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

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.