In Situ Generation of Regularly Ordered 2D Ultrathin Covalent Organic Framework Films for Highly Sensitive...

Developing new photoactive materials and electrode preparation technology with high stability, repeatability, easy fabrication, and a low electron-hole recombination rate is promising for ideal photoelectrochemical (PEC) biosensors, but it remains a great challenge. Here, a porous and crystalline oriented two-dimensional (2D) ultrathin covalent organic framework film (D-TA COF film) was formed in situ on indium-doped tin oxide (ITO) substrates under very mild conditions. The structure and morphology of D-TA COF film were characterized by means of Raman spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, and powder X-ray diffraction. Compared with the randomly oriented D-TA COF powder drop-coated on ITO, the photocurrent of the D-TA COF film grown on the ITO surface in situ achieved as high as ∼333-fold increase. This photocurrent can be further amplified by O₂ (acting as electron acceptors). Benefiting from the fabrication in situ, D-TA COF film also exhibited tough adhesion, assuring the film was difficult to separate from the electrode. Accordingly, D-TA COF film was applied as the photoactive material to build a PEC biosensor for H₂O₂ detection based on coupling with large amounts of catalase (CAT) through simple adsorption. The introduced CAT catalyzed the decomposition of H₂O₂ to O₂, leading to an enhancement of the photocurrent response. As a result, a "signal-on" PEC biosensor was fabricated with good sensitivity, rapid response, and high stability, and it can also detect H₂O₂ released from living cells. Taking into account these advantages, the D-TA COF film is expected to be an ideal photoactive material to construct various PEC biosensors, which as far as we know have not been reported.