Highly active copper-intercalated weakly crystallized δ-MnO<sub>2</sub> for low-temperature oxidation of CO in dry and humid air

doi:10.1007/s11783-024-1822-5

Front. Environ. Sci. Eng.

2024, Vol. 18

Issue (5) : 62 https://doi.org/10.1007/s11783-024-1822-5

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

Hao Zhang¹, Huinan Li¹, Pengyi Zhang^1,²(

), Tingxia Hu¹, Xianjie Wang^1,³

¹. State Key Joint Laboratory of Environment Simulation and Pollution Control, School of Environment, Tsinghua University, Beijing 100084, China
². Beijing Key Laboratory for Indoor Air Quality Evaluation and Control, Beijing 100084, China
³. Midea Corporate Research Center, Foshan 528311, China

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Abstract

● 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.

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.

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

Corresponding Author(s): Pengyi Zhang

Issue Date: 11 March 2024

Cite this article:

Hao Zhang,Huinan Li,Pengyi Zhang, et al. Highly active copper-intercalated weakly crystallized δ-MnO₂ for low-temperature oxidation of CO in dry and humid air[J]. Front. Environ. Sci. Eng., 2024, 18(5): 62.

URL:

https://academic.hep.com.cn/fese/EN/10.1007/s11783-024-1822-5
https://academic.hep.com.cn/fese/EN/Y2024/V18/I5/62

Scheme1 The schematic diagram of the experimental setup.

Fig.1 XRD patterns of MnO₂ and Cu-doped MnO₂ catalysts.

Fig.2 SEM images of (a) MnO₂, (b) MnO₂-10Cu, (c) MnO₂-40Cu, (d) MnO₂-150Cu. TEM and HRTEM images of (e, f) MnO₂ and (g, h) MnO₂-150Cu.

Tab.1 Physicochemical parameters of as-prepared samples

Fig.3 XPS spectra of (a) Mn 3s and (b) O 1s.

Fig.4 (a) H₂-TPR and (b) O₂-TPD profiles of different samples.

Fig.5 (a) Temperature dependent of CO conversion over different catalysts under dry air condition; (b) Stability of MnO₂-150Cu at ?10 °C under dry air condition. Test condition: CO inlet concentration 250 ppm, WHSV 150 L/(g·h).

Fig.6 (a) The performance of MnO₂-150Cu for 1000 ppm CO conversion under dry N₂ condition at 30 °C (WHSV 30 L/(g·h)) and its regeneration ability under dry O₂ at 150 °C for 2 h (WHSV 120 L/(g·h)); (b) The performance of MnO₂-150Cu for 1000 ppm CO conversion under dry N₂ condition at 20 and 60 °C (WHSV 30 L/(g·h)).

Fig.7 (a) The effect of moisture on CO oxidation over MnO₂-150Cu at 30 °C; (b) The effect of reaction temperature on CO oxidation over MnO₂-150Cu under 1.3% moisture. Test condition: CO inlet concentration 250 ppm, WHSV 150 L/(g·h).

Fig.8 In situ DRIFTS of (a) MnO₂ and (b,c,d) MnO₂-150Cu under dry and wet 2% CO/O₂ conditions. (a, b) 35 °C, dry; (c) 35 °C, 4.0% H₂O; (d) 90 °C, 4.0% H₂O.

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