There is tremendous motivation to know the energies of adsorbed catalytic reaction intermediates and transition states on different surfaces, for these are the factors that determine the differences in activity and selectivity between one catalyst material and another. There is also strong motivation to know the energies of the surface atoms of catalyst materials, and how their energies can be predicted based on details on the catalyst structure, such as nanoparticle size, the support material to which they are attached, and the presence of additives. These energies correlate with both the reactivity of those surface atoms and the rate at which the catalyst material deactivates with time on stream. All these energies, when accurately measured, provide benchmarks for testing the energy accuracy of computational methods for surface chemistry. Many of these energies can only be measured by direct calorimetric methods. I review here calorimetric methods for experimentally measuring the energies of adsorbates on clean single-crystal model catalyst surfaces, and the energies of catalytic metal atoms within bimetallic surfaces and within small (<5 nm) metal nanoparticles supported on planar single-crystal support surfaces and powdered catalyst support materials. I also briefly review methods for studying surface reaction energies during metal film deposition on polymer surfaces and during Atomic Layer Deposition (ALD). I focus here on adsorption calorimetry methods developed by my own group based on pyroelectric heat detectors in physical contact with the materials whose surfaces are being studied.
Charles T. Campbell (Sun,) studied this question.