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

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 100 h, with the reactant solution passing through a single 50 µm-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.

Molecularly Selective Polymer Interfaces for Electrochemical Separations.

The molecular design of polymer interfaces has been key for advancing electrochemical separation processes. Precise control of molecular interactions at electrochemical interfaces has enabled the removal or recovery of charged species with enhanced selectivity, capacity, and stability. In this Perspective, we provide an overview of recent developments in polymer interfaces applied to liquid-phase electrochemical separations, with a focus on their role as electrosorbents as well as membranes in electrodialysis systems. In particular, we delve into both the single-site and macromolecular design of redox polymers and their use in heterogeneous electrochemical separation platforms. We highlight the significance of incorporating both redox-active and non-redox-active moieties to tune binding toward ever more challenging separations, including structurally similar species and even isomers. Furthermore, we discuss recent advances in the development of selective ion-exchange membranes for electrodialysis and the critical need to control the physicochemical properties of the polymer. Finally, we share perspectives on the challenges and opportunities in electrochemical separations, ranging from the need for a comprehensive understanding of binding mechanisms to the continued innovation of electrochemical architectures for polymer electrodes.

Facile Synthesis of Robust and Pore-Size-Tunable Nanoporous Covalent Framework Membrane by Simultaneous Gelation and Phase Separation of Covalent Network/Poly(methyl methacrylate) Mixture.

We report a facile route toward the preparation of organic-solvent-resistant and three-dimensionally continuous nanoporous covalent framework membrane. The membrane was prepared from the blend of linear poly(methyl methacrylate) and the cross-linked polyurea-based organic network, followed by selective removal of the linear polymer part. The pore morphologies, porosity, and solvent permeation properties of the membrane could be simply modified by the initial composition of the poly(methyl methacrylate) added to a sol of the organic network. The pore was three-dimensionally continuous with pore size ranging from 5 nm to tens of nanometers. Despite the broad pore size distribution, ultrafiltration of sub-10 nm solutes was realized with a molecular size cutoff near 5 nm thanks to the bicontinuous pore structure of the membrane. The nanoporous structure exhibited long-term resistance to organic solvents as well as thermal stability and mechanical strength. The separation performance remained unchanged in organic-rich medium for a prolonged time. Our strategy provides a synthetic route to a structurally robust, three-dimensionally continuous nanoporous polymeric membrane for potential application that necessitates the use of organic solvent.

Bicontinuous Nanoporous Frameworks: Caged Longevity for Enzymes.

The preparation of bicontinuous nanoporous covalent frameworks, which are promising for caging active enzymes, is demonstrated. The frameworks have three- dimensionally continuous, hydrophilic pores with widths varying between 5 and 30 nm. Enzymes were infiltrated into the bicontinuous pore by applying a pressured enzyme solution. The new materials and methods allowed the amount of caged proteins to be controlled precisely. The resulting enzyme-loaded framework films could be recycled many times with nearly no loss of catalytic activity. Entropic trapping of proteins by a bicontinuous pore with the right size distribution is an unprecedented strategy toward facile in vitro utilization of biocatalysts.