Impact of quantum size effects to the band gap of catalytic materials: a computational perspective.

The evolution of nanotechnology has facilitated the development of catalytic materials with controllable composition and size, reaching the sub-nanometer limit. Nowadays, a viable strategy for tailoring and optimizing the catalytic activity involves controlling the size of the catalyst. This strategy is underpinned by the fact that the properties and reactivity of objects with dimensions on the order of nanometers can differ from those of the corresponding bulk material, due to the emergence of quantum size effects. Quantum size effects have a deep influence on the band gap of semiconducting catalytic materials. Computational studies are valuable for predicting and estimating the impact of quantum size effects. This perspective emphasizes the crucial role of modeling quantum size effects when simulating nanostructured catalytic materials. It provides a comprehensive overview of the fundamental principles governing the physics of quantum confinement in various experimentally observable nanostructures. Furthermore, this work may serve as a tutorial for modeling the electronic gap of simple nanostructures, highlighting that when working at the nanoscale, the finite dimensions of the material lead to an increase of the band gap because of the emergence of quantum confinement. This aspect is sometimes overlooked in computational chemistry studies focused on surfaces and nanostructures.

Key Ingredients for the Screening of Single Atom Catalysts for the Hydrogen Evolution Reaction: The Case of Titanium Nitride.

A computational screening of Single Atom Catalysts (SACs) bound to titanium nitride (TiN) is presented, for the Hydrogen Evolution Reaction (HER), based on density functional theory. The role of fundamental ingredients is explored to account for a reliable screening of SACs. Namely, the formation of H2-complexes besides the classical H* one impacts the predicted HER activity, in line with previous studies on other SACs. Also, the results indicate that one needs to adopt self-interaction-corrected functionals. Finally, predicting an active catalyst is of little help without an assessment of its stability. Thus, it is included in the theoretical framework the analysis of the stability of the SACs in working conditions of pH and voltage. Once unconventional intermediates and stability are considered in a self-interaction corrected scheme, the number of potential good catalysts for HER is strongly reduced since i) some potentially good catalysts are not stable against dissolution and ii) the formation of unconventional intermediates leads to thermodynamic barriers. This study highlights the importance of including ingredients for the prediction of new systems, such as the formation of unconventional intermediates, estimating the stability of SACs, and the adoption of self-interaction corrected functionals. Also, this study highlights some interesting candidates deserving of dedicated work.