Photo-Sensitive Pb5S2I6 crystal incorporated polydopamine biointerface coated on nanoporous TiO2 as an efficient signal-on photoelectrochemical bioassay for ultrasensitive detection of Cr(VI) ions.

An ultrasensitive Visible light-triggered photoelectrochemical (PEC) sensor was designed based on ideal photoactive lead sulfoiodide (Pb5S2I6) as low band gap crystal, which hydrothermally synthesized rapidly at low temperature (160 °C) in hydrochloride acid media followed by its incorporation into polydopamine as reactive photo-biointerface, through a facile in situ electropolymerization method, coated on nanoporous TiO2 grown by anodization on Ti foil. The structure of as-prepared samples and their photoelectrochemical properties were fully characterized. This unique photo-sensitive Pb5S2I6 catalyst-based PEC bioassay was constructed for the detection of low-abundant Cr(VI) ion in real samples. Applying central composite design, individual and mutual interaction effects were evaluated to obtain optimized solution pH, applied potential and radiant light wavelength as operational factors influencing the PEC efficiency for Cr(VI) detection. At optimal condition, the proposed sensor due to effective suppress in electron-hole recombinations showed a very low detection limit of 3.0 nM, over a broad linear concentration range of 0.01-80 μM in addition to high sensitivity versus 1.9 μA/μM Cr(VI). Proposed PEC sensor displayed high selectivity, reproducibility and stability as well as improved excitation conversion efficiency, which make it highly applicable using solar energy. The potential applicability of the designed sensor was evaluated in water, tomato juice and hair color.