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The partial oxidation of methane to dimethyl ether (DME) was studied on palladium supported on SiO2 , SiO2-ZrO2 , and ZrO2 at 225-375 degrees C and 0.1 MPa using either O-2 or a mixture of NO and O(2 )as the oxidants. The NO + O-2 mixture was more reactive than the O-2 toward methane, probably due to the formation of active surface nitrate species. The formation of DME on the catalysts was influenced by the support, with the Pd/ZrO2 catalyst producing DME and the Pd/ SiO2 catalyst producing only CO2 , irrespective of the oxidant used. The Pd/SiZrO2 catalyst formed DME only when O2 alone was used as the oxidant. For the reaction with NO + O-2 , in situ Fourier transform infrared (FTIR) measurements showed that the partial oxidation activity on Pd/ZrO2 was related to its ability to form surface-bridged nitrate species, likely due to the presence of basic sites. However, an inhibitory effect of basicity on CH4 turnover frequency (TOF) was attributed to surface nitrate-induced structural modification deduced from X-ray absorption fine structure spectroscopy measurements. For the reaction with only O-2 , the formation of DME over Pd/ZrO2 and Pd/SiZrO(2 )was attributed to the reported ability of ZrO2 to retain methoxy intermediates. Furthermore, a weak structural effect on the TOF observed with O-2 was attributed to competing effects of decreasing activity for C-H activation and increasing resistance to Pd oxidation with increasing particle size.
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ACS CATALYSIS
ISSN: 2155-5435
Year: 2022
Issue: 18
Volume: 12
Page: 11190-11205
1 2 . 9
JCR@2022
1 1 . 7 0 0
JCR@2023
ESI HC Threshold:74
JCR Journal Grade:1
CAS Journal Grade:1
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ESI Highly Cited Papers on the List: 0 Unfold All
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30 Days PV: 0
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