The Role of In Situ / Operando IR Spectroscopy in Unraveling Adsorbate-Induced Structural Changes in Heterogeneous Catalysis.

Heterogeneous catalysts undergo thermal- and/or adsorbate-induced dynamic changes under reaction conditions, which consequently modify their catalytic behavior. Hence, it is increasingly crucial to characterize the properties of a catalyst under reaction conditions through the so-called " operando " approach. Operando IR spectroscopy is probably one of the most ubiquitous and versatile characterization methods in the field of heterogeneous catalysis, but its potential in identifying adsorbate- and thermal-induced phenomena is often overlooked in favor of other less accessible methods, such as XAS spectroscopy and high-resolution microscopy. Without detracting from these techniques, and while aware of the enormous value of a multitechnique approach, the purpose of this Review is to show that IR spectroscopy alone can provide relevant information in this field. This is done by discussing a few selected case studies from our own research experience, which belong to the categories of both "single-site"- and nanoparticle-based catalysts.