A hair-ball heterostructure of MnS-MnS2/CdS with compact linking interface for ultrasensitive photoelectrochemical bioanalysis of carcinoembryonic antigen

The heterostructured photoelectric material is supposed to markedly promote the photoelectrochemical (PEC) property. Herein, the species heterostructured MnS/CdS and MnS-MnS2/CdS(1∼2) composites derived from Mn-ZIF MOFs via a sulfofication reaction using Cd(NO3)2, CdC12 cadmium source, respectively. Under irradiation, the PEC tests showed that the photocurrent response of MnS-MnS2/CdS(1∼2) signally enhanced compared to globose MnS/CdS heterostructure and pure MnS or CdS. It was ascribed to the matching band-gap to form type II heterojunction in MnS-MnS2/CdS(1∼2) which dramatically facilitated photo-induced electron/hole (e-/h+) separation and transfer. The hair-ball morphologies structure of MnS-MnS2/CdS(1∼2) with large number of pores was beneficial to improve penetrating efficiency of the electrolyte liquid. Meanwhile, the well-synergistic effect on the MnS, MnS2, CdS components and with tight connecting heterojunction interface among MnS-MnS2/CdS(1∼2) which also led to violently photocurrent output. Besides, the chitosan (CS) was covalently coupled with glutaraldehyde (GLD) to obtain steady composite film, and the cross-linker of GLD can achieve the high efficiency to graft the Apt-CEA (aptamer) biomolecules, which resulting in the promotion of hybridization reaction efficiency of the CEA target. Hence, this created biosensor of Apt-CEA/GLD-CS/MnS-MnS2/CdS(1)/ITO for the CEA detection displayed a wide linear range from 0.001 to 18 ng mL-1 and with ultralow detection limit of 0.313 pg mL-1. This research innovatively prepared a contact heterojunction interface with special porosities structure, which had superior PEC nature for the fabrication of high-performance biosensor.