Heterogeneous Catalytic Reduction of Perchlorate in Water
Hurley, Keith D.
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https://hdl.handle.net/2142/84327
Description
Title
Heterogeneous Catalytic Reduction of Perchlorate in Water
Author(s)
Hurley, Keith D.
Issue Date
2008
Doctoral Committee Chair(s)
Shapley, John R.
Department of Study
Chemistry
Discipline
Chemistry
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
Chemistry, Inorganic
Language
eng
Abstract
To probe the ligand effect, a series of catalyst were prepared by supporting trans-[Re(O)2L4]+ X, (L = pyridine, 4-methylpyridine, 4-methoxypyridine, or 4dimethylaminopyridine, X = Cl - or [ReO4]-) or trans-[ReO 2(L-L)2]I (L-L = ethylenediamine) on nominally 5 wt.% Pd on activated carbon by incipient wetness. All of the supported Re(V) complexes examined by XPS yielded binding energies showing only a +7 oxidation state, while examination of an unsupported complex clearly showed both Re(V) and Re(VII) as being present. Unlike previous materials, these complexes had never been demonstrated as oxygen atom transfer catalysts. All materials completely reduced perchlorate to chloride in the presence of 2mM excess Cl- while exhibiting pseudo-first order kinetics. Supported catalyst activity increased with the e--donating ability of the para-substituent on the pyridine ligands.
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