Catalytic oxidation of toluene by manganese oxides: Effect of K+ doping on oxygen vacancy

J Environ Sci (China). 2024 Aug:142:43-56. doi: 10.1016/j.jes.2023.07.036. Epub 2023 Jul 29.

Abstract

Alkali metal potassium was beneficial to the electronic regulation and structural stability of transition metal oxides. Herein, K ions were introduced into manganese oxides by different methods to improve the degradation efficiency of toluene. The results of activity experiments indicated that KMnO4-HT (HT: Hydrothermal method) exhibited outstanding low-temperature catalytic activity, and 90% conversion of toluene can be achieved at 243°C, which was 41°C and 43°C lower than that of KNO3-HT and Mn-HT, respectively. The largest specific surface area was observed on KMnO4-HT, facilitating the adsorption of toluene. The formation of cryptomelane structure over KMnO4-HT could contribute to higher content of Mn3+ and lattice oxygen (Olatt), excellent low-temperature reducibility, and high oxygen mobility, which could increase the catalytic performance. Furthermore, two distinct degradation pathways were inferred. Pathway Ⅰ (KMnO4-HT): toluene → benzyl → benzoic acid → carbonate → CO2 and H2O; Pathway ⅠⅠ (Mn-HT): toluene → benzyl alcohol → benzoic acid → phenol → maleic anhydride → CO2 and H2O. Fewer intermediates were detected on KMnO4-HT, indicating its stronger oxidation capacity of toluene, which was originated from the doping of K+ and the interaction between KOMn. More intermediates were observed on Mn-HT, which can be attributed to the weaker oxidation ability of pure Mn. The results indicated that the doping of K+ can improve the catalytic oxidation capacity of toluene, resulting in promoted degradation of intermediates during the oxidation of toluene.

Keywords: Catalytic oxidation; Cryptomelane; Mn(3+) and lattice oxygen; Preparation method.

MeSH terms

  • Benzoic Acid
  • Carbon Dioxide
  • Catalysis
  • Manganese Compounds*
  • Manganese* / chemistry
  • Oxidation-Reduction
  • Oxides / chemistry
  • Oxygen / chemistry
  • Toluene*

Substances

  • Toluene
  • Manganese
  • Oxygen
  • Carbon Dioxide
  • manganese oxide
  • Oxides
  • Benzoic Acid
  • Manganese Compounds