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A layered tungstic acid H2W2O7 x nH2O with a double-octahedral sheet structure: conversion process from an
Manabu Kudo1, Hajime Ohkawa, Wataru Sugimoto
1Department of Applied Chemistry, School of Science and Engineering, Waseda University, Shinjuku-ku, Tokyo 169-8555, Japan.
Abstract:
The conversion process of an Aurivillius phase, Bi(2)W(2)O(9), into a layered tungstic acid by hydrochloric acid treatment has been investigated, and resultant H(2)W(2)O(7) x nH(2)O has been fully characterized. The c parameter of Bi(2)W(2)O(9) [2.37063(5) nm] decreases to 2.21(1) nm in an acid-treated product dried at ambient temperature. The a and b parameters of Bi(2)W(2)O(9) [a = 0.54377(1) nm and b = 0.54166(1) nm] also decrease slightly to a = 0.524(1) nm and b = 0.513(1) nm in the acid-treated product dried at ambient temperature, indicating structural changes in the ReO(3)-like slabs in Bi(2)W(2)O(9) upon acid treatment. Drying at 120 degrees C leads to a further decrease in the c parameter [1.86(1) nm] with no notable change in the a and b parameters [a = 0.5249(2) nm and b = 0.513(2) nm]. The formation of an expandable layered structure is demonstrated by the successful intercalation of n-octylamine [interlayer distance 2.597(9) nm] and n-dodecylamine [interlayer distance 3.56(2) nm]. The compositions of the acid-treated products are determined to be H(2)W(2)O(7) x nH(2)O typically with n = 0.58 for the air-dried product and n = 0 for the product dried at 120 degrees C. As a consequence, the composition of the layer is H(2)W(2)O(7), and the decrease in the c parameter upon drying is ascribable to the loss of interlayer water. Scanning electron microscopy reveals no morphological change during acid treatment, which strongly suggests a selective leaching of the bismuth oxide sheets as a reaction mechanism. High-resolution transmission electron microscopy (HREM) observation of the acid-treated product shows consistency with a structural model for H(2)W(2)O(7), derived from Bi(2)W(2)O(9) through removal of the bismuth oxide sheets and contraction along the c axis. HREM observation also reveals that the WO(6) octahedra arrangement changes slightly with acid treatment. A one-dimensional electron density map projected on the c axis for the product dried at 120 degrees C, H(2)W(2)O(7), shows good consistency with that calculated for the structural model.