Dimensionality- and Pathway-Engineered Charge Transport Dynamics Mediate Divergent Product Selectivity in...

Area of Science:

• Materials Science
• Catalysis
• Photochemistry

Background:

• Conventional catalyst design relies on thermodynamic properties.
• Regulating charge transport dynamics offers a new methodology for catalyst design.
• Developing advanced photocatalysts is crucial for efficient chemical conversion.

Purpose of the Study:

• To develop a general strategy for synthesizing Sv-chalcogenide/Ti3C2 photocatalytic architectures.
• To investigate how controlled charge transport behavior influences molecular catalytic behavior.
• To achieve selective polyethylene terephthalate (PET) photoreforming into specific products.

Main Methods:

• Metal-organic frameworks-templated topotactic transformation and defect-mediated heterocomponent anchorage were used for synthesis.
• Core-shell dual-tunable parameters were engineered in the photocatalysts.
• Charge transport dimensionality and pathways were controlled to dictate reaction selectivity.

Main Results:

• The synthesized catalysts demonstrated tunable charge transport dimensionality and pathways.
• Zn0.5Cd0.5S lattice transformation controlled catalyst-substrate interaction and intermediate activation.
• An interfacial built-in electric field (BIEF) in Zn0.5Cd0.5S/Ti3C2 created directional charge transport pathways.
• Selective PET conversion yielded dehydrogenation-dominated CHOCOOH (81% selectivity) or hydrodeoxygenation-driven CH3COOH (86% selectivity).

Conclusions:

• This work establishes a pioneering paradigm for catalyst design by linking geometrical transformation, charge transport dimensionality, and reaction pathway switching.
• Interfacial engineering and control of charge transport pathways significantly improve catalytic activity.
• Charge transport behavior plays a substantial role in determining specific molecular catalytic outcomes.