Aiming at understanding how plasmonic reactions depend on important parameters such as metal loading and strong metal–support interaction (SMSI), we report the plasmonic photodegradation of formic acid (FA) under green LED irradiation employing three TiO₂ supports (stoichiometric TiO₂, N-doped TiO₂, black TiO₂) modified with Au nanoparticles (NPs) 3–6 nm in size. The rate of FA photooxidation follows different trends depending on Au loading for stoichiometric and doped Au/TiO₂ materials. In the first case, the only contribution of hot electron transfer produces a volcano-shaped curve of photoreaction rates with increasing Au loading. When TiO₂ contains intra-bandgap states the photoactivity increases linearly with the amount of Au NPs due to the concomitant enhancement produced by hot electron transfer and plasmon resonant energy transfer (PRET). The role of PRET is supported by finite element method simulations, which show that the increase in both Au NP inter-distance and SMSI enhances the probability of charge carrier generation at the Au/TiO₂ interface.

Copper–zirconia catalysts find many applications in different reactions owing to their unique surface properties and relatively easy manufacture. The so-called methanol economy, which includes the CO₂ and CO valorization and the hydrogen production, and the emerging (bio)alcohol upgrading via dehydrogenative coupling reaction, are two critical fields for a truly sustainable development in which copper–zirconia has a relevant role. In this review, we provide a systematic view on the factors most impacting the catalytic activity and try to clarify some of the discrepancies that can be found in the literature. We will show that contrarily to the large number of studies focusing on the zirconia crystallographic phase, in the last years, it has turned out that the degree of surface hydroxylation and the copper–zirconia interphase are in fact the two mostly determining factors to be controlled to achieve high catalytic performances.