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 Lp is smaller than 1.0 nm while the separation efficiency ηsep 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. An effective solution to the problem of serious charge recombination in metallic photocatalysts is described. The concept is demonstrated by encapsulating individual metallic MoO2 particles in a hydrothermal carbonation carbon (HTCC) matrix. When integrating with HTCC, MoO2 exhibits enhanced charge separation efficiency and photocatalytic activity because of an internal electric field and appropriate band alignment.