On the way to the creation of next generation photoactive materials
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Transition from first- to second-generation photocatalysts has followed the notion that greater absorption of light in the visible region would yield greater spectral sensitivity and greater photoactivity. Though a promising strategy, in practice, it did not meet expectation because of various side issues, which in many cases has led to loss of photoactivity and chemical reactivity. This article examines some earlier notions that arose from applications of different metal oxides (e.g., TiO2, ZnO, MgO among others) that made these oxides good photocatalysts in many processes.
Phenomena that proved relevant in developing next generation photoactive materials are considered: the dependence of the activity of photocatalysts on the band gap energy, the spectral variations of the activity of photoactive materials, and the spectral variations of selectivity of photoactive materials. The tendency to decrease the energy of actinic photons through doping in forming second-generation photocatalysts is completely opposite the fundamental observation in first-generation photocatalysts whereby the activity increased with increasing band gap energy. Extension of spectral sensitivity of second-generation photoactive materials also caused a decrease of their photoactivity; hence, some notions are reconsidered to produce next(third) generation photoactive materials.
The article proposes the following concepts to develop next generation photocatalysts: (1) multi(two)-photon excitation of photoactive materials with lower energy photons to achieve the same excited state as with higher energy photons, (2) utilization of heterojunctions to drive electronic processes in the desired direction, and (3) selective photoexcitation of localized electronic states to gain better selectivity.
KeywordsHeterogeneous photocatalysis Metal oxides Photoactivity Selectivity Spectral sensitivity Heterostructures
This work was partially supported by a Grant from the Russian Foundation for Basic Research (No. 10-03-00638-a). One of us (NS) thanks Prof. Albini of the Universita di Pavia for his continued kind hospitality in his laboratory. We are particularly grateful to Prof. Basov for providing us with the original data for Fig. 1.
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