Two-dimensional (2D) porous polymers with a planar architecture and high specific atomically dispersed transition-metal active sites. In this review, the rational synthetic approaches for 2D porous polymers with Csp 2 bonding are summarized. Finally, their current practical photoelectric applications, including for gas separation, luminescent sensing and imaging, electrodes for batteries and supercapacitors, and photocatalysis are discussed.
Cobalt-doped graphene-coupled hypercrosslinked polymers (Co-GHCP) have been successfully prepared on a large scale, using an efficient RAFT (Reversible Addition-Fragmentation Chain Transfer Polymerization) emulsion polymerization and nucleophilic substitution reaction with Co (II) porphyrin. The Co-GHCP could be transformed into cobalt-doped porous carbon nanosheets (Co-GPC) through direct pyrolysis treatment. Such a Co-GPC possesses a typical 2D morphology with a high specific surface area of 257.8 m2 g−1. These intriguing properties of transition metal-doping, high conductivity, and porous structure endow the Co-GPC with great potential applications in energy storage and conversion. Utilized as an electrode material in a supercapacitor, the Co-GPC exhibited a high electrochemical capacitance of 455 F g−1 at a specific current of 0.5 A g−1. After 2000 charge/discharge cycles, at a current density of 1 A g−1, the specific capacitance increased by almost 6.45%, indicating the excellent capacitance and durability of Co-GPC. These results demonstrated that incorporation of metal porphyrin into the framework of a hypercrosslinked polymer is a facile strategy to prepare transition metal-doped porous carbon for energy storage applications.
Due to the growing demand for energy and imminent environmental issues, hydrogen energy has attracted widespread attention as an alternative to traditional fossil energy. Platinum (Pt) catalytic hydrogen evolution reaction (HER) is a promising technology to produce hydrogen because the consumed electricity can be generated from renewable energy. To overcome the high cost of Pt, one effective strategy is decreasing the Pt nanoparticle (NP) size from submicron to nano-scale or even down to single atom level for efficient interacting water molecules. Herein, atomically dispersed Pt and ultra-fine Pt NPs embedded porous carbons were prepared through the pyrolysis of Pt porphyrin-based conjugated microporous polymer. As-prepared electrocatalyst exhibit high HER activity with overpotential of down to 31 mV at 10 mA cm−2, and mass activity of up to 1.3 A mgPt−1 at overpotential of 100 mV, which is double of commercial Pt/C (0.66 A mgPt−1). Such promising performance can be ascribed to the synergistic effect of the atomically dispersed Pt and ultra-fine Pt NPs. This work provides a new strategy to prepare porous carbons with both atomically dispersed metal active sites and corresponding metal NPs for various electrocatalysis, such as oxygen reduction reaction, carbon dioxide reduction, etc.
Metal porphyrins, which possess metal-N coordination centers, are important building blocks for construction of porous organic materials with catalytic performance. However, most of previous work focused on controlling metal elements...
Transition metal‐based nanoparticle‐embedded carbon materials have received increasing attention for constructing next‐generation electrochemical catalysts for energy storage and conversion. However, designing hybrid carbon materials with controllable hierarchical micro/mesoporous structures, excellent dispersion of metal nanoparticles, and multiple heteroatom‐doping remains challenging. Here, a novel pyridinium‐containing ionic hypercrosslinked micellar frameworks (IHMFs) prepared from the core–shell unimicelle of s‐poly(tert‐butyl acrylate)‐b‐poly(4‐bromomethyl) styrene (s‐PtBA‐b‐PBMS) and linear poly(4‐vinylpyridine) were used as self‐sacrificial templates for confined growth of molybdenum disulfide (MoS2) inside cationic IHMFs through electrostatic interaction. After pyrolysis, MoS2‐anchored nitrogen‐doped porous carbons possessing tunable hierarchical micro/mesoporous structures and favorable distributions of MoS2 nanoparticles exhibited excellent electrocatalytic activity for hydrogen evolution reaction as well as small Tafel slope of 66.7 mV dec−1, low onset potential, and excellent cycling stability under acidic condition. Crucially, hierarchical micro/mesoporous structure and high surface area could boost their catalytic hydrogen evolution performance. This approach provides a novel route for preparation of micro/mesoporous hybrid carbon materials with confined transition metal nanoparticles for electrochemical energy conversion.
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