CuBi₂O₄ (CBO) semiconductor composed of low cost and environmentally friendly Cu, Bi, and O elements possesses relatively narrow band gap, appropriate energy band position, and very positive photocurrent onset potential, which make it promising for photoelectrochemical (PEC) O₂ reduction reaction (ORR). However, low separation and transfer efficiency of photogenerated carriers and poor product selectivity limit its further application in PEC ORR toward H₂O₂ production. In this work, we report F⁻ ions doped CuBi₂O₄ (F-CBO) nanorod arrays with enhanced PEC ORR performance for H₂O₂ generation. PEC ORR activity of CBO nanorod arrays was obviously enhanced through decreasing the sizes of nanorods. Furthermore, the doping of F⁻ ions into CBO lattice promoted the separation and transfer of photogenerated carriers and significantly improved the selectivity of ORR toward H₂O₂ path. As a result, 0.85 mmol/L of H₂O₂ could be achieved on the F-CBO photocathode within 45 min under simulated AM1.5G sunlight illumination (100 mW cm⁻²), which is 2.8 times higher than that obtained on the pristine counterpart. The roles of fluorine doping were revealed based on experimental results and density functional theory (DFT) calculations. The combination of morphology and surface doping engineering provides a new strategy for designing highly efficient photocathod for PEC ORR to H₂O₂ production.

由低成本、环保的Cu、Bi和O元素组成的CuBi ₂ O ₄ (CBO)半导体具有相对窄的带隙、合适的能带位置和非常正的光电流起始电位，使其有望用于光电化学(PEC) O ₂还原反应（ORR）。然而，光生载流子的分离和转移效率低，产物选择性差，限制了其在PEC ORR中向H ₂ O ₂生产的进一步应用。在这项工作中，我们报告了 F ^-离子掺杂的 CuBi ₂ O _{4 (F-CBO) 纳米棒阵列，其对 H 2} O ₂具有增强的 PEC ORR 性能一代。通过减小纳米棒的尺寸，CBO 纳米棒阵列的 PEC ORR 活性明显增强。此外，F ^-离子掺杂到CBO晶格中促进了光生载流子的分离和转移，显着提高了ORR对H ₂ O ₂路径的选择性。结果，在模拟 AM1.5G 太阳光照射（100 _mW ^cm _-2)，比原始对应物高出 2.8 倍。基于实验结果和密度泛函理论 (DFT) 计算揭示了氟掺杂的作用。_{形态学和表面掺杂工程的结合为设计用于 PEC ORR 生产 H 2} O ₂的高效光阴极提供了新的策略。