text: Operando spectroscopy is a class of methodology, rather than a specific spectroscopic technique such as FTIR or NMR. Operando spectroscopy is a logical technological progression in in situ studies. Catalyst scientists would ideally like to have a "motion picture" of each catalytic cycle, whereby the precise bond-making or bond-breaking events taking place at the active site are known; this would allow a visual model of the mechanism to be constructed. The ultimate goal is to determine the structure-activity relationship of the substrate-catalyst species of the same reaction. Having two experiments—the performing of a reaction plus the real-time spectral acquisition of the reaction mixture—on a single reaction facilitates a direct link between the structures of the catalyst and intermediates, and of the catalytic activity/selectivity. Although monitoring a catalytic process in situ can provide information relevant to catalytic function, it is difficult to establish a perfect correlation because of the current physical limitations of in situ reactor cells. Complications arise, for example, for gas phase reactions which require large void volumes, which make it difficult to homogenize heat and mass within the cell. The crux of a successful operando methodology, therefore, is related to the disparity between laboratory setups and industrial setups, i.e., the limitations of properly simulating the catalytic system as it proceeds in industry.
  The purpose of operando spectroscopy is to measure the catalytic changes that occur within the reactor during operation using time-resolved (and sometimes spatially-resolved) spectroscopy. Time-resolved spectroscopy theoretically monitor the formation and disappearance of intermediate species at the active site of the catalyst as bond are made and broken in real time. However, current operando instrumentation often only works in the second or subsecond time scale and therefore, only relative concentrations of intermediates can be assessed. Spatially resolved spectroscopy combines spectroscopy with microscopy to determine active sites of the catalyst studied and spectator species present in the reaction.