Bismuth Oxyiodide Couples with Glucose Oxidase: A Special Synergized Dual-Catalysis Mechanism for Photoelectrochemical Enzymatic Bioanalysis

On the basis of a special synergized dual-catalysis mechanism, this work reports the preparation of a BiOI-based heterojunction and its use for cathodic photoelectrochemical (PEC) oxidase biosensing, which, unexpectedly, revealed that hydrogen peroxide (H 2 O 2 ) had a greater impact than dioxygen (O 2 ). Specifically, the BiOI layer was in situ formed on the substrate through an impregnating hydroxylation method for the following coupling with the model enzyme of glucose oxidases (GOx). The constructed cathodic PEC enzyme sensor exhibited a good analytical performance of rapid response, high stability, and good selectivity. Especially, glucose-induced H 2 O 2 -controlled enhancement of the photocurrent was recorded rather than the commonly observed O 2 -dependent suppression of the signal. This interesting phenomenon was attributed to a special synergized dual-catalysis mechanism. Briefly, this study is expected to provide a new BiOI-based photocathode for general PEC bioanalysis development and to inspire more interest in the design and construction of a novel heterojunction for advanced photocathodic bioanalysis. More importantly, the mechanism revealed here would offer a totally different perspective for the use of a biomimetic catalyst in the design of future PEC enzymatic sensing and the understanding of relevant signaling routes as well as the implementation of innovative PEC devices.