Recent Advances in Heterogeneous Photo‐Driven Oxidation of Organic Molecules by Reactive Oxygen Species

Abstract

The photo-driven oxidation of organic molecules into corresponding high-value-added products has become a promising method in chemical synthesis. This strategy can drive thermodynamically non-spontaneous reactions and achieve challenging thermocatalytic processes under ambient conditions. Reactive oxygen species (ROS) are not only significant intermediates for producing target products via photoinduced oxidation reactions but also contribute to the creation of sustainable chemical processes. Here, the latest advances in heterogeneous photo-driven oxidation reactions involving ROS are summarized. The major types of ROS and their generation are introduced, and the behaviors of various ROS involved in photo-driven processes are reviewed in terms of the formation of different bonds. Emphasis is placed on unraveling the reaction mechanisms of ROS and establishing strategies for their regulation, and the remaining challenges and perspectives are summarized and analyzed. This Review is expected to provide an in-depth understanding of the mechanisms of ROS involved in photo-driven oxidation processes as an important foundation for the design of efficient catalysts. Clarifying the role of ROS in oxidation reactions has important scientific significance for improving the atomic and energy efficiency of reactions in practical applications.

Integrating TEMPO into a Metal–Organic Framework for Cooperative Photocatalysis: Selective Aerobic Oxidation of Sulfides

“…The measured generation of the ROS is of great importance in confirming the occurrence of photocatalytic oxidation reactions. 62 By introducing various scavengers, the quenching tests under the same reaction conditions were conducted to determine the ROS (Table 3). The process could not be performed when the atmosphere was supplied with N 2 to eliminate O 2 , implying that the origin of the ROS is O 2 (Table 3, entry 2).…”

Photoelectrochemical alcohols oxidation over polymeric carbon nitride photoanodes with simultaneous H2 production

“…The cO 2 À radicals play the important role of promoting the rapid consumption of photogenerated e À in the reaction, thus accelerating the separation of photogenerated e À and h + , which is benecial for the BnOH oxidation. 51,52 Subsequently, the BZD molecules are oxidized by h + at the electrode to form carboncentered radicals, which themselves react with cO 2 À to form BZA. During the oxidation process, most e À transfer to the Pt counter electrode (the cathode), thanks to the applied bias, where they reduce the adsorbed hydrogen (H ads ) formed by water dissociation into H 2 .…”

Precious Metal-Free LaMnO3 Perovskite Catalyst with an Optimized Nanostructure for Aerobic C–H Bond Activation Reactions: Alkylarene Oxidation and Naphthol Dimerization

“…In the past two decades, catalytic functionalization of unactivated C–H bonds has attracted broad attention across various fields of chemistry as it presents a profound potential to change the way we think about chemical synthesis. − In this respect, C–H oxidation reactions constitute an important subclass of such C–H functionalization reactions where unactivated CH x groups are generally oxidized to value-added alcohols or carbonyl-containing functional groups. − Among the various catalytic processes developed for C–H oxidation reactions, those that involve nonprecious, earth-abundant transition-metal salts or complexes as catalysts and molecular oxygen as the stoichiometric oxidant are particularly attractive from an environmental as well as an economical perspective. ,− …”