Improved Efficiency for Partial Oxidation of Methane by Controlled Copper Deposition on Surface-Modified ZSM-5

Thomas Sheppard, Helen Daly, Alexandre Goguet, Jillian M. Thompson

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

The mono(μ-oxo) dicopper cores present in the pores of Cu-ZSM-5 are active for the partial oxidation of methane to methanol. However, copper on the external surface reduces the ratio of active, selective sites to unselective sites. More efficient catalysts are obtained by controlling the copper deposition during synthesis. Herein, the external exchange sites of ZSM-5 samples were passivated by bis(trimethylsilyl) trifluoroacetamide (BSTFA) followed by calcination, promoting selective deposition of intraporous copper during aqueous copper ion exchange. At an optimum level of 1–2 wt % SiO2, IR studies showed a 64 % relative reduction in external copper species and temperature-programmed oxidation analysis showed an associated increase in the formation of methanol compared with unmodified Cu-ZSM-5 samples. It is, therefore, reported that the modified zeolites contained a significantly higher proportion of active, selective copper species than their unmodified counterparts with activity for partial methane oxidation to methanol.
LanguageEnglish
Pages562 -570
Number of pages9
JournalCHEMCATCHEM
Volume8
Issue number3
Early online date04 Dec 2015
DOIs
Publication statusPublished - 05 Feb 2016

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Methane
Copper
methane
copper
Oxidation
oxidation
Methanol
methyl alcohol
Ion exchange
Zeolites
zeolites
Calcination
roasting
proportion
porosity
catalysts
Catalysts
synthesis
ions

Cite this

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title = "Improved Efficiency for Partial Oxidation of Methane by Controlled Copper Deposition on Surface-Modified ZSM-5",
abstract = "The mono(μ-oxo) dicopper cores present in the pores of Cu-ZSM-5 are active for the partial oxidation of methane to methanol. However, copper on the external surface reduces the ratio of active, selective sites to unselective sites. More efficient catalysts are obtained by controlling the copper deposition during synthesis. Herein, the external exchange sites of ZSM-5 samples were passivated by bis(trimethylsilyl) trifluoroacetamide (BSTFA) followed by calcination, promoting selective deposition of intraporous copper during aqueous copper ion exchange. At an optimum level of 1–2 wt {\%} SiO2, IR studies showed a 64 {\%} relative reduction in external copper species and temperature-programmed oxidation analysis showed an associated increase in the formation of methanol compared with unmodified Cu-ZSM-5 samples. It is, therefore, reported that the modified zeolites contained a significantly higher proportion of active, selective copper species than their unmodified counterparts with activity for partial methane oxidation to methanol.",
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Improved Efficiency for Partial Oxidation of Methane by Controlled Copper Deposition on Surface-Modified ZSM-5. / Sheppard, Thomas; Daly, Helen; Goguet, Alexandre; Thompson, Jillian M.

In: CHEMCATCHEM, Vol. 8, No. 3, 05.02.2016, p. 562 -570.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Improved Efficiency for Partial Oxidation of Methane by Controlled Copper Deposition on Surface-Modified ZSM-5

AU - Sheppard, Thomas

AU - Daly, Helen

AU - Goguet, Alexandre

AU - Thompson, Jillian M.

PY - 2016/2/5

Y1 - 2016/2/5

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AB - The mono(μ-oxo) dicopper cores present in the pores of Cu-ZSM-5 are active for the partial oxidation of methane to methanol. However, copper on the external surface reduces the ratio of active, selective sites to unselective sites. More efficient catalysts are obtained by controlling the copper deposition during synthesis. Herein, the external exchange sites of ZSM-5 samples were passivated by bis(trimethylsilyl) trifluoroacetamide (BSTFA) followed by calcination, promoting selective deposition of intraporous copper during aqueous copper ion exchange. At an optimum level of 1–2 wt % SiO2, IR studies showed a 64 % relative reduction in external copper species and temperature-programmed oxidation analysis showed an associated increase in the formation of methanol compared with unmodified Cu-ZSM-5 samples. It is, therefore, reported that the modified zeolites contained a significantly higher proportion of active, selective copper species than their unmodified counterparts with activity for partial methane oxidation to methanol.

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