American Chemical Society
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Catalytic Thermal Decomposition of NO2 by Iron(III) Nitrate Nonahydrate-Doped Poly(Vinylidene Difluoride)

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journal contribution
posted on 2022-11-17, 15:03 authored by Lasanthi Sumathirathne, Carson Lawrence Hasselbrink, Dugan Hayes, William B. Euler
The products of thermal decomposition of iron nitrate nonahydrate doped into poly­(vinylidene difluoride) are examined using Mössbauer spectroscopy. Very little of the expected nitrogen dioxide product is observed, which is attributed to Fe3+ catalysis of the decomposition of NO2. The active site of the catalysis is shown to be Fe­(OH)3 in the polymer matrix, which is, unexpectedly, reduced to Fe­(OH)2. Thermodynamic calculations show that the reduction of Fe3+ is exergonic at sufficiently high temperatures. A reaction sequence, including a catalytic cycle for decomposition of NO2, is proposed that accounts for the observed reaction products. The role of the polymer matrix is proposed to inhibit transport of gas-phase products, which allows them to interact with Fe­(OH)3 doped in the polymer.