Experimental measurements of the energetics of surface reactions

Microcalorimetric measurements of the adsorption energies of well-defined surface species are reviewed, using selected examples mainly from our own group to demonstrate the types of information that can be achieved with this technique. The adsorption energies of molecules on single crystal transition metal surfaces to produce well-characterized molecular or dissociated adsorbates allow determination of the standard enthalpies of formation of key catalytic reaction intermediates. The adsorption energies for metal atoms during metal thin-film growth allow quantitative estimates of metal-substrate bond energies, metal film/substrate adhesion energies and the energetic costs associated with lattice mismatch during thin film growth. Results for several metals on MgO(1 0 0) reveal that they bind weakly to terrace sites. Metals from the right side of the periodic table also bind weakly to step and kink sites (although more strongly than on terraces), whereas alkali and alkaline earth metals bind very strongly to these defects. At 300 K, metals tend to form 2D or 3D clusters nucleated on MgO(1 0 0) defects, via a transiently adsorbed precursor (mobile adatoms on terraces). Calorimetric measurement of the energy of metal atoms in supported 3D metal nanoparticles as a function of particle size reveals a very strong size dependence below 6 nm diameter. Metal atoms also adsorb weakly on polymer surfaces and nucleate 3D metal particles, sometimes in kinetic competition with migration to and strong reaction with the more reactive, subsurface organic functional groups. Measurements of the energies for adsorbed proteins on calcium phosphate crystals, which have been structurally characterized by NMR, reveal extremely weak binding dominated by the entropy gained from release of organized water. These experimental measurements of the energies of well-defined adsorbates serve as benchmarks against which to compare theoretical computations for accuracy, thus enabling improvement upon quantum mechanical methods. Comparisons of calorimetric adsorption energies on single crystal surfaces with state-of-the-art DFT calculations show that the latter can often be in substantial (⩾20%) error.