Establishing Interfacial Charge-Transfer Transitions on Ferroelectric Perovskites: An Efficient Route for Photoelectrochemical Bioanalysis

Abstract

This work presents the concept of establishing interfacial charge-transfer transitions (ICTT) on ferroelectric perovskites for efficient photoelectrochemical (PEC) bioanalysis. The model system was exemplified by using representative lead titanate (PbTiO3) and an enzyme tandem consisting of the isocitrate dehydrogenase (ICDH) and p-hydroxybenzoate hydroxylase (PHBH). The enzymatic generation of protocatechuic acid (PCA) can coordinate onto the surface of the PbTiO3 and hence form the ICTT that enables direct ligand-to-metal charge transfer from the highest occupied molecular orbital (HOMO) of PCA to the conduction band (CB) of PbTiO3 under light irradiation. Due to the ferroelectric polarization induced electric field of PbTiO3 and the surface polarity of PCA modification, enhanced charge separation of the ICTT contributes to the generation of anodic photocurrent and thus underlies a unique route for detecting the enzymatic activity or its substrate. For dehydrogenase detection, this strategy has better performance than some classical methodologies in terms of high sensitivity and improved selectivity. This work not only features ICTT establishment on ferroelectric perovskites for unique bioanalysis but also provides new insights into the utilization of ferroelectric perovskites for advanced PEC bioanalysis.

Type-II Band Alignment Enhances Unassisted Photoelectrochemical Water-Splitting Performance of the BaTiO3/CdS Ferroelectric Heterostructure Photoanode under Solar Light Irradiation

“…In recent years, ferroelectric materials with a spontaneous polarization electric field (SPEF) have been introduced into the PEC water-splitting field because the SPEF can promote the effective transport and separation of photogenerated charge carriers, thus improving the PEC properties of ferroelectric material-based photoanodes. , As one of the typical ferroelectric materials, BaTiO 3 (BTO) possesses a perovskite structure with a band gap of 3.2 eV. Most importantly, it has suitable band positions to split water into hydrogen and oxygen. − Thus, BTO has attracted extensive attention in the field of PEC water splitting due to its unique structure features and outstanding ferroelectric properties.…”

Bioinduced Surface Oxygen Vacancies on Bismuth Trioxide Nanocrystals for Photocathodic Bioassays

“…After reaction, the additional characteristic peaks that resulted from PCA were distinguishable, such as the aromatic C−O stretching vibration (at 1250 cm −1 ) as well as the aromatic C− H stretching vibration (at 1491 cm −1 ), from which it can be inferred that PCA was coordinated with the surface of Bi 2 O 3 . As shown in the Raman spectra, in addition to the lattice vibration (at 216 cm −1 ) and Bi−O stretching vibration (at 287, 320, 419, 454, and 478 cm −1 ) of Bi 2 O 3 , 29 the characteristic Raman shifts from PCA, such as the C−H bending vibration (at 1460 cm −1 ) and the ring stretching vibration (at 1525 cm −1 ) 30 were observed for the Bi 2 O 3 /PCA. Moreover, it is worth noting that the peak intensity of the Bi−O stretching vibration at 478 cm −1 was obviously augmented for the Bi 2 O 3 / PCA, which can be explained by the fact that the coordination of PCA contributed to the change of the Bi 2 O 3 surface structure (Figure 1C).…”

Photoelectrochemical detection of copper ions based on a covalent organic framework with tunable properties

“…14–16 The PEC detection method uses photosensitive materials to generate current signals under light to detect target analytes, and these materials have the advantages of high sensitivity, good selectivity, low cost and simple operation. 17–20 Unfortunately, most of the currently used photosensitive materials are inorganic semiconductors 21 or organic polymers, 22 which usually have problems such as poor stability and easy aggregation or shedding.…”