Band Engineering Induced by Sulphur Vacancies in MoS2/g-C3N4 or Selective CO2 Photoreduction to CH3OH

Developing photocatalysts with both high efficiency and reaction pathway selectivity is essential for achieving efficient and sustainable CO₂ conversion. By incorporating sulphur vacancies into MoS₂, an S-scheme heterojunction photocatalyst (MoS₂-SVs/g-C₃N₄) was developed, achieving efficient and selective CO₂ photoreduction to CH₃OH. The structural and photoelectronic characterisation of the system shows that the heterogeneous interface between MoS₂ and g-C₃N₄ is in close contact. The introduction of SVs effectively modulates the electronic structure and surface activity of MoS₂, which in turn enhances the CO₂ reduction performance. Optical and electronic structure analyses reveal that the heterojunction promotes favourable band alignment and interfacial electric potential gradients, which together suppress charge recombination and enhance directional carrier separation. Under irradiation, the MoS₂-SVs/g-C₃N₄ photocatalyst exhibited outstanding photocatalytic CH₃OH production with a yield of 10.06 μmol·h^-1·g^-1, significantly surpassing the performance of control samples while demonstrating excellent product selectivity and remarkable stability. Mechanistic studies further verify that vacancy-induced energy band modulation with Fermi energy level enhancement significantly reduces the multi-electron transfer barrier, thus preferentially driving the CH₃OH generation pathway. This work proposes a universal structural design strategy that synergistically coordinates vacancy engineering with band structure modulation, establishing both theoretical principles and practical methodologies for developing selective multi-electron CO₂ reduction systems.