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)

Abstract

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.