本文要点：
苯并噻二唑提供了一个有效的电荷转移通道，是构建给体-受体(D-A)共价-有机骨架的合适单元，但对含苯并噻二唑的共价-有机骨架的系统研究尚不多见。
在此，作者构建了四个高度结晶的COFs，并仔细研究了它们的H2O2光合效率。将供体单元从苯基改为萘基有效地将H2O2产率提高了近3倍，突出了调节D-A构型的重要性。
优化的COF (BTpaNda)表现出10122 μmol·g–1·h–1的高H2O2产率。理论计算表明，BTpaNda COF在限速含氧中间体形成中具有最低的吉布斯自由能，证实了极好的H2O2光合作用。
此外，BTpaNda COF在含氧中间体的参与下表现出良好的稳定性和优异的细菌消除效果。因此，证明了含苯并噻二唑的COFs对光催化H2O2产生和与含氧中间体产生的级联细菌消除的结构调节。
Figure 1. Experimental (gray circle) and Pawley refined PXRD patterns (red) of (a) BTpaNda COF, (b) BTpaPda COF, (c) BTpaBIda COF, and (d) BTpaMPda COF.
Figure 2. Optical property characterization of BTpaNda, BTpaPda, BTpaBIda, and BTpaMPda COFs. (a) Solid-state UV–vis absorption spectra. (b) Tau plots derived from UV–vis spectra. (c) Band structure diagram. (d) Solid-state photoluminescence (PL) spectra. (e) Time-resolve photoluminescence decay curves excited at 325 nm with emission at 525 nm. (f) Transient photocurrent response over six light on–off cycles.
Figure 3. Examination of photocatalytic H2O2 generation. (a) Photocatalytic H2O2 generation of BTpaNda, BTpaPda, BTpaBIda, and BTpaMPda COFs. (b) Cycling photocatalytic H2O2 generation of BTpaNda. (c) EPR spectra of BTpaNda COF measured in the presence of DMPO trapping agent without or with light irradiation for 2 and 5 min. (d) H2O2 generation of BTpaNda COF in the presence of varied scavengers. Conditions: water (30 mL), COF catalyst (5 mg), 300 W Xe lamp, λ > 400 nm.
Figure 4. Photocatalytic reaction pathway analysis. (a) Oxygen adsorption energy for BTpaNda, BTpaPda, BTpaBIda, and BTpaMPda COFs. (b) Gibbs free energy diagram of oxygen reduction reaction over BTpaNda, BTpaPda, BTpaBIda, and BTpaMPda COFs. (c) Proposed photocatalytic H2O2 generation pathway on BTpaNda COF.
Figure 5. Antibacterial efficacy of the BTpaNda COF. (a) Survival visualization of the P. aeruginosa and MRSA on agar plate after treating with BTpaNda COF upon light irradiation for 0.5, 1, and 2 h, respectively. (b) Live–dead staining and (c) DCFDA staining of P. aeruginosa and MRSA without or with BTpaNda COF treatment for 1 h under light irradiation.
https://doi.org/10.1021/acsmaterialslett.4c02312
