Carbon diffusion mechanism as an effective stability enhancement strategy: The case study of Ni-based catalyst for photothermal catalytic dry reforming of methane

doi:10.1016/S1872-2067(24)60249-4

Abstract

Abstract:

Photothermal catalytic methane dry reforming (DRM) technology can convert greenhouse gases (i.e. CH₄ and CO₂) into syngas (i.e. H₂ and CO), providing more opportunities for reducing the greenhouse effect and achieving carbon neutrality. In the DRM field, Ni-based catalysts attract wide attention due to their low cost and high activity. However, the carbon deposition over Ni-based catalysts always leads to rapid deactivation, which is still a main challenge. To improve the long-term stability of Ni-based catalysts, this work proposes a carbon-atom-diffusion strategy under photothermal conditions and investigates its effect on a Zn-doped Ni-based photothermal catalyst (Ni₃Zn@CeO₂). The photothermal catalytic behavior of Ni₃Zn@CeO₂ can maintain more than 70 h in DRM reaction. And the photocatalytic DRM activity of Ni₃Zn@CeO₂ is 1.2 times higher than thermal catalytic activity. Density functional theory (DFT) calculation and experimental characterizations indicate that Ni₃Zn promotes the diffusion of carbon atoms into the Ni₃Zn to form the Ni₃ZnC_0.7 phase with body-centered cubic (bcc) structure, thus inhibiting carbon deposition. Further, in-situ diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy and DFT calculation prove Ni₃Zn@CeO₂ benefits the CH₄ activation and inhibits the carbon deposition during the DRM process. Through inducing carbon atoms diffusion within the Ni₃Zn lattice, this work provides a straightforward and feasible strategy for achieving efficient photothermal catalytic DRM and even other CH₄ conversion implementations with long-term stability.

Key words: Photothermal catalysis, Methane dry reforming, Ni-based catalyst, Stability enhancement, Carbon atom diffusion

Dezheng Li, Huimin Liu, Xuewen Xiao, Manqi Zhao, Dehua He, Yiming Lei. Carbon diffusion mechanism as an effective stability enhancement strategy: The case study of Ni-based catalyst for photothermal catalytic dry reforming of methane[J]. Chinese Journal of Catalysis, 2025, 70: 399-409.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60249-4

https://www.cjcatal.com/EN/Y2025/V70/I3/399

Figures/Tables 6

Fig. 1. Characterizations of phase and structures. (a) XRD patterns of Ni@CeO2 and Ni3Zn@CeO2. HR-TEM (b) and HAADF-STEM images with corresponding EDS mapping (c) of Ni3Zn@CeO2.

Fig. 2. Thermal and photothermal catalytic DRM performances. Conversion rates of CH4 (a) and CO2 (b) over Ni@CeO2 and Ni3Zn@CeO2 under thermal and photothermal conditions during DRM reactions. Reaction conditions: CH4: CO2 = 1:1, temperature: 500 °C, pressure: 1 bar, WHSV: 6 × 103 mL ·min?1·gcat?1, light source: visible light, sample: 0.1 g.

Fig. 3. Characterizations of optical, metal-support interaction, and CO2 absorption properties. (a) UV-vis spectra of CeO2, Ni@CeO2, and Ni3Zn@CeO2. (b) H2-TPR curves of Ni@CeO2 and Ni3Zn@CeO2. (c) CO2-TPD curves of Ni@CeO2 and Ni3Zn@CeO2.

Fig. 4. Stability test of the Ni3Zn@CeO2 catalyst during 70 h DRM reaction. Conversion rates of CH4 and CO2 over Ni3Zn@CeO2 during photothermal catalytic DRM reaction. Reaction conditions: CH4: CO2 = 1: 1, temperature: 500 °C, pressure: 1 bar, WHSV: 6 × 103 mL?min?1?gcat?1, light source: visible light, sample: 0.1 g.

Fig. 5. Characterizations of phase, structures, carbon deposition states, and elemental states of Ni@CeO2 and Ni3Zn@CeO2 after DRM reactions. (a) The XRD pattern of Ni@CeO2, Ni@CeO2-AR, Ni3Zn@CeO2, and Ni3Zn@CeO2-AR. TEM images of Ni@CeO2 (b), Ni@CeO2-AR (c), Ni3Zn@CeO2 (d), and Ni3Zn@CeO2-AR (e). (f) HR-TEM image of Ni3Zn@CeO2-AR. (g) HAADF-STEM images with corresponding EDS mapping of Ni3Zn@CeO2-AR. (h) TGA curves of Ni@CeO2-AR and Ni3Zn@CeO2-AR. (i) XPS spectra of Ni 2p in Ni@CeO2, Ni3Zn@CeO2, and Ni3Zn@CeO2-AR. (j) The structures of Ni3Zn and Ni3ZnC0.7 with face-center cubic and body-center cubic structures.

Fig. 6. Characterization and theoretical studies of DRM reaction mechanism. (a) In-situ DRIFTS spectra of the Ni3Zn@CeO2 catalyst. Operating conditions: 25-500 °C, heating rate: 7 °C min?1, sampling time interval: 5 min, CH4: CO2 = 1: 1, total flow rate: 10 mL·min?1, 0.1 g of catalyst, with visible light irradiation (300 W Xe lamp). (b) Free energy on Ni NPs and Ni3ZnC0.7 during CH4 dissociation steps.

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