Aromatic Cation-π Interaction-Driven Scalable Biomimetic Pockets Embedded Supramolecular Coassemblies for...

Area of Science:

• Supramolecular Chemistry
• Photocatalysis
• Carbon Dioxide Reduction

Background:

• Controlling selectivity in carbon dioxide reduction (CO2RR) is vital for sustainable energy solutions.
• Organic supramolecular systems lack defined sites to stabilize reaction intermediates, hindering selectivity.
• Biomimetic approaches inspired by protein active sites offer a potential solution.

Purpose of the Study:

• To design and demonstrate organic supramolecular photocatalysts with biomimetic pockets for controllable CO2RR.
• To achieve high selectivity between carbon monoxide (CO) and methane (CH4) production.
• To investigate the role of dynamic self-adaptive pockets in stabilizing intermediates.

Main Methods:

• Fabrication of one-dimensional supramolecular coassemblies (1DCA) with embedded biomimetic pockets.
• Utilizing cation-π interactions and self-adaptive cage structures to stabilize C1 intermediates.
• Employing photocatalysis for CO2 reduction and analyzing product selectivity (CO vs. CH4).

Main Results:

• TA-1DCA demonstrated 95.8% selectivity for methane production (>90 μmol g⁻¹ h⁻¹).
• BE-1DCA showed 79.9% selectivity for carbon monoxide production (~67 μmol g⁻¹ h⁻¹).
• The biomimetic pockets dynamically adjusted to stabilize specific intermediates, guiding the reaction pathway.

Conclusions:

• Scalable biomimetic pockets in supramolecular coassemblies enable controllable CO2RR selectivity.
• Dynamic self-adaptive behavior of the pockets is key to stabilizing intermediates and directing product formation.
• This approach offers a promising strategy for designing efficient photocatalysts for CO2 conversion.