W Single-Atoms Anchored on Rutile TiO2 for Direct Methane Photocatalytic Conversion under Mild Conditions

Photo-driven direct CH4 4 conversion to value added liquid oxygenates attracts great attention for its enormous energy and environment benefits. However, because of the intrinsic inertness of CH4 , 4 , realizing highly efficient direct CH4 4 conversion and prevent peroxidation remains a great challenge. Herein, a novel photo- catalyst of rutile TiO2 2 supported W single-atoms was prepared for CH4 4 direct conversion to C1 products with 100% selectivity. The electron deficient property of the atomically-dispersed W active sites together with the photo-excited electron transferring from Ti to W can facilitate H2O2 2 O 2 adsorption and decomposition, and promote CH4 4 activation and conversion to varied products with a yield as high as 7 mmol g cat-1 h-1.-1 . This yield equaled to 238.5 mol molW-1 W-1 h-1 ,-1 , 82 times higher than that of the reported Cr single-atoms. In-situ ESR, FTIR and DFT simulation were combined to elucidate the CH4 4 conversion mechanism.