Ethanol Solution Plasma Loads Carbon Dots onto 2D HNb₃O₈ for Enhanced Photocatalysis

Layered metal oxoacids hold potential as photocatalysts due to their facile exfoliation to two-dimensional (2D) nanosheets with a large surface area and a short migration distance for photoexcited charge carriers. However, the utilization of electrons in photocatalytic processes is restricted by the competitive trapping of electrons by metal ions. In this work, we attempt to improve the utilization of photogenerated electrons over exfoliated HNb₃O₈ nanosheets by solution plasma activation. On dispersing exfoliated HNb₃O₈ nanosheets in ethanol solution plasma, the defects in HNb₃O₈ can be engineered, and carbon dots (CDs) can be anchored on the surface of HNb₃O₈ nanosheets in situ. In comparison with pristine HNb₃O₈ nanosheets, the rate of photocatalytic hydrogen evolution can be increased by 317.7 times over the HNb₃O₈/C heterojunction, and the apparent quantum efficiency of hydrogen production can be as high as 5.05%. The reason for the high photocatalytic performance is explored by the comparison of activation between plasma-in-ethanol and plasma-in-water, which reveals that CD anchoring and defect engineering indeed promote charge separation and hence lead to enhanced photocatalytic activity. This work provides an alternative approach to synthesize CDs and activate 2D-layered compounds with MO₆ (M = Nb, Ti, and W) octahedral building blocks in the host layer for enhanced photocatalytic evolution of hydrogen.