title: First steps in combining modulation excitation spectroscopy with synchronous dispersive EXAFS/DRIFTS/mass spectrometry for in situ time resolved study of heterogeneous catalysts.
abstract: The synchronous combination of time resolved (energy dispersive) EXAFS, diffuse reflectance infrared spectroscopy (DRIFTS), and mass spectrometry (MS), applied within the general framework of concentration modulation spectroscopy, is demonstrated for in situ and time-resolved study of the behaviour of Rh/Al(2)O(3) and Pd/Al(2)O(3) catalysts during CO/NO redox cycling at 573 K. We show that by applying a phase sensitive detection technique the quality of information arising from the experiment is significantly improved. Moreover, in the case of the dispersive EXAFS the acuity of this technique is greatly enhanced and a surface sensitivity in the normally bulk sensitive EXAFS measurement can be induced. Lastly we apply this approach to a system (0.3 wt% Rh/Al(2)O(3)) that cannot normally be studied in any meaningful way with transmission based and highly time resolved EXAFS, and show that this method may provide a novel experimental window through which it is possible to restore highly time resolved structural-kinetic information from previously intractable systems.
authors.affiliation: Empa, Swiss Federal Laboratories for Materials Testing and Research, Laboratory for Solid State Chemistry and Catalysis, Ueberlandstrasse 129, CH-8600, Dübendorf, Switzerland. davide.ferri@empa.ch
authors.forename: Davide
authors.initials: D
authors.lastname: Ferri
authors.forename: M Santosh
authors.initials: MS
authors.lastname: Kumar
authors.forename: Ronny
authors.initials: R
authors.lastname: Wirz
authors.forename: Arnim
authors.initials: A
authors.lastname: Eyssler
authors.forename: Oxana
authors.initials: O
authors.lastname: Korsak
authors.forename: Paul
authors.initials: P
authors.lastname: Hug
authors.forename: Anke
authors.initials: A
authors.lastname: Weidenkaff
authors.forename: Mark A
authors.initials: MA
authors.lastname: Newton