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

Shifting from conventional thermodynamic descriptors toward charge transport dynamics regulation has emerged as an innovative-catalyst-design methodology. A general strategy is developed for synthesizing Sv-chalcogenide/Ti₃C₂ photocatalytic architectures (Sv represents sulfur vacancies; chalcogenides include Zn_0.5Cd_0.5S, ZnIn₂S₄, CdIn₂S₄, CdS) featuring core-shell dual-tunable parameters via metal-organic frameworks-templated topotactic transformation and defect-mediated heterocomponent anchorage. These nanoreactors leverage controlled charge transport behavior, encompassing charge transport dimensionality and charge transport pathway, to manipulate specific molecular catalytic behavior, dictating polyethylene terephthalate (PET) photoreforming pathway bifurcation between dehydrogenation (glyoxylic acid, CHOCOOH) and hydrodeoxygenation (acetic acid, CH₃COOH). Specifically, the Zn_0.5Cd_0.5S topotactic lattice transformation regulates charge transport dimensionality to control the catalyst-substrate interaction/distortion energy, thereby enabling electronic-configuration-dependent adsorption and selective activation of key intermediates for divergent product generation. The Zn_0.5Cd_0.5S/Ti₃C₂ interfacial built-in electric field (BIEF) establishment creates directional charge transport pathways that induce photocarrier localization/delocalization, resulting in robust productivity feedback. These adjustable-configuration catalysts achieve dehydrogenation-dominated CHOCOOH (81% selectivity, 2.63 mmol·g^-1·h^-1) on Sv-Zn_0.5Cd_0.5S-thin/Ti₃C₂ and hydrodeoxygenation-driven CH₃COOH (86% selectivity, 1.53 mmol·g^-1·h^-1) on Sv-Zn_0.5Cd_0.5S-bulk/Ti₃C₂ during PET conversion. This work establishes a pioneering paradigm for geometrical transformation-charge transport dimensionality-reaction pathway switching and interfacial engineering-charge transport pathway-catalytic activity improvement, elucidating the substantial impact of charge transport behavior on specific molecular catalytic behavior.