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In this work, a Pt catalyst supported on an equimolar Al 2 O 3 –CeO 2 binary oxide (Pt–Al–Ce) was prepared and applied in photo-thermo-chemical dry reforming of methane (DRM) driven by concentrated solar irradiation. It was found that the Pt–Al–Ce catalyst showed good stability in DRM reactions and significant enhancements in H 2 and CO production rates compared with Pt/CeO 2 (Pt–Ce) and Pt/Al 2 O 3 (Pt–Al) catalysts. At a reaction temperature of 700 °C under 30-sun equivalent solar irradiation, the Pt–Al–Ce catalyst exhibits a stable DRM catalytic performance at a H 2 production rate of 657 mmol g −1 h −1 and a CO production rate of 666 mmol g −1 h −1 , with the H 2 /CO ratio almost equal to unity. These production rates and the H 2 /CO ratio were significantly higher than those obtained in the dark at the same temperature. The light irradiation was found to induce photocatalytic activities on Pt–Al–Ce and reduce the reaction activation energy. In situ diffuse reflectance infrared Fourier transform spectroscopy ( in situ DRIFTS) was applied to identify the active intermediates in the photo-thermo-chemical DRM process, which were bidentate/monodentate carbonate, absorbed CO on Pt, and formate. The benefits of the binary Al 2 O 3 –CeO 2 substrate could be ascribed to Al 2 O 3 promoting methane dissociation while CeO 2 stabilized and eliminated possible coke formation, leading to high catalytic DRM activity and stability.
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Balancing elementary steps enables coke-free dry reforming of methane
Abstract Balancing kinetics, a crucial priority in catalysis, is frequently achieved by sacrificing activity of elementary steps to suppress side reactions and enhance catalyst stability. Dry reforming of methane (DRM), a process operated at high temperature, usually involves fast C-H activation but sluggish carbon removal, resulting in coke deposition and catalyst deactivation. Studies focused solely on catalyst innovation are insufficient in addressing coke formation efficiently. Herein, we develop coke-free catalysts that balance kinetics of elementary steps for overall thermodynamics optimization. Beginning from a highly active cobalt aluminum oxide (CoAl2O4) catalyst that is susceptible to severe coke formation, we substitute aluminum (Al) with gallium (Ga), reporting a CoAl0.5Ga1.5O4-R catalyst that performs DRM stably over 1000 hours without observable coke deposition. We find that Ga enhances DRM stability by suppressing C-H activation to balance carbon removal. A series of coke-free DRM catalysts are developed herein by partially substituting Al from CoAl2O4with other metals.
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- Award ID(s):
- 2108307
- PAR ID:
- 10527962
- Publisher / Repository:
- Springer Nature
- Date Published:
- Journal Name:
- Nature Communications
- Volume:
- 14
- Issue:
- 1
- ISSN:
- 2041-1723
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript
- Journal Article:
- https://doi.org/10.1038/s41467-023-43277-0
