Heterocyclic Modulated Electronic States of Alkynyl-Containing Conjugated Microporous Polymers for Efficient Oxygen Reduction.

The oxygen reduction reaction (ORR) is a key process in green energy conversion technology. Heteroatom doping has been proven to be a prospective strategy to prepare metal-free carbon-based electrocatalysts, but such methods often suffer from uncontrollable catalyst frameworks and imprecise active sites. Herein, an organic heterocyclic strategy is adopted to modulate the charge redistribution of alkynyl-containing conjugated microporous polymers (CMPs) by introducing varied five-membered heterocyclic structures. Among these CMPs, the S, 2N-containing thiadiazole heterocyclic molecule (CMP-Tdz) with carbonized alginate materials (CCA ) displays a remarkable quasi-four-electron-transfer ORR pathway, exhibiting an excellent half-wave potential (E1/2 ) of 0.77 V, coupled with superior methanol tolerance and electrochemical stability, which are among the highest performance in the metal-free organic catalytic material systems. Density functional theory calculations prove that the high catalytic performance of these catalysts originates from the sp-hybridized C atom (site-2) which is activated by their adjacent heterocyclic structures. Importantly, the five-membered heterocyclic structures can also modulate the local charge distribution, and increase dipole moment, with significantly improved catalytic kinetics. This incorporation of chemically designed heterocyclic-containing alkynyl-CMPs provides a new approach to developing efficient metal-free carbon-based electrocatalysts for fuel cells.

Metal-Free Carbon-Based Covalent Organic Frameworks with Heteroatom-Free Units Boost Efficient Oxygen Reduction.

Accurate identification of carbon-based metal-free electrocatalyst (CMFE) activity and enhancing their catalytic efficiency for O2 conversion is an urgent and challenging task. This study reports a promising strategy to simultaneously develop a series of covalent organic frameworks (COFs) with well-defined heterocyclic-free biphenyl or fluorenyl units. Unlike heteroatom doping, the developed method not only supplies methyl-induced molecular configuration to promote activity, but also provides a direct opportunity to identify heteroatom-free carbon active centers. The introduction of methyl groups (MGs) with reversible valence bonds into a pristine biphenyl-based COF results in an excellent performance with a half-wave potential of 0.74 V versus the reversible hydrogen electrode (RHE), which is among the highest values for CMFE-COFs as oxygen reduction reaction (ORR) electrocatalysts. Combined with in situ Raman spectra and theoretical calculations, the MG-bound skeleton (DAF-COF) is found to produce ortho activation, confirming the ortho carbon (site-5) adjacent to MGs as active centers. This may be attributed to the opening and binding of MGs, which effectively regulate the molecular configuration and charge redistribution, as well as improve charge transfer and reduce the energy barrier. This study provides insight into the design of highly efficient metal-free organic electrocatalysts via the regulation of valence bonds.

Drug-loaded mesoporous carbon with sustained drug release capacity and enhanced antifungal activity to treat fungal keratitis.

Fungal keratitis is a severe infectious corneal disease with a high rate of incidence and blindness. Since traditional treatments natamycin (NATA) eye drops, exhibit poor dissolution and bioavailability, and the efficacy of current therapeutic approaches remains limited. In this study, we innovatively utilized mesoporous carbon (Meso-C) and microporous carbon (Micro-C) as nanocarriers loaded with the antifungal drug NATA and silver nanoparticles (Ag-NPs). Porous carbon loaded with NATA and Ag-NPs has not previously been studied in fungal keratitis. Due to the mesoporous structure, high surface area and larger pore volume of Meso-C, it displayed greater superiority in sustained drug release and drug dispersity than Micro-C. Moreover, Meso-C could adsorb inflammatory cytokines during fungal infection. In vitro, Meso-C/NATA/Ag showed excellent antifungal effects. In vivo, compared with pure NATA treatment, Meso-C/NATA/Ag exhibited significantly improved therapeutic effects and reduced dosing frequency when treating fungal keratitis. Our study is the first to report the sustained drug release and improved drug dispersity of Meso-C/NATA and demonstrates that NATA and Ag-NPs-loaded Meso-C has therapeutic effects against fungal keratitis.