Partial oxidation of methane by photocatalysis

Methane chemistry is one of the “Holy Grails of catalysis”. It is highly desirable but challenge to transform methane into value-added chemicals, because of its high C-H bonding energy (435 kJ mol−1), lack of π bonding or unpaired electrons. Currently, commercial methane conversion is usually carried out in harsh conditions with enormous energy input. Photocatalytic partial oxidation of methane to liquid oxygenates (PPOMO) is a future-oriented technology towards realizing high efficiency and high selectivity under mild conditions. The selection of oxidant is crucial to the PPOMO performance. Hence, attentions are paid to the research progress of PPOMO with various oxidants (O2, H2O, H2O2 and other oxidants). Moreover, the activation of the selected oxidants is also highly emphasized. Meanwhile, we summarized the methane activation mechanisms focusing on the C-H bond that was broken mainly by •OH radical, O− specie or photogenerated hole (h+). Finally, the challenges and prospects in this subject are briefly discussed. [Display omitted] Progress in partial oxidation of methane to liquid oxygenates with various oxidants (H2O, H2O2 or O2) by photocatalysis is systematically summarized. The activation of selected oxidant is highlighted. Methane activated mainly by •OH radicals, O− species or photogenerated hole (h+) is also highly emphasized.