Direct growth of two-dimensional phthalocyanine-based COF on Cu-MOF to construct a photoelectrochemical-electrochemical dual-mode biosensing platform for high-efficiency determination of Cr(III).

A photoelectrochemical (PEC)-electrochemical (EC) dual-mode biosensing strategy based on COF@MOF heterostructure was developed for efficiently analyzing Cr(III) ions. A two-dimensional phthalocyanine-based COF (CoPc-PT-COF) was in situ grown on a Cu-based MOF (Cu-MOF) substrate via covalent binding between carboxyl groups in Cu-MOF and amino groups in CoPc-PT-COF (denoted as CoPc-PT-COF@Cu-MOF). The coexistence of both phthalocyanine and bipyridine in CoPc-PT-COF@Cu-MOF affords the outperformed electro- and photo-activities, thus serving as a photoelectric beacon with favorable energy-band configuration and amplified electrochemical response. Due to the high porosity and rich functionality of the obtained heterostructure, the DNA strands can be tightly anchored over CoPc-PT-COF@Cu-MOF via diverse interactions. Thanks to the specific recognition between DNA strands and Cr3+ ions, the CoPc-PT-COF@Cu-MOF-based biosensor can be used to determine Cr3+ ions in an aqueous environment by PEC-EC mode. The gained biosensor shows an extremely low limit of detection (LOD) of 14.5 fM (for PEC) and 22.9 fM (for EC) within the Cr3+ concentration range from 0.1 pM to 100 nM, along with high selectivity, good reproducibility and stability. Moreover, this novel biosensor exhibits acceptable applicability for analyzing the trace Cr3+ from diverse samples (e.g., river and tap water). As a result, this work provides new insights into the construction of a high-efficiency PEC-EC dual-mode biosensor for detecting heavy metal ions from complex environments.