A wavelength-resolved ratiometric photoelectrochemical technique: design and sensing applications

In this work, a wavelength-resolved ratiometric photoelectrochemical (WR-PEC) technique was investigated and employed to construct a new type of PEC sensor with good sensitivity and anti-interference ability. The WR-PEC hybrid photoelectrodes were stepwise assembled using semiconductor quantum dots (QDs) and photoactive dyes. Under continuous irradiation, the photocurrent–wavelength (I–λ) curves reveal the dependence of the photocurrent on the wavelength. By monitoring the ratios of the two different PEC peak values, a wavelength-resolved ratiometric strategy was realized. Using CdS QDs and methylene blue (MB) as photoactive models, a dual-anodic WR-PEC sensor was established for sensitive detection of Cu(2+). This ratiometric strategy was identified to be based on the quenching effect of Cu(2+) towards CdS QDs and enhancement of the MB photocurrent through catalytic oxidation of leuco-MB. Under continuous illumination from 400 nm to 800 nm at a 0.1 V bias potential, a WR-PEC sensor for Cu(2+) was developed with a wide linear range and a detection limit of 0.37 nM. This WR-PEC had a greatly improved anti-interference ability in a complex environment, and showed acceptable stability. Moreover, using the CdS/magnesium phthalocyanine (MgPc) and CdTe/MgPc as photoelectrodes, anodic–cathodic and dual-cathodic WR-PEC sensors were established, respectively. The WR-PEC technique could serve as a novel concept for designing ratiometric or multi-channel PEC sensors.