Copper Sulfide Distribution in the Phase of Copper Carboxylate
Polymeric Fiber after the Catalytic Oxidation of Sulfide Anion
with Molecular Oxygen

M. P. Zhilenko, A. P. Rudenko, F. M. Spiridonov, A. G. Bogdanov, and V. A. Moskalev

Faculty of Chemistry, Moscow State University, Moscow, 119899 Russia

Received June 10, 1996

Abstract—It is revealed that copper sulfide complexes formed in VION KN-1 copper carboxylate polymeric
fiber yield the Cu_1.934S phase during the catalytic oxidation of the S² anion with molecular oxygen. The sulfide
phase forms rodlike domains (200–400 Å), which are uniformly distributed in the bulk of the fiber at
[Cu(II)]_f1.23 mmol/g and are segregated in the subsurface layer at higher concentrations, while prior to catal-
ysis, the copper is distributed uniformly at all the values of [Cu(II)]_f. It is shown that, at high values of [Cu(II)]_f,
a clear boundary between the segregated layer and the central region of the fiber exists, which is formed by
close-packed spherical domains 30 Å in diameter. It is established that this boundary (“polysulfide front”) is
related to the migration of copper ions to the surface from the bulk, deceleration of the diffusion of S² anions
into the bulk of the fiber, and to the nature of the driving forces of these processes. It is noted that the joint crys-
tallization of the polymeric and sulfide phases yields simplectic penetrations at high concentrations of Cu(II)
in the fiber.

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