Communication
ChemComm
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species in two different environments, perhaps interacting with
one and two silicon atoms, respectively.
Minor changes in the UV-vis spectra also occurred upon
contact with propane (see Fig. S4–S8 in the ESI†). The band at
23 000 cmÀ1 on Cu-ZSM-5 disappeared immediately, which is
consistent with the high reactivity of the mono-m-oxo species.
However, admission of propane on the oxidized small-pore
materials did not help identify a similarly reactive species. This
scenario is essentially the same as that reported by Smeets
et al.,14 who also tested several medium and large-pore copper
zeolites for conversion of methane to methanol and failed to
connect the amount of methanol produced with any particular
chromophore.
This report shows that copper-containing small-pore zeolites
and zeotypes, in addition to copper-containing medium and
large pore zeolites, can also produce methanol from methane and
water. With the exception of SAPO-34 and mordenite, materials
exchanged with copper(II) acetate produced more methanol than
materials exchanged with copper(I) chloride. The amount of
methanol produced per gram of material (or per mole of copper)
was greater than amounts reported previously, which is attributed
in part to the high-temperature water vapor extraction protocol.
UV-vis spectroscopy revealed evidence of species containing
non-framework Cu–O bonds that are stable at high temperature
on Cu-ZSM-5 and Cu-SAPO-34. The structure of the active sites
on the small-pore materials remains an open question. However,
the structural simplicity of the materials should facilitate future
spectroscopic investigation of the active site. It is possible that
the active sites on the copper-containing small-pore zeolites are
the same as those active for decomposition of NO.
This manuscript was prepared under cooperative agreement
70NANB10H256 from NIST, U.S. Department of Commerce.
The statements, findings, conclusions and recommendations
are those of the author(s) and do not necessarily reflect the view
of NIST or the U.S. Department of Commerce. T. Pham is
acknowledged for synthesizing SSZ-16 and SSZ-39.
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