The state-of-art signal transduction mechanism of anodic photoelectrochemistry is constrained to the hole oxidation reaction, which greatly hinders its application for prospective biosensing applications. Herein, we present an innovative strategy for signal transduction by exploiting the in situ formation of surface oxygen vacancies (V_Os) on Fe₂O₃ nanorods (NRs) through the self-coordination of 2,3-dihydroxynaphthalene (2,3-DHN) on their surfaces. The 2,3-DHN was connected with Fe(Ⅲ) on the surface of Fe₂O₃ NRs vis the formation of the five-membered ring structures accompanied by the generation of V_Os. And the generated V_Os introduced a new defect energy level for trapping the photogenerated holes, which enhanced the charge separation and realized the enhancement of photocurrent signal. The developed signal transduction strategy was validated by the first photoelectrochemical (PEC) sensing platform for β-glucoside (β-Glu) and lipase (LPS), which can catalyze the hydrolysis of 3-hydroxy-2-naphthalenyl-β-D-glucoside and naphthalene-2,3-diol diacetate, respectively, to produce 2,3-DHN for signal stimuli. The β-Glu and LPS were detected with linear ranges of 0.01–10.0 U/mL and 0.001–5.0 mg/mL, respectively. Detection limits of 3.3 × 10⁻³ U/mL and 0.32 μg/mL (S/N = 3) were achieved, for β-Glu and LPS, respectively. The present study not only provides a new strategy for spontaneous induction of V_Os in situ for n-type semiconductors, but also innovates the anodic PEC signal transduction strategy with broadened biosensing applications.

阳极光电化学最先进的信号转导机制仅限于空穴氧化反应，这极大地阻碍了其在未来生物传感应用中的应用。在此，我们提出了一种创新的信号转导策略_，通过2,3-二_羟基萘₍ 2,3- DHN）在他们的表面上。_{2,3-DHN在Fe 2} O _{3 NRs}表面与Fe(Ⅲ)相连形成五元环结构并伴随着V _O s的产生。和生成的 V_O s 引入了新的缺陷能级来捕获光生空穴，增强了电荷分离，实现了光电流信号的增强。所开发的信号转导策略通过第一个光电化学 (PEC) 传感平台对 β-葡萄糖苷 (β-Glu) 和脂肪酶 (LPS) 进行验证，可催化 3-hydroxy-2-naphthalenyl-β-D-glucoside 的水解和萘-2,3-二醇二乙酸酯，分别产生用于信号刺激的 2,3-DHN。检测到的 β-Glu 和 LPS 的线性范围分别为 0.01–10.0 U/mL 和 0.001–5.0 mg/mL。检测限为 3.3 × 10 ^-3β-Glu 和 LPS 分别达到了 U/mL 和 0.32 μg/mL (S/N = 3)。本研究不仅为 n 型半导体原位自发诱导 V _O s提供了新策略，而且创新了阳极 PEC 信号转导策略，拓宽了生物传感应用。