Pt
and PtSn catalysts supported on SiO2 and H-ZSM-5
were studied for methane conversion under nonoxidative conditions.
Addition of Sn to Pt/SiO2 increased the turnover frequency
for production of ethylene by a factor of 3, and pretreatment of the
catalyst at 1123 K reduced the extent of coke formation. Pt and PtSn
catalysts supported on H-ZSM-5 zeolite were prepared to improve the
activity and selectivity to non-coke products. Ethylene formation
rates were 20 times faster over a PtSn(1:3)/H-ZSM-5 catalyst with
SiO2:Al2O3 = 280 in comparison to
those over PtSn(3:1)/SiO2. H-ZSM-5-supported catalysts
were also active for the formation of aromatics, and the rates of
benzene and naphthalene formation were increased by using more acidic
H-ZSM-5 supports. These catalysts operate through a bifunctional mechanism,
in which ethylene is first produced on highly dispersed PtSn nanoparticles
and then is subsequently converted to benzene and naphthalene on Brønsted
acid sites within the zeolite support. The most active and stable
PtSn catalyst forms carbon products at a rate, 2.5 mmol of C/((mol
of Pt) s), which is comparable to that of state-of-the-art Mo/H-ZSM-5
catalysts with same metal loading operated under similar conditions
(1.8 mmol of C/((mol of Mo) s)). Scanning transmission electron microscopy
measurements suggest the presence of smaller Pt nanoparticles on H-ZSM-5-supported
catalysts, in comparison to SiO2-supported catalysts, as
a possible source of their high activity. A microkinetic model of
methane conversion on Pt and PtSn surfaces, built using results from
density functional theory calculations, predicts higher coupling rates
on bimetallic and stepped surfaces, supporting the experimental observations
that relate the high catalytic activity to small PtSn particles.