Simultaneous Measurement of X-ray Absorption Spectra and Kinetics: A Fixed-bed, Plug-flow Operando Reactor

Abstract

An inexpensive fixed-bed, plug-flow operando reactor is described in which X-ray absorbance and kinetic data can be measured simultaneously. Pt L₃ (11.56 keV) XANES and EXAFS data were obtained on a 1.5% Pt/silica catalyst in borosilicate glass reactors of different diameters, 3–6 mm, and thicknesses, 0.3–1.2 mm, some of which are capable of operation at pressures up to about 40 atm. Additionally, polyimide tubular reactors with low absorbance can be used for lower energy edges of the 3d transition metals, or fluorescence detection for low concentration or highly absorbing supports. With the polyimide reactor, however, the pressure is limited to ~3.5 atm and the reaction temperature to about 300 °C. To validate the reactor, the rate and activation energies for the water-gas shift reaction on 2% Pd, 13.7% Zn on Al₂O₃ catalyst were within 15% of those obtained in a standard laboratory reactor, which is within laboratory reproducibility. In addition, the Pd K edge (24.35 keV) XANES and EXAFS data on pre-reduced catalyst were identical to that previously determined on a regular cell. The EXAFS data show that the degree of Pd–Zn alloy formation changes with reaction temperature demonstrating the importance of characterizing the catalyst under reaction conditions.