Synergy of Surface Phosphates and Oxygen Vacancies Enables Efficient Photocatalytic Methane Conversion at Room...

Room-temperature photocatalytic conversion of CH₄ into liquid oxygenates with O₂/H₂O provides an appealing route for sustainable chemical industry, which, however, suffers from poor efficiency due to the undesired carrier kinetics and low yield of reactive oxygen species of the currently available photocatalysts. Here, we report an effective surface engineering strategy where concurrent constructions of oxygen vacancies and phosphate sites on TiO₂ nanosheets address the above challenge. The surface oxygen vacancies and phosphates are respective acceptors of photogenerated electrons and holes for promoted separation and migration of charge carriers. Moreover, in addition to the facilitated activation of O₂ to ^•OH by electrons at oxygen vacancies, the surface phosphates also facilely adsorb H₂O via hydrogen bonds and thus effectively transfer holes to H₂O for enhanced ^•OH production, thereby boosting CH₄ conversion. As a result, compared with TiO₂ sheets with only oxygen vacancies, a 2.8 times improvement in liquid oxygenate production with near-unity selectivity is achieved by virtue of the synergy of surface oxygen vacancies and phosphate sites, together with an unprecedent quantum efficiency of 19.8% under 365 nm irradiation.