The Effect of Surface Area and Crystal Structure on the Catalytic Efficiency of Iron(III) Oxide Nanoparticles in Hydrogen Peroxide Decomposition

Iron(II) oxalate dihydrate has been used as a readily decomposable substance for the controlled synthesis of nanosized iron(III) oxides. The polymorphous composition, particle size and surface area of these iron oxide nanoparticles were controlled by varying the reaction temperature between 185 and 500 degrees C. As-prepared samples were characterized by XRD, low-temperature and in-field Mossbauer spectroscopy, BET surface area and the TEM technique. They were also tested as heterogeneous catalysts in hydrogen peroxide decomposition. At the selected temperatures, the formed nanomaterials did not contain any traces of amorphous phase, which is known to considerably reduce the catalytic efficiency of iron(III) oxide catalysts. As the thickness of the sample (approximate to 2 mm) was above the critical value, a temporary temperature increase ("exo effect") was observed during all quasi-isothermal decompositions studied, irrespective of the reaction temperature. Increasing the reaction temperature resulted in a shift of the exo effect towards shorter times and an increased content of maghemite phase. The maghemite content decreases above 350 degrees C as a result of a thermally induced polymorphous transition into hematite. The catalytic data demonstrate that the crystal structure of iron(III) oxide (i.e. the relative contents of maghemite and hematite) does not influence the rate of hydrogen peroxide decomposition. However, the rate constant increases monotonously with increasing sample surface area (and decreasing thermolysis temperature), reaching a maximum of 27 x 10(-3) min(-1)(g/L)(-1) for the sample with a surface area of 285 m(2)g(-1). This rate constant is currently the highest reported value of all known iron oxide catalytic systems and is even slightly higher than that observed for the most efficient catalyst reported to date, which has a significantly larger surface area of 337 m(2)g(-1). This surprisingly high catalytic activity at relatively low surface area can be ascribed to the absence of a amorphous phase in the samples prepared in this study. Taking into account these new findings, the contributions of the key factors highlighted above (surface area, particle size, crystal structure, crystallinity) to the overall activity of iron oxides for hydrogen peroxide decomposition are discussed.