A Study on the Influence of FeOx Doping into CeO2 Nanocrystal on Selective Oxidative Chlorination
of Methane

Abstract

Abstract:

Objective: The paper is to study the influence of FeOx doping into CeO2 nanocrystal on the crystal structure, morphology
and the catalytic performance on oxidative chlorination of methane. Methods: Crystal structure of materials was detected by XRD, and
the morphology was observed by TEM and HRTEM. Catalytic performance on the oxidative chlorination of methane over CeO2 and
FeOx - CeO2 nanorods at different reaction temperatures was investigated, and the apparent activation energy was also calculated.
Results: The unit cell of CeO2 nanocatalysts contracted slightly after doping with FeOx. The morphology of FeOx-CeO2 nanorods had a
trend of changing into cube after reaction. However, for FeOx-CeO2 nanocubes, the morphology and size were almost unchanged. For
CeO2 nanorods, the apparent activation energy was dropped from 106 kJ/mol to 84 kJ/mol after doping with FeOx. Conclusion: CeO2
and FeOx probably formed solid solution. The catalytic performance on the oxidative chlorination of methane was improved for CeO2
nanocatslysts after doping with FeOx.

Key words: methane, oxidative chlorination, methyl chloride, FeOx-CeO2 nanocatalysts

CLC Number:

He Jieli, Yan Ya, Yang Rong, Li Jingwei*. A Study on the Influence of FeOx Doping into CeO2 Nanocrystal on Selective Oxidative Chlorination
of Methane[J]. , 2018, 3(6): 48-54.

References

〔1〕OLAH G A，GUPTA B，FELBERG J D，et al. Selective
Monohalogenation of Methane over Supported Acid or Plati?
num Metal Catalysts and Hydrolysis of Methyl Halides over
γ- Alumina- Supported Metal Oxide/Hydroxide Catalysts.
A Feasible Path for the Oxidative Conversion of Methane in?
to MethylAlcohol/DimethylEther〔J〕.JAmChemSoc，1985，
107（24）：7097-7105.
〔2〕ZHOU X P，YILMAZ A，YILMAZ G A，et al. An integrated

process for partial oxidation of alkanes〔J〕. Chem Commun，
2003（18）：2294-2295.
〔3〕GTL technology of alkane conversion to chemicals through
bromination process〔EB/OL〕〔. 2012-03-31〕.http：//www. grtinc.
com/go/technology/grt-technology/.
〔4〕WANG K X，XU H F，LI W S，et al. Acetic acid synthesis
from methane by non-synthesis gas process〔J〕. J Mol Catal
A：Chem，2005，225（1）：65-69.
〔5〕WANG K X，XU H F，LI W S，et al. The synthesis of acetic
acid from methane via oxidative bromination，carbonyl?
ation，and hydrolysis〔J〕. Applied Catalysis A：General，
2006，304：168-177.
〔6〕YANG F，LIU Z，LI W S，et al. The Oxidative Bromination
of Methane Over Rh/SiO2 Catalyst〔J〕. Catal Lett，2008，
124（3/4）：226-232.
〔7〕LIN R H，DING Y J，GONG L F，et al. Oxidative bromina?
tion of methane on silica-supported non-noble metal oxide
catalysts〔J〕. Appl Catal A：Gen，2009，353（1）：87-92.
〔8〕LIN R H，DING Y J，GONG L F，et al. Efficient and stable
silica-supported iron phosphate catalysts for oxidative bro?
mination of methane〔J〕. J Catal，2010，272（1）：65-73.
〔9〕PERINGER E，PODKOLZIN S G，JONES M E，et al. LaCl3-
based catalysts for oxidative chlorination of CH4〔J〕. Top
Catal，2006，38（1/2/3）：211-220.
〔10〕PODKOLZIN S G，STANGLAND E E，JONES M E，et al.
Methyl Chloride Production from Methane over Lantha?
num- Based Catalysts〔J〕. J Am Chem Soc，2007，129
（9）：2569-2576.
〔11〕PERINGER E，SALZINGER M，HUTT M，et al. Modified
Lanthanum Catalysts for Oxidative Chlorination of Meth?
ane〔J〕. Top Catal，2009，52（9）：1220-1231.
〔12〕HE J L，XU T，WANG Z H，et al. Transformation of Meth?
ane to Propylene：A Two-Step Reaction Route Catalyzed
by Modified CeO2 Nanocrystals and Zeolites〔J〕. Angew
Chem Int Ed，2012，51（10）：2438-2442.
〔13〕MAI H X，SUN L D，ZHANF Y W，et al. Shape-selective
synthesis and oxygen storage behavior of ceria nanopolyhe?
dra，nanorods，and nanocubes〔J〕. J Phys Chem B，2005，
109（51）：24380-24385.
〔14〕LI G，SMITH R L，INOMATA H. Synthesis of Nanoscale
Ce1-xFexO2 SolidSolutionsviaaLow-TemperatureApproach
〔J〕. J Am Chem Soc，2001，123（44）：11091-11092.