3D-Continuous Nanoporous Covalent Framework Membrane Nanoreactors with Quantitatively Loaded Ultrafine Pd Nanocatalysts.

Abstract

The confinement effect of catalytic nanoreactors containing metal catalysts within nanometer-sized volumes has attracted significant attention for their potential to enhance reaction rate and selectivity. Nevertheless, unregulated catalyst loading, aggregation, leaching, and limited reusability remain obstacles to achieving an efficient nanoreactor. A robust and durable catalytic membrane nanoreactor prepared by incorporating palladium nanocatalysts within a 3D-continuous nanoporous covalent framework membrane is presented. The reduction of palladium precursor occurs on the pore surface within 3D nanochannels, producing ultrafine palladium nanoparticles (Pd NPs) with their number density adjustable by varying metal precursor concentrations. The precise catalyst loading enables controlling the catalytic activity of the reactor while preventing excess metal usage. The facile preparation of Pd NP-loaded free-standing membrane materials allows hydrodechlorination in both batch and continuous flow modes. In batch mode, the catalytic activity is proportional to the loaded Pd amount and membrane area, while the membrane retains its activity upon repeated use. In continuous mode, the conversion remains above 95% for over 100h, with the reactant solution passing through a single 50µm-thick Pd-loaded membrane. The efficient nanoporous film-type catalytic nanoreactor may find applications in catalytic reactions for small chemical devices as well as in conventional chemistry and processes.