Identification of the Active Sites on Metallic MoO<sub>2−<i>x</i></sub>Nano‐Sea‐Urchin for Atmospheric CO<sub>2</sub>Photoreduction Under UV, Visible, and Near‐Infrared Light Illumination
Xi Wu, Wenlei Zhang, Jun Li, Quanjun Xiang, Zhongyi Liu, Bin Liu
Abstract
Abstract We report an oxygen vacancy (V o )‐rich metallic MoO 2− x nano‐sea‐urchin with partially occupied band, which exhibits super CO 2 (even directly from the air) photoreduction performance under UV, visible and near‐infrared (NIR) light illumination. The V o ‐rich MoO 2− x nano‐sea‐urchin displays a CH 4 evolution rate of 12.2 and 5.8 μmol g catalyst −1 h −1 under full spectrum and NIR light illumination in concentrated CO 2 , which is ca. 7‐ and 10‐fold higher than the V o ‐poor MoO 2− x , respectively. More interestingly, the as‐developed V o ‐rich MoO 2− x nano‐sea‐urchin can even reduce CO 2 directly from the air with a CO evolution rate of 6.5 μmol g catalyst −1 h −1 under NIR light illumination. Experiments together with theoretical calculations demonstrate that the oxygen vacancy in MoO 2− x can facilitate CO 2 adsorption/activation to generate *COOH as well as the subsequent protonation of *CO towards the formation of CH 4 because of the formation of a highly stable Mo−C−O−Mo intermediate.