Solar-driven activation of molecular oxygen (O₂) offers an appealing strategy to realize aerobic oxidation catalysis at room temperature, while the efficiency of photocatalytic O₂ activation is severely limited by lacking O₂ adsorption sites and poor carrier utilization. Herein, an efficient Ni₂P/Bi₃O₄Br-OVs heterojunction is firstly proposed to overcome the limitation by the dual-site design of oxygen vacancies (OVs) and on Ni₂P cocatalyst. By the joint observations from spectroscopic measurements and theoretical simulations, the introduction of OVs and Ni₂P on Bi₃O₄Br nanosheets can not only optimize the light absorption, facilitate the separation and transfer of photogenerated charge carrier through the S-scheme mechanism, but also provide active sites for effective adsorption and activation of oxygen molecules, thereby contributing to highly efficient generation of •O₂⁻ radicals. Benefiting from the more oxidative active species of •O₂⁻ and h⁺, the Ni₂P/Bi₃O₄Br-OVs photocatalyst achieves near-unity conversion rate and selectivity in aerobic oxidation of sulfide to sulfoxide, and it also exhibits outstanding photoactivity in the aerobic degradation of phenolic pollutants under visible light. This study showcases a feasible O₂ activation approach by defect and heterojunction engineering, and provides a new perspective for designing high-performance photocatalysts in the field of aerobic oxidation catalysis.

太阳能驱动的分子氧（O ₂）活化为在室温下实现好氧氧化催化提供了一种有吸引力的策略，而光催化O ₂活化的效率由于缺乏O ₂吸附位点和较差的载流子利用率而受到严重限制。在此，首先提出了一种高效的Ni ₂ P/Bi ₃ O ₄ Br-OVs异质结，以克服氧空位（OVs）和Ni ₂ P助催化剂双位点设计的限制。通过光谱测量和理论模拟的联合观察，在Bi ₃ O _{4上引入OVs和Ni 2} PBr纳米片不仅可以优化光吸收，通过S型机制促进光生载流子的分离和转移，还可以为氧分子的有效吸附和活化提供活性位点，从而有助于高效生成•O ₂ ^-部首。Ni ₂ P/Bi ₃ O ₄受益于 •O ₂ ^-和 h ^{+的更具氧化活性的物质}Br-OVs光催化剂在硫化物好氧氧化为亚砜的过程中实现了近乎统一的转化率和选择性，并且在可见光下好氧降解酚类污染物中也表现出优异的光活性。本研究通过缺陷和异质结工程展示了一种可行的O ₂活化方法，并为有氧氧化催化领域的高性能光催化剂设计提供了新的视角。