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This work shows that the hydrogen evolution performance of conjugated microporous polymer (CMP)-based photocatalysts can be enhanced through their hollow shape engineering. Using a hollow microporous organic polymer (H-MOP) as a template, hollow Stille coupling-based CMP photocatalysts with Pd nanoparticles (H-MOP@SCMP-Pds) were prepared, showing enhanced hydrogen evolution rates up to 7100 μmol h−1 g−1 and apparent quantum yields up to 3.72% (@420 nm).

Conjugated microporous polymers (CMPs) have significant potential as electrode materials for electric energy storage devices due to their high surface areas, conjugation features, and chemical stability. However, low conductivity has limited their electrochemical performance. To realize the maximum capability of CMPs, a synthetic strategy for enhancing their conductivity is required. This work shows that during the synthesis of CMPs, carbon black (CB) nanoparticles can be entrapped in situ. Moreover, redox-active benzoquinone (BQ) species could be generated at the CMP to form CMP-BQ through post-synthetic modification. The resultant CB@CMP-BQs with the entrapped CB nanoparticles showed enhanced electrochemical performance as electrode materials for pseudocapacitors, compared with CMP-BQ. They showed capacitances up to 424 and 373 F g−1 at current densities of 0.5 and 1 A g−1, respectively. In addition, the optimal CB@CMP-BQ3 showed excellent cycling performance for 10 000 cycles.

This work introduces, for the first time, the energy harvesting performance of conjugated microporous polymers (CMPs) as tribo-positive materials for triboelectric nanogenerators (TENGs). Various nano or submicron CMP particles (CMP-X) were prepared by the Sonogashira coupling of 1,3,5-triethynylbenzene with 1,4-diiodoarenes. Optimized CMP-X nanoparticles in a polyurethane (PU) matrix showed excellent triboelectrification performance, displaying peak-to-peak voltages of up to 411 V and a maximum power density of 0.80 mW cm−2. Moreover, an optimized 5.0% CMP-H@PU-based TENG could be utilized as a power source for the charging of an electrolytic capacitor and for the operation of 100 LEDs.

This work unravels the unified mechanistic principle of the tubular shape evolution of microporous organic polymers (MOPs) prepared by the Sonogashira coupling of ethynylarenes and haloarenes. Using ionic building blocks (self-templates), in situ generated salts (in situ templates), or salt additives (additive templates), tubular MOP materials could be engineered. The assembled ionic species can act as morphology templates in the covalent assembly of building blocks to form MOP tubes.

Conjugated microporous polymer films (CMP-Fs) bearing tetraphenylethylene moieties showed aggregation-induced emission behavior, which can be utilized for the emission quenching-based sensing of nitrotoluenes. In this work, macroporous CMP-Fs (MA-CMP-Fs) were engineered using assembled silica spheres as templates. The MA-CMP-Fs showed much better sensing performance toward nitrotoluenes with Stern–Volmer constants (KSV) of up to 1.39 × 105 M−1, compared with CMP-Fs (KSV up to 5.57 × 104 M−1). The sensing performance of the MA-CMP-F is superior to those of recent emissive CMP materials (KSV in the range of 2.08 × 103 to 6.78 × 104 M−1 for nitroarenes) in the literature, which is attributable to the additional macroporosity of the CMP-F. Also, we demonstrated that various functional CMP films with macroporous inner structures can be developed using tailored building blocks.

Redox active 1,4-bis(3-phenylpropynoyl)benzene moieties were incorporated into a hollow conjugated microporous polymer via carbonylative Sonogashira coupling of 1,3,5-triethynylbenzene with 1,4-diiodobenzene in the presence of carbon monoxide. The resultant redox active material showed enhanced energy storage performance for pseudocapacitors.

Hollow and microporous organic polymers bearing pyrrolidines (H-MOP-P) were prepared by template synthesis and post-synthetic modification. H-MOP-P showed enhanced organocatalytic performance, compared to nonhollow microporous catalysts.

Pure silica zeolite (Silicalite-1) bricks with a 2D morphology were assembled on a slide glass and used as templates for the preparation of microstructured organic network films (MONFs) with a hollow space and holes by the Sonogashira coupling of tetrakis(4-ethynylphenyl)methane and 1,4-diiodobenzene and silica etching. The MONFs were adhesive to polyethylene terephthalate (PET) films due to their unique structural effects. Cu was loaded on the MONF/PET by electroless deposition. The Cu/MONF/PET showed excellent retention of conductivities in repeated severe bending.

Hollow and microporous metal free/Cr-porphyrin networks were prepared via the Sonogashira coupling of metal-free or Cr-tetra(4-ethynylphenyl) porphyrins and 1,4-diiodobenzene on the surface of silica templates followed by silica etching. Zinc was introduced into a hollow and microporous metal free porphyrin network (H–MPN) through post-synthetic modification to form a H–MZnPN. Hollow and microporous Cr(III)–F porphyrin networks (H–MCrPNs) showed the best catalytic activities in room temperature CO2 fixation with epoxides to cyclic carbonates. In addition, the H–MCrPN could be reused at least for five runs, maintaining the original catalytic activity. The good performance of the H–MCrPN is attributed to its microporosity, the shortened diffusion pathways for substrates due to the hollow structure, and the efficient Lewis acidic activity of Cr(III)–F moieties.