Modulating Polarization of Perovskite-Based Heterostructures via In Situ Semiconductor Generation and Enzyme Catalysis for Signal-Switchable Photoelectrochemical Biosensing

Abstract

Polarization of photoactive materials in current photoelectric (PE) systems is difficult to be adjusted, and thus electron-transfer routes of these systems are unchangeable, which limits their performance in photoelectrochemical (PEC) analysis. Herein, we attempted to modulate the polarization of perovskitebased heterostructures by both in situ semiconductor generation and enzyme catalysis. Owing to their band alignments, Cs 3 Bi 2 Br 9 quantum dots (QDs) and BiOBr are confirmed to construct a Zscheme structure, leading to a large anodic photocurrent. In the presence of ascorbic acid 2-phosphate (AAP), BiPO 4 is generated on the surface of the Cs 3 Bi 2 Br 9 QDs/BiOBr heterostructure, reassigning energy bands of BiOBr. Accordingly, polarization of the photoactive materials is converted, and a new Z-scheme structure with a reversed electron-transfer route is constructed, which leads to an evident cathodic photocurrent. Furthermore, abundant electron donors can be obtained by catalyzing AAP with alkaline phosphatase (ALP). In this case, photogenerated holes in BiOBr are preferentially annihilated by electron donors, thereby blocking transfer of photogenerated electrons in the Cs 3 Bi 2 Br 9 QDs/BiOBr/BiPO 4 heterostructure. Consequently, a second polarization conversion is triggered by enzyme catalysis, resulting in the recovery of an anodic photocurrent. Benefited from the polarization conversion, a PEC biosensor with a feature of two-wing signal switch is designed, which remarkably enlarges the range of the signal response and subsequently improves the analytical performance. As a result, ALP in small volume of human serum can be quantified with this method. In this work, polarization of perovskite-based photoactive materials is tuned, proposing an alternative perspective on the design of advanced PE systems.

Novel Aggregation-Enhanced PEC Photosensitizer Based on Electrostatic Linkage of Ionic Liquid with Protoporphyrin IX for Ultrasensitive Detection of Molt-4 Cells

“…6−8 Furthermore, lower background signal and higher selectivity show tremendous potential in life analysis. 9,10 For the high-performance PEC assays, photoactive materials are essential, which usually include semiconductor quantum dots (e.g., CdSe), 11 metal−organic frameworks (e.g., PCN-224), 12 perovskite (e.g., CsPbBr 3 ), 13 and organic compounds (e.g., porphyrin). 14 Impressively, porphyrin and its derivatives have high molar absorptivity and rich functional groups, which usually work as high-quality photosensitizers in construction of PEC biosensors.…”

Photo-Assisted Robust Anti-Interference Self-Powered Biosensing of MicroRNA Based on Pt–S Bonds and the Inorganic–Organic Hybridization Strategy

“…Photo-assisted biofuel cells (PBFCs) are a class of photoelectric conversation technology that uses the integration of photoelectrochemistry (PEC) and biofuel cells (BFCs). − They have attracted extensive attention and have been widely applied in analysis and energy . Notably, PBFC-based self-powered biosensors (PBFC-SPBs) have demonstrated the advantages of no need for external power supply, ease of sensing design, and simple instrument. , In particular, compared to BFC-based SPBs, the enzyme component in these biosensors is replaced by a photoanode, in which the electron donor could consume photogenerated holes and the remaining electrons would transfer to the cathode via the external circuit.…”

“…Photo-assisted biofuel cells (PBFCs) are a class of photoelectric conversation technology that uses the integration of photoelectrochemistry (PEC) 19 and biofuel cells (BFCs). 20−22 They have attracted extensive attention and have been widely applied in analysis and energy.…”

Gold Nanoparticle-Attached Perovskite Cs3Bi2Br9 QDs/BiOBr Heterostructures for Photoelectrochemical Biosensing

“…Furthermore, recent reports have demonstrated that the in situ generation of heterostructures by self-passivated Cs 3 Bi 2 Br 9 QDs with BiOBr could prominently improve the stability. 27 However, the application of the Bi-based perovskite in the field of PEC biosensing has rarely been exploited, 28 especially, the introduction of some synergistic effects is expected to improve the photoelectric performance. 29,30 Some studies have reported that traces of water treatment could encapsulate Cs 3 Bi 2 Br 9 QDs within the BiOBr matrix.…”

“…Furthermore, recent reports have demonstrated that the in situ generation of heterostructures by self-passivated Cs 3 Bi 2 Br 9 QDs with BiOBr could prominently improve the stability . However, the application of the Bi-based perovskite in the field of PEC biosensing has rarely been exploited, especially, the introduction of some synergistic effects is expected to improve the photoelectric performance. , Some studies have reported that traces of water treatment could encapsulate Cs 3 Bi 2 Br 9 QDs within the BiOBr matrix. The water treatment process has been demonstrated to be an effective way to improve the stability and PL performance, although the inherent improvement mechanisms remain unclear in this field, which provide a unique perspective to explore strategies for Bi-based perovskite PEC sensing.…”