Biomimetic Parallel Vein-like Two-Dimensional Supramolecular Layers Containing Embedded One-Dimensional Conduits...

Area of Science:

• Materials Science
• Supramolecular Chemistry
• Photocatalysis

Background:

• Two-dimensional supramolecular assemblies (2DSAs) show promise in photocatalysis.
• Achieving effective electron transport and multiple active sites in 2DSAs remains a challenge.
• Existing 2DSAs lack structural paradigms for optimal intermolecular orbital overlap and substrate contact.

Purpose of the Study:

• To design and synthesize biomimetic 2DSAs with enhanced photocatalytic performance.
• To overcome limitations in electron transport and active site accessibility in 2DSAs.
• To create a novel structural paradigm inspired by plant venation.

Main Methods:

• Hierarchical self-assembly of cationically modified, rigid multiarmed monomers.
• Construction of parallel vein-like two-dimensional supramolecular layers (PV-2DSLs) with integrated 1D conduits.
• Characterization of structural features, including long-range aromatic cation-π stacking and embedded conduits.

Main Results:

• PV-2DSLs exhibit long-range aromatic cation-π stacking facilitating electron transport.
• Embedded 1D conduits promote multielectron transfer pathways, enhancing charge separation.
• Achieved hydrogen production rates of 3.5 mmol g⁻¹ h⁻¹, a 17.5-fold increase compared to controls.

Conclusions:

• The biomimetic PV-2DSLs provide a novel structural paradigm for advanced 2DSAs.
• The integrated 1D conduits are crucial for improved charge separation and carrier transport.
• These findings offer a promising strategy for enhancing photocatalytic efficiency in supramolecular materials.