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[Display omitted] • ZnS/CdS was fabricated with type-II heterostructure by growing ZnS QDs on CdS NWs. • Low-bandgap CdS NWs and wide-bandgap ZnS QDs act separately as photosensitizer and Hg2+ probe. • A selective PEC sensor was developed for the analysis of Hg2+ with "turn-on" signal output. • Hg2+ induces the in-situ formation of HgS/ZnS/CdS with double type-II heterostructure. • The PEC sensor can detect Hg2+ with concentrations down to about 0.40 pM. An ultrasensitive and selective photoelectrochemical (PEC) platform has been developed for determining Hg2+ with "turn-on" signal output by synergistically using CdS nanowires (NWs) and ZnS quantum dots (QDs). CdS NWs was first prepared and then deposited with ZnS QDs to yield ZnS/CdS nanocomposite with type-II heterostructure. It was found that the as-constructed ZnS/CdS heterostructure can exhibit excellent photoelectrochemical characteristics by separately employing CdS NWs and ZnS QDs as the photosensitizer and Hg2+-recognition probe. What's more, the constructed analysis platform could display specifically enhanced photocurrent responses to Hg2+ under the visible light via the selective ion-exchange reaction. The in-situ formation of ternary HgS/ZnS/CdS could be thus expected with double type-II heterostructures so as to further enhance the transferring and separation of charges. A linear response can be achieved for Hg2+ in the concentration range from 0.0010 to 5.0 nM, with a detection limit of 0.40 pM. Moreover, the application feasibility of the developed sensor with ZnS/CdS heterostructure could be testified by detecting Hg2+ ions in environmental waters. Such a route of in-situ formation of double type-II heterostructure might promise the wide applications for designing different visible light-driven PEC sensors for probing heavy metals like Hg2+ with the "turn-on" signal output. [ABSTRACT FROM AUTHOR]

• A photoelectrochemical sensor was developed for the "signal-on" analysis of Hg2+. • Hollow CoS x @CdS polyhedrons were fabricated by ZIF-67-templated solvothermal route. • Direct Z-scheme CoS x @CdS photocatalysts were utilized as the recognition probes. • New Z-scheme heterojunction of CoS x @CdS/HgS was formed by the selective ion-exchange. • This PEC sensor can facilitate the detection of Hg2+ with concentrations down to 2.0 pM. A visible-light-driven photoelectrochemical (PEC) sensor has been developed for probing Hg2+ with "turn-on" signal output using hollow CoS x @CdS polyhedron as direct Z-scheme photocatalyst and Hg2+-recognition probe. The CoS x @CdS heterojunction photocatalysts were fabricated by growing CdS nanoparticles on the surface of cobalt sulfide (CoS x) via one-pot solvothermal route using metal-organic frameworks (MOFs) of ZIF-67 polyhedrons as the sacrificial templates and cobalt precursors. It was discovered that the photocurrent responses of the CoS x @CdS-modified ITO electrodes could be specifically turned on by Hg2+, in contrast to these of the CoS x or CdS-modified ones showing no significant Hg2+-induced photocurrent. Under visible light irradiation, herein, the synergetic combination of CoS x and CdS components could improve the carriers transferring of PEC system. More importantly, the photocurrents of the PEC sensor could be greatly enhanced in the presence of Hg2+ through the selective ion-exchange reaction to trigger the in-situ formation of a new Z-scheme heterojunction of CoS x @CdS/HgS photocatalysts, achieving the further promoted charge transferring and suppressed recombination of photogenerated electron-hole pairs. The developed double heterojunctions-based PEC sensors can detect Hg2+ with the concentrations ranging from 0.010 to 1000 nM, which performances are much better than those of the current PEC analysis methods. Besides, such a MOF-templated one-pot construction route may pave the way toward the design of various direct Z-scheme heterojunction photocatalysts of PEC probes of great interest. [ABSTRACT FROM AUTHOR]