A water-resistant and stable Pd-Co3O4 catalytic interface for complete methane oxidation with insights on active structures and reaction pathway

doi:10.1016/S1872-2067(25)64728-0

Abstract

Abstract:

Palladium-based catalysts have long been considered the benchmark for methane combustion; however, the authentic phase of catalytic active sites remains a subject of ongoing debate. Additionally, challenges like water-poisoning and long-term stability need to be addressed to advance catalyst performance. Herein, we investigate Pd on Co₃O₄ nanorods as a highly effective catalyst for catalytic oxidation of methane, demonstrating long-term stability and water tolerance during a 100-h continuous operation at 350 °C. Comprehensive characterizations reveal the presence of an active Pd-oxygen vacancy (O_v)-cobalt interface in Pd/Co₃O₄, which effectively adsorbs molecular O₂. The absorbed oxygen species on this interface are activated and directly participate in methane combustion. Moreover, near-ambient pressure X-ray photoelectron spectroscopy demonstrates that Pd nanoparticles undergo a rapid phase transition and predominantly remain in the metallic state during the reaction. This behavior is attributed to the electronic metal-support interaction between Pd and Co₃O₄. Furthermore, in situ Fourier transformed infrared spectrum reveals that under reaction conditions, HCO₃* species are formed initially and subsequently transformed into formate species, indicating that the formate pathway is the dominant mechanism for CH₄ oxidation.

Key words: Methane combustion, Complete oxidation, Palladium catalyst, Water tolerance, Co₃O₄, Oxygen activation, Near-ambient pressure X-ray photoelectron spectroscopy

Yuanjie Xu, Run Hou, Kunxiang Chi, Bo Liu, Zemin An, Lizhi Wu, Li Tan, Xupeng Zong, Yihu Dai, Zailai Xie, Yu Tang. A water-resistant and stable Pd-Co₃O₄ catalytic interface for complete methane oxidation with insights on active structures and reaction pathway[J]. Chinese Journal of Catalysis, 2025, 74: 191-201.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64728-0

https://www.cjcatal.com/EN/Y2025/V74/I7/191

Figures/Tables 8

Fig. 1. Catalytic performance of the catalysts. (a) Temperature dependence of CH4 conversion over Co3O4, Pd/Co3O4, and Pd/Al2O3 for COM reaction. (b) Arrhenius plots of Co3O4, Pd/Co3O4, and Pd/Al2O3 for COM reaction. (c) Catalytic performance of Co3O4, Pd/Co3O4, and Pd/Al2O3 for COM reaction at 350 °C against time on stream. Conditions: 50 mg catalysts, a mixture of 20 mL/min 10 vol% CH4/Ar and 10 mL/min pure O2. (d) Long-term performance of Pd/Co3O4 and Pd/Al2O3 for complete oxidation of methane under wet feed conditions at 350 °C. The feed contains 2000 ppm CH4, 1%O2, and 3% H2O balanced with Ar (50 mL/min).

Fig. 2. XRD patterns of fresh catalyst of Co3O4 spent Co3O4 catalyst after complete oxidation of methane, fresh catalyst of Pd/Co3O4, and spent Pd/Co3O4 catalyst after complete oxidation of methane. Scan rate of 1°/min with 0.01 step in the 2θ range from 20° to 70°.

Fig. 3. STEM images of Pd/Co3O4 after catalytic combustion of methane.

Fig. 4. (a) DRIFTS-CO spectra of Co3O4, fresh catalyst of Pd/Co3O4, and spent Pd/Co3O4 catalyst after complete oxidation of methane. Conditions: all the samples were pretreated at 200 °C under Ar for 1h, and tested CO adsorption at room temperature. (b) Raman spectra of fresh catalyst of Co3O4, spent Co3O4 catalyst after complete oxidation of methane, fresh catalyst of Pd/Co3O4, and spent Pd/Co3O4 catalyst after complete oxidation of methane.

Fig. 5. Redox properties of Co3O4 and Pd/Co3O4 catalysts. (a) H2-TPR profile; (b) CH4-TPR profile; (c) O2-TPD profile.

Table 1 The H2 consumption of the as-prepared catalysts.

Samples	Peak 1 (mmol/g)	Peak 2 (mmol/g)
Co₃O₄	3.16	11.51
Pd/Co₃O₄	2.39	4.49

Fig. 6. NAP-XPS studies of Pd/Co3O4 under COM reactions. (a) Photoemission feature of Co 2p and Pd 3d of Pd/Co3O4 under various gas-phase conditions at 250 °C. Data were collected across four sequential stages by altering the gas composition. (I) 1 Torr O2; (II) 0.2 Torr CH4; (III) 1 Torr O2; (IV) 0.2 Torr CH4. (b) Pd chemical states deconvoluted from NAP-XPS experiment. (c) NAP-XPS studies of Pd/Co3O4 catalyst for the steady state spectra of Pd 3d under the COM reactant gases at different temperatures.

Fig. 7. (a) In situ DRIFTS studies of Pd/Co3O4 under steady state complete oxidation of methane at 200 °C as the function of time. (b) Schematic diagram of complete oxidation of methane on Pd/Co3O4 catalyst.

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A water-resistant and stable Pd-Co₃O₄ catalytic interface for complete methane oxidation with insights on active structures and reaction pathway

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