Montmorillonite
(MMT), a layered hydrated aluminum silicate mineral,
emerges as a promising catalyst support due to its substantial specific
surface, ion storage capacity, thermal stability, and cost-effectiveness.
Despite the success of MMT-based photocatalysts in degrading compounds,
their potential for the photocatalytic hydrogen evolution reaction
(HER) is underexplored. Furthermore, the reliance on noble metals
and dye sensitization in MMT-based photocatalysts leads to elevated
costs. This study introduces an MMT-based photocatalyst modified with
Fe species (denoted as Fe@MMT) for photocatalytic HER without the
reliance on noble metals and dye sensitization. The incorporation
of Fe species has a dual impact, expanding the light harvesting region
of MMT and modulating the aluminum-silicate framework. Simultaneously,
it facilitates the exfoliation of individual sheets from stacked MMT
layers, generating abundant active sites and inner electronic fields
that can promote the separation of photoexcited electrons and enhance
the photon-to-electron conversion. In comparison to pristine MMT,
Fe@MMT exhibits a 43% reduction in the charge transfer resistance
in the dark and a 52% reduction under illumination. Additionally,
the majority carrier density within the space charge region increased
by 33%. Due to these advantages, the photocatalytic HER efficiency
over Fe@MMT was improved, approximately 2.9 times that of pristine
MMT.