Conjugated Microporous Polymers-Based Catalytic Membranes with Hierarchical Channels for High-Throughput Removal of Micropollutants.

Engineering a catalytic membrane capable of efficiently removing emerging organic microcontaminants under ultrahigh flux conditions is of significance for water purification. Herein, drawing inspiration from the functional attributes of lymphatic vessels involved in immunosurveillance and fluid transport with minimal energy consumption, a novel hierarchical porous catalytic membrane is engineered. This membrane, based on an innovative nitrogen-rich conjugated microporous polymer (polytripheneamine, PTPA), is synthesized using an electrospinning coupled in situ polymerization approach. The resulting bioinspired membrane with hierarchical channels comprises a thin layer (≈1.7 µm) of crosslinked PTPA nanoparticles covering the interconnected electrospun nanofibers. This unique design creates an intrinsic microporous angstrom-confined system capable of activating peroxymonosulfate (PMS) to generate 98.7% singlet oxygen (1O2), enabling durable and highly efficient degradation of microcontaminants. Additionally, the presence of a thin layer of mesoporous structure between PTPA nanoparticles and macroporous channels within the interwoven nanofibers enhances mass transfer efficiency and facilitates high flux rates. Notably, the prepared hierarchical porous organic catalytic membrane demonstrates enduring high-efficiency degradation performance with a superior permeance (>95% and >2500 L m-2 h-1 bar-1) sustained over 100 h. This work introduces an innovative pathway for the design of high-performance catalytic membranes for the removal of emerging organic microcontaminants.

Hierarchical meso-micro porous FeNC derived from tripolycyanamide-based microporous polymer as efficient electrocatalyst for oxygen reduction reaction.

Designing porous FeNC nanomaterials with highly efficient active sites is an effective strategy for constructing high-performance oxygen reduction reaction (ORR) electrocatalysts. N-containing porous organic polymers (POPs) have emerged as promising candidates for the preparation of porous FeNC catalysts. Here, N-rich tripolycyanamide-based microporous polymer (TCAMP)-coated SiO2 nanospheres (SiO2@TACMP) were prepared as the precursors of an Fe-N doped hierarchical meso-micro porous carbon (Fe-N-HMC) electrocatalyst for the ORR. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM) characterizations demonstrated that the Fe-N-HMC catalyst possessed a higher content percentage of Fe-Nx active sites and a better distribution of Fe nanoparticles than its Fe-N doped microporous carbon (Fe-N-MC) counterpart. N2 adsorption-desorption isotherm analysis showed that Fe-N-HMC catalyst exhibited a hierarchical meso-micro porous system, with a Brunauer-Emmett-Teller (BET) surface area (SBET) of 733 m2 g-1 (∼2 times of Fe-N-MC's SBET). As a result, Fe-N-HMC catalyst presented a highly efficient ORR performance with a half-wave potential of 0.856 mV, which is similar to the commercial grade 20 wt% Pt/C catalyst and superior to the Fe-N-MC catalyst. Moreover, the as-synthesized Fe-N-HMC catalyst displayed a better durability and methanol tolerance than the commercial Pt/C catalyst. Therefore, Fe-N-HMC shows great promise as an ORR catalyst for fuel batteries and metal-air cells due to its low-cost, high activity, and good stability.