Enhancing Charge Separation in Metallic Photocatalysts: A Case Study of the Conducting Molybdenum Dioxide

A new visible‐light responsive metallic photocatalyst, nanostructured MoO₂, has been discovered. The metallic nature of MoO₂ is confirmed by valance X‐ray photoelectron spectroscopy spectrum and theoretical calculations. However, MoO₂ itself shows only moderate activity due to the serious charge recombination, a general disadvantage of metallic photocatalysts. The findings suggest that its effective charge diffusion length L_p is smaller than 1.0 nm while the separation efficiency η_sep is less than 10%. Therefore, only the periphery of the metallic MoO₂ can effectively contribute to photocatalysis. This limitation is overcome by integrating MoO₂ in a hydrothermal carbonation carbon (HTCC) matrix (mainly contains semiconductive polyfuran). This simple chemical modification brings two advantages: (i) an internal electric field is formed at the interface between MoO₂ and HTCC due to their appropriate band alignment; (ii) the nanostructured MoO₂ and the HTCC matrix are intertwined with each other intimately. Their small size and large contact area promote charge transfer, especially under the internal electric field. Therefore, the separation rate of photoexcited charge carrier in MoO₂ is greatly enhanced. The activity increases by 2.4, 16.8, and 4.0 times in photocatalytic oxygen evolution, dyes degradation, and photoelectrochemicl cell, respectively. The new approach is helpful for further development of metallic photocatalysts.