The development of the catalytic science has been extensively justified by the great industrial importance of catalytic processes. In this perspective, understanding structure-reactivity relationships in catalytic systems is a fundamental issue for the realization of efficient new catalysts. These reasons help to explain the success of homogeneous catalysts which offer the possibility of precise molecular structure control. By contrast, heterogeneous catalysts are widely used in chemical industry because they are easy to handle, separate, and recycle. The last three decades have witnessed attempts to transfer homogeneous molecular approaches to heterogeneous catalysis. In this context, analogues of well-defined homogeneous catalytic structures have been obtained for heterogeneous catalysis by the direct grafting of organometallic complexes on metal oxide surfaces. Today, single-site supported catalysts have attracted interest for both fundamental scientific and technological reasons, due to the molecular level control of catalyst-substrate interactions and selectivity that they afford. Although experimental results argue that such adsorbate complexes play a significant role in the surface and catalytic chemistry, many important kinetic and mechanistic details of such catalytic processes remain to be elucidated. In this context, theoretical investigations represent a powerful tool for understanding in detail, important aspects of both complex/surface interactions as well as operative catalytic mechanisms. The present contribution focuses on the DFT modeling capabilities in the explanation of the peculiar catalytic behavior of the single-site supported catalyst. In particular, analysis focused on the interaction of prototypical complexes with suited surfaces. Moreover, the individuation of the catalytic mechanism as the preferred reaction path is investigated for the most representative adsorbate species chemisorbed on the surface. The model of the solid support is driven by the wide experimental use in many studies related to heterogeneous catalysis and by the pronounced Lewis or Brønsted acid chemistry that allows direct comparison with analogous homogeneous catalytic systems.

DFT approach for the investigation of single-site supported catalysts

253rd National Meeting (2017)

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