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Frontiers of Environmental Science & Engineering

ISSN 2095-2201

ISSN 2095-221X(Online)

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Front. Environ. Sci. Eng.    2019, Vol. 13 Issue (2) : 21    https://doi.org/10.1007/s11783-019-1113-8
RESEARCH ARTICLE
Mechanism of dichloromethane disproportionation over mesoporous TiO2 under low temperature
Yuzhou Deng1,2, Shengpan Peng1,2, Haidi Liu1,3, Shuangde Li1,3, Yunfa Chen1,3()
1. State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China
2. University of Chinese Academy of Sciences, Beijing 100049, China
3. Center for Excellence in Regional Atmospheric Environment, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen 361021, China
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Abstract

• 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.

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.
Keywords Dichloromethane      Disproportionation      Mechanism      Anatase (001)      Water dissociation     
Corresponding Author(s): Yunfa Chen   
Issue Date: 08 April 2019
 Cite this article:   
Yuzhou Deng,Shengpan Peng,Haidi Liu, et al. Mechanism of dichloromethane disproportionation over mesoporous TiO2 under low temperature[J]. Front. Environ. Sci. Eng., 2019, 13(2): 21.
 URL:  
https://academic.hep.com.cn/fese/EN/10.1007/s11783-019-1113-8
https://academic.hep.com.cn/fese/EN/Y2019/V13/I2/21
Fig.1  Conversion of DCM (a), selectivity of CO (b open), CO2 (b solid) and CH3Cl (c). Reaction conditions: 1000 ppm DCM, 1 vol.% H2O, WHSV= 60000 mL/(g·h).
Fig.2  Concentrations as a function of time-on-stream over T1 catalyst. Step A: 1000 ppm DCM, 20% O2, N2 balanced; Step B: cut off DCM feed, 20% O2, N2 balanced; Step C: 1000 ppm DCM, 20% O2, N2 balanced; Step D: 1000 ppm DCM, 1% H2O, 20% O2, N2 balanced; Step E: 1000 ppm DCM, 0.1% H2O, 20% O2, N2 balanced. All the steps were carried out at 300℃ steady, WHSV= 60000 mL/(g·h).
Fig.3  In situ IR patterns of T1 under different temperatures. Gas feed: 100 mL/min 1000 ppm DCM, 1% H2O. (a) Global view, (b) C-H stretching region.
Fig.4  In situ IR spectrum of continuous flow of feed on T1 at 250°C, feed flow was 100 mL/min. A: 1000 ppm DCM, 20% O2, N2 balanced, 0.4 vol.% H2O. B: cut off DCM feed. C: elevated to 350℃ for 1 h and cool down to 250°C. D: restore DCM feed.
Wavenumber (cm−1) Description Ref.
3864 n(OH) Primet et al. (1971); Maira et al. (2001)
3250 n(H,OH), molecular H2O coordinated with Ti4+ Maira et al. (2001)
2955 nas(CH3) van den Brink et al. (1998)
2935 nas(CH2) van den Brink et al. (1998)
2886 ns(CH3) van den Brink et al. (1998)
2865 n(CH) of formate species van den Brink et al. (1998)
2835 ns(CH2) van den Brink et al. (1998)
2738 n(CH), Fermi resonance of overtone of d(H-C) van den Brink et al. (1998)
1560 nas(COO), monodentate Greenler (1962); van den Brink et al. (1998); Maupin et al., (2012)
1540 nas(COO), bridge-dentate Kozlov et al. (2000)
1396 b(CH) of HCOO in-plane bending Greenler (1962); van den Brink et al. (1998); Maupin et al. (2012)
1373 ns(COO), bridge-dentate Greenler (1962); van den Brink et al. (1998); Maupin et al., (2012)
1360 ns(COO), monodentate Greenler (1962); van den Brink et al. (1998); Maupin et al. (2012)
Tab.1  Assignment of IR adsorption peaks
Catalyst Phase Specific Area (m2/g)a) Pore volume (cm3/g)b) Average pore diameter (nm)b) T50 (℃)
T1 Anatase+ Rutile 105.0 0.197 3.8 280
T2 Anatase 84.5 0.435 14.0 305
T3 Rutile 35.1 0.213 20.1 >400
Tab.2  Texture properties of the catalysts
Fig.5  XRD patterns of three types of TiO2.
Fig.6  TEM images of T1 (a), (b), T2 (c), T3 (d).
Fig.7  Adsorption and desorption isotherms, pore distributions of T1, T2 and T3.
Fig.8  Scheme 1 Two adsorption modes of DCM over TiO2 (a), disproportionation route (b), oxidation route (c), recovery of TiO2 (d)
Fig.9  Scheme 2 Mechanism of DCM disproportionation over TiO2
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