Diffusion-programmed catalysis in nanoporous material.

In the realm of heterogeneous catalysis, the diffusion of reactants into catalytically active sites stands as a pivotal determinant influencing both turnover frequency and geometric selectivity in product formation. While accelerated diffusion of reactants can elevate reaction rates, it often entails a compromise in geometric selectivity. Porous catalysts, including metal-organic and covalent organic frameworks, confront formidable obstacles in regulating reactant diffusion rates. Consequently, the chemical functionality of the catalysts typically governs turnover frequency and geometric selectivity. This study presents an approach harnessing diffusion length to achieve improved selectivity and manipulation of reactant-active site residence time at active sites to augment reaction kinetics. Through the deployment of a thin film composed of a porous metal-organic framework catalyst, we illustrate how programming reactant diffusion within a cross-flow microfluidic catalytic reactor can concurrently amplify turnover frequency (exceeding 1000-fold) and enhance geometric selectivity ( ~ 2-fold) relative to conventional nano/microcrystals of catalyst in one-pot reactor. This diffusion-programed strategy represents a robust solution to surmount the constraints imposed by bulk nano/microcrystals of catalysts, marking advancement in the design of porous catalyst-driven organic reactions.