A Supramolecular-Nanocage-Based Framework Stabilized by π-π Stacking Interactions with Enhanced Photocatalysis.

Area of Science:

• Supramolecular Chemistry
• Materials Science
• Photocatalysis

Background:

• π frameworks are porous supramolecular materials with potential in photocatalysis, but examples are scarce.
• Supramolecular self-assembly offers a route to engineer complex porous architectures.

Purpose of the Study:

• To construct and characterize a novel supramolecular-cage-based π framework.
• To evaluate its performance as a photocatalyst for hydrogen evolution.

Main Methods:

• Synthesis of a photoactive Cu(I) complex unit.
• Self-assembly of 24 units into a sodalite-topology nanocage via π-π stacking.
• Formation of a 3D porous π framework (π-2).
• Incorporation of ultrafine platinum (Pt) subnanometer particles as a co-catalyst.

Main Results:

• A stable, porous π framework (π-2) with a 2.8 nm inner diameter was formed.
• π-2 demonstrated adsorption capabilities for CO2, iodine, and methyl orange.
• Photocatalytic hydrogen evolution rate reached 524,012 μmol/gPt/h with Pt co-catalyst, a record high.
• High activity attributed to ultrafine Pt particles and efficient electron transfer.

Conclusions:

• π-2 represents a unique, stable supramolecular-cage-based π framework.
• The material exhibits excellent photocatalytic activity for hydrogen evolution.
• This work opens new avenues for designing advanced porous materials in photocatalysis.