In heterogeneous catalysis, dynamic behaviors involving supposedly inert reactor dilutant and the catalyst are not rare, but related understanding is lacking and inconsistent. Here we present the effects of anatase TiO2 dilutant on the reverse water-gas shift (rWGS) reaction over Pt/Al2O3. Combining detailed kinetic data with microscopic and spectroscopic results, we demonstrate that such effect depends on temperature. At high temperature (400 °C), Pt migrate from Al2O3 to TiO2, resulting in higher dispersion and activity, without changing reaction mechanisms. Similar dynamics are also present with various oxide dilutants, resonant with our previous work using TiO2 to dilute Pd/TiO2. In contrast, at low temperature (250 °C), carboxylic acids, in particular acetic acid, present in the ambient air and adsorbed on TiO2 are transferred onto Al2O3 in close contact, effectively blocking the formate rWGS pathway. As a result, the rWGS can only proceed through the carboxyl pathway, and hence is significantly slower. The acetate transfer affects catalysts of different Pt nuclearity and support, but is unique to anatase TiO2 dilutant. As the acetate layer is slowly removed under H2 or the rWGS stream, the activity recovers. This work elucidates the complicated dynamics between catalysts and dilutants, which has general implications in heterogeneous catalysis, and resolves inconsistency in related reports in the literature. The impacts that anatase TiO2 dilution has on the rWGS also unveil mechanistic understanding that further confirms the two co-existing rWGS pathways.

Dynamics between supported metal catalysts and oxide dilutant during the reverse water gas shift (rWGS) reaction: metal transfer and acetate migration

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