XPS spectra.

Catalyst
	Pd			Co			O
	Pd²⁺	Pd⁴⁺	Co³⁺		Co²⁺	O_sur		O_ads	O_latt
Co₃O₄-Q	—	—	49.8		50.2	6.8		25.7	67.6
1%Pd@Co₃O₄-Z	54.5	45.5	45.5		54.5	4.1		28.4	67.6
1%Pd@Co₃O₄-S	56.6	43.4	44.2		55.8	4.6		29.6	65.8
1%Pd@Co₃O₄-T	57.6	42.4	34.9		65.1	3.2		31.8	64.9
1%Pd@Co₃O₄-Q	58.8	41.2	31.7		68.3	2.6		33.3	64.1

Fig. 4. CH4-TPR curves of as-prepared catalysts. (A) Co3O4-Q; (B) 1%Pd@Co3O4-Z; (C) 1%Pd@Co3O4-S; (D) 1%Pd@Co3O4-T; (E) 1%Pd@Co3O4-Q.

Fig. 5. (A,B) The catalytic activity of the as-prepared catalysts for methane combustion. (C) Arrhenius plots for methane combustion over the as-prepared catalysts. (D) Evaluation of the catalyst stability at 335 °C. Reaction conditions: 50 mg catalyst, reactant gas mixture of 1 vol% CH4 and 20 vol% O2 balanced with Ar, SV = 20000 mL·g-1·h-1.

Table 2 Catalytic activities and Ea of the catalysts for methane combustion at SV = 20000 mL·g-1·h-1.

Catalyst	Methane combustion			Methane combustion at 260 °C		E_a (kJ·mol^-1)
Catalyst	T₁₀ (°C)	T₅₀ (°C)	T₉₀ (°C)	Conversion (%)	Reaction rate (mmol·g^-1·s^-1)	E_a (kJ·mol^-1)
Co₃O₄-Q	277	356	434	5.90	1.47	85.40
1%Pd@Co₃O₄-Z	262	324	377	8.98	2.23	77.93
1%Pd@Co₃O₄-S	260	322	375	9.96	2.48	74.07
1%Pd@Co₃O₄-T	254	317	371	11.63	2.89	71.15
1%Pd@Co₃O₄-Q	243	305	356	16.34	4.06	66.58

Fig. 6. In-situ DRIFT spectra of methane combustion carried out over Co3O4-Q (A) and 1%Pd@Co3O4-Q (B) catalyst. Differential charge density map of the Pd13/Co3O4 (311) interface. The green and blue isosurfaces represent electron accumulation and depletion respectively. (C) The calculated Bader charge indicates that approximately 0.1627 e- of electrons are transferred from the Pd cluster to the Co3O4 support. PDOS of Co 3d orbitals on the surfaces of pure Co3O4 and Pd/Co3O4 catalysts. (D) The vertical dashed line represents the calculated position of the d-band center, the Fermi level is set to 0 eV. (E) Comparison of oxygen vacancy formation energies of Co3O4 and Pd/Co3O4 catalysts. (F) Comparison of C-H bond dissociation energies of Co3O4 and Pd/Co3O4 catalysts. (G) Comparison of free energies for surface intermediate conversion of Co3O4 and Pd/Co3O4 catalysts.

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Efficient methane combustion by engineering surface oxygen vacancies on MOF-derived multi-shell Pd@Co₃O₄

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