Molecular layer-by-layer re-stacking of MoS2–In2Se3 by electrostatic means: assembly of a new layered photocatalyst

2D-layered transition metal chalcogenides are useful semiconductors for a wide range of opto-electronic applications. Their similarity as layered structures offers exciting possibility to modify their electronic properties by creating new heterojunction assemblies from layer-by-layer restacking of individual monolayer sheets, however, the lack of specific interaction between these layers could induce phase segregation. Here, we employed a chemical method using n-BuLi to exfoliate MoS2 and In2Se3 into their monolayer-containing colloids in solution. The bulky Se atoms can be selectively leached from In2Se3 during Li treatment which gives positively charged surface monolayers in neutral pH whereas the strong polarization of Mo–S with moderate S leaching gives a negatively charged surface. Specific interlayer electrostatic attraction during their selective assembly gives a controllable atomic AB-type of layer stacking as supported by EXAFS, STEM with super-EDX mapping, TAS/TRPL and DFT calculations. Using this simple but inexpensive bottom-up solution method, a new photocatalyst assembled from layers for photo water splitting can be tailor-made with high activity.