Measuring Transient Reaction Rates from Nonstationary Catalysts

Up to now, methods for measuring rates of reactions on catalysts required long measurement times involving signal averaging over many experiments. This imposed a requirement that the catalyst return to its original state at the end of each experiment-a complete reversibility requirement. For real catalysts, fulfilling the reversibility requirement is often impossible-catalysts under reaction conditions may change their chemical composition and structure as they become activated or while they are being poisoned through use. It is therefore desirable to develop high-speed methods where transient rates can be quickly measured while catalysts are changing. In this work, we present velocity-resolved kinetics using high-repetition-rate pulsed laser ionization and high-speed ion imaging detection. The reaction is initiated by a single molecular beam pulse incident at the surface, and the product formation rate is observed by a sequence of pulses produced by a high-repetition-rate laser. Ion imaging provides the desorbing product flux (reaction rate) as a function of reaction time for each laser pulse. We demonstrate the principle of this approach by rate measurements on two simple reactions: CO desorption from and CO oxidation on the 332 facet of Pd. This approach overcomes the time-consuming scanning of the delay between CO and laser pulses needed in past experiments and delivers a data acquisition rate that is 10-1000 times higher. We are able to record kinetic traces of CO₂ formation while a CO beam titrates oxygen atoms from an O-saturated surface. This approach also allows measurements of reaction rates under diffusion-controlled conditions.