Niobates are layered compounds formed by [NbO6] octahedral units with an extended 2D arrangement. It provides not only electronic and structural advantages due to the high surface area and electron mobility but also an easy modification by intercalation, superficial modification, or exfoliation. Nevertheless, its photoactivity is ruled by the wide bandgap energy close to 3.5 eV and the high affinity for the photogenerated H2O2. Therefore, some strategies are required to increase the photocatalytic potential and to unveil the redox processes of this material. In this sense, surface grafting is a soft and simple method that has gain attention for inducing new electronic process on the catalyst surface without changing crystallinity and electronic structure in the bulk. In our work, the surface grafting with metallic ions such as Co(II) and Fe(III) could be applied to increase the performance of the exfoliated hexaniobate. In comparison to the bare niobate, 0.1 % of the metallic cation was able to improve the evolution of H2 from water in the applied conditions. The properties and dynamics of the photocatalysts will be discussed based on steady-state and time-resolved spectroscopies.