Electrophilicity in heterogeneous catalysis: role of surface and sub-surface modification

Efforts to bridge the gap between homogeneous and heterogeneous catalysis include the use of surface organometallic chemistry, single atom catalysis and monodispersed metal nanoparticles, among others. In the case of metal and supported metal catalysts, the electrophilic nature induced in the case of metal single crystals or metal NPs shows remarkable effects on catalytic activities. The electrophilicity can be induced by surface and sub-surface modification. This mini-review discusses key approaches to introduce electrophilicity in heterogeneous catalysts by surface treatment and the use of appropriate sub-surface species. © The Royal Society of Chemistry 2021.