Mechanism of dichloromethane disproportionation over mesoporous TiO₂ under low temperature

Highlights

• Mechanism of DCM disproportionation over mesoporous TiO₂ was studied.

• DCM was completely eliminated at 350℃ under 1 vol.% humidity.

• Anatase (001) was the key for disproportionation.

• A competitive oxidation route co-existed with disproportionation.

• Disproportionation was favored at low temperature.

Abstract

Mesoporous TiO₂ was synthesized via nonhydrolytic template-mediated sol-gel route. Catalytic degradation performance upon dichloromethane over as-prepared mesoporous TiO₂, pure anatase and rutile were investigated respectively. Disproportionation took place over as-made mesoporous TiO₂ and pure anatase under the presence of water. The mechanism of disproportionation was studied by in situ FTIR. The interaction between chloromethoxy species and bridge coordinated methylenes was the key step of disproportionation. Formate species and methoxy groups would be formed and further turned into carbon monoxide and methyl chloride. Anatase (001) played an important role for disproportionation in that water could be dissociated into surface hydroxyl groups on such structure. As a result, the consumed hydroxyl groups would be replenished. In addition, there was another competitive oxidation route governed by free hydroxyl radicals. In this route, chloromethoxy groups would be oxidized into formate species by hydroxyl radicals transfering from the surface of TiO₂. The latter route would be more favorable at higher temperature.

Graphical abstract

Keywords

Dichloromethane / Disproportionation / Mechanism / Anatase (001) / Water dissociation

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Acknowledgements

This work was supported by Key Program of the Chinese Academy of Sciences (No. ZDRW-ZS-2016-5-3) and National Key Research and Development Program of China (Grant No. 2017YFC0211503).

Supplementary material

is available in the online version of this article at https://doi.org/10.1007/s11783-019-1113-8 and is accessible for authorized users.

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