NMR studies of acetylene absorbed on supported platinum catalysts
Sakaie, Ken Earl
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Permalink
https://hdl.handle.net/2142/18847
Description
Title
NMR studies of acetylene absorbed on supported platinum catalysts
Author(s)
Sakaie, Ken Earl
Issue Date
1996
Doctoral Committee Chair(s)
Slichter, C.P.
Department of Study
Physics
Discipline
Physics
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
Nuclear magnetic resonance (NMR)
acetylene
platinum catalysts
Language
en
Abstract
"This thesis describes NMR measurements involving carbon-13, deuterons, and
protons in acetylene (C2H2) adsorbed at room temperature on supported platinum
catalysts.
Measurements from 77""K to 158°K of the spin-lattice relaxation behavior of
carbon-13 reveal multiple-exponential behavior. Calculations rule out an anisotropic T 1 as
an explanation for the multiple-exponential behavior. Carbon-proton SEDOR
measurements indicate that each time constant, T 1, in the spin-lattice relaxation of carbon
corresponds to a mixture of adsorbate structures. The T 1 seems to exhibit a linear
temperature dependence, indicating interaction with conduction electrons of the platinum
. clusters. However, the spectrum measurements indicate no Knight shift, a deviation from
the Korringa relation. Such a deviation implies that electronic states at the Fermi energy
involve hybrids of the platinum conduction band with adsorbate molecular orbitals with no
spatial density at the carbon nucleus.
Measurements of the deuterium spectrum reveal no obvious features that would
prove useful in identifying different adsorbate structures. Spectrum and spin-locking
measurements indicate no motion of deuteron groups at 77°K The deuterium spin-lattice
relaxation rate exhibits multiple-exponential behavior.
Measurements of the coupling between the magnetic dipole moments of deuterons
determine bond angles and internuclear distances. A single-resonance ""slow beat""
measurement finds, in deuterated ethylidyne (CCD3) , a distance between deuterons ofr00
= 1.673±0.004A. A double resonance method, demonstrated in a test sample ofD20 in
gypsum, can provide bond angle and internuclear distance information. Coherence
transfer between carbon and deuterium indicates that deuterium NMR measurements at
lower temperatures may offer significant advantages in terms of signal to noise ratios."
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