Plasmonic O₂ dissociation and spillover expedite selective oxidation of primary C–H bonds

Abstract

Room-temperature O2 dissociation and spillover, as driven by plasmonic Ru on oxygen-deficient TiO2, expedite the selective oxidation of primary C–H bonds in alkyl aromatics for synthesizing industrially important organic compounds.

Surface Boronizing Can Weaken the Excitonic Effects of BiOBr Nanosheets for Efficient O2 Activation and Selective NO Oxidation under Visible Light Irradiation

“…To address this huge hurdle, nature has evolved families of metalloproteins bearing unpaired d-electrons to metabolize O 2 through stepwise reduction . Inspired by the functionality of metalloproteins, heterogeneous catalysts (noble metals or transition metal oxides) with redox centers have been developed for artificial O 2 activation, which, however, usually suffer from harsh reaction conditions (high temperature) or high cost. − With the employment of low-cost semiconductors as catalysts and solar light as the energy source, the photocatalytic activation of O 2 to radical or anionic reactive oxygen species (ROS: • O – , • O 2 – , • O 2 2– ) mediated by photoelectrons provides a more environmentally friendly and cost-effective alternative. − …”

Targeted NO Oxidation and Synchronous NO2 Inhibition via Oriented 1O2 Formation Based on Lewis Acid Site Adjustment

“…The ppb-level nitrogen oxides (NO x , x = 1, 2, the proportion of NO is about 95%) are an important precursor to participate in the formation of secondary organic aerosols and ozone, leading to current atmospheric environmental problems. − Over the past decades, substantial efforts have been made on searching purification strategies for trace NO; photocatalytic oxidation stands out from the crowd, holding the advantage of a more convenient, lower cost, and smaller environmental footprint. − Nevertheless, as an odd-electron molecule, NO exhibits excellent reactivity and thus owns various reaction pathways. , There is a sacrifice in environmental benefits when NO 2 emerges as an end-product, whose exposure is linked to serious respiratory illness, decreased lung function, and airway inflammation. , Considering the multiple reaction pathways of NO and the toxicity of NO 2 , an effective strategy of inhibiting the formation of NO 2 during photocatalytic NO oxidation should be well developed to guarantee better environmental significance. Proverbially, reactive oxygen species (ROS) dominate the performance of oxidation process. − In other words, a rational design of photocatalysts, aiming to achieve precise regulation of the ROS evolution process and thus oriented ROS formation, is the root of highly efficient photocatalytic NO oxidation with synchronous NO 2 inhibition.…”

Oxygen and Chlorine Dual Vacancies Enable Photocatalytic O2 Dissociation into Monatomic Reactive Oxygen on BiOCl for Refractory Aromatic Pollutant Removal

“…Therefore, the deep oxidation of refractory aromatic heterocyclic pollutants often seeks help from thermocatalytic oxidation by means of O 2 dissociation toward monatomic oxygen (•O) generation, which is a more powerful ROS than •O 2 – and O 2 2– . − Unfortunately, direct O 2 dissociation into monatomic ROS is kinetically limited by the stubborn O–O double bond under ambient conditions. Recently, researchers have demonstrated that plasmonic electrons are able to alleviate the energy-demanding O 2 dissociation by transiently populating the antibonding orbitals of O 2 , which, however, are limited to expensive noble metals. − Thus, direct photocatalytic O 2 dissociation into monatomic ROS with inexpensive photocatalysts is of great significance but still challenging.…”