Highly active copper-intercalated weakly crystallized δ-MnO₂ for low-temperature oxidation of CO in dry and humid air

Highlights

● Copper intercalated weakly crystallized δ-MnO₂ was synthesized via one-pot process.

● Intercalated copper ions greatly enhanced the adsorption of CO.

● MnO₂-150Cu achieved a 100% conversion of CO even at −10 °C under dry air.

● MnO₂-150Cu exhibited a high CO oxidation capacity in an inert atmosphere at 30 °C.

● MnO₂-150Cu maintained a 100% conversion of CO for 35 h at 70 °C in 1.3% moisture air.

Abstract

Copper intercalated birnessite MnO₂ (δ-MnO₂) with weak crystallinity and high specific surface area (421 m²/g) was synthesized by a one-pot redox method and investigated for low-temperature CO oxidation. The molar ratio of Cu/Mn was as high as 0.37, which greatly weakened the Mn-O bond and created a lot of low-temperature active oxygen species. In situ DRIFTS revealed strong bonding of copper ions with CO. As-synthesized MnO₂-150Cu achieved 100% conversion of 250 ppm CO in normal air (3.1 ppm H₂O) even at −10 °C under the weight-hourly space velocity (WHSV) of 150 L/(g·h). In addition, it showed high oxygen storage capacity to oxidize CO in inert atmosphere. Though the concurrent moisture in air significantly inhibited CO adsorption and its conversion at ambient temperature, MnO₂-150Cu could stably convert CO in 1.3% moisture air at 70 °C owing to its great low-temperature activity and reduced competitive adsorption of water with increased temperature. This study discovers the excellent low-temperature activity of weakly crystallized δ-MnO₂ induced by high content intercalated copper ions.

Graphical abstract

Keywords

CO oxidation / Birnessite / Interlayer copper / Low-temperature / Oxygen storage capacity

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (No. 22076094), the Science & Technology Innovation Program of Shunde of Foshan City (China) (No. 2130218002526), and the Tsinghua-Foshan Innovation Special Fund (China) (No. 2021THFS0503).

Conflict of Interests

The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11783-024-1822-5 and is accessible for authorized users.

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