Tailoring Charge Flow in Carbon-Defective Cu-MOF with Pd Nanoparticles: A Boost for Visible Light Organic Photoelectrochemical Transistor in Bioanalysis.

ABSTRACT

The photoactive material was of significant importance in organic photoelectrochemical transistor (OPECT) bioanalysis as it influences the photoinduced voltage and the µC* product, resulting in a varying sensor sensitivity. The utilization of metal-organic frameworks (MOFs) as photoactive materials in OPECT analysis is promising, yet it remains a grand challenge due to the inherently narrow light absorption range and high electron-hole recombination rate. Herein, Pd NPs were encapsulated as electron acceptors into the Cu-MOF using a double-solvent method, followed by pyrolysis at the proper temperature. After pyrolysis, Cu-MOF transformed into a carbon defect-rich composite of CuO and Cu2O while retaining its high porosity and structural morphology. The resulting carbon defect-rich pyrolysis Cu-MOF (p-Cu-MOF) served as an active support, facilitating the separation of electrons and holes. The photoelectrons trigger the electron transfer of adjacent active metal components and the formation of a Schottky junction between Pd and the MOFs. This effect induces the electron donation from the MOFs. Moreover, Pd/pyrolysis Cu-MOF exhibits significantly higher visible light absorption, better water stability, and higher electrical conductivity compared to Cu-MOF and Pd/Cu-MOF. An OPECT sensor was fabricated by utilizing Pd/p-Cu-MOF as the photoactive material and poly(3,4-ethylenedioxythiophene)poly(styrenesulfonate) (PEDOTPSS) as the channel material on an integrated laser-etched FTO. The aptamer was used as the recognition element, enabling sensitive and efficient detection of residual isocarbophos.