S型0.5Co-BiOCl/Co3O4：异质结与自旋极化协同调控电荷分离增强光降解性能

doi:10.1016/j.actphy.2026.100401

摘要/Abstract

摘要： 自旋极化调控可从电子自旋本征层面抑制光生载流子复合，显著提升电荷分离效率。本研究提出自旋极化与S型异质结协同策略：通过水热-煅烧耦合法在BiOCl (BOC)纳米片中引入Co掺杂以诱导自旋极化效应，同时与立方状Co₃O₄复合构筑0.5Co-BOC/Co₃O₄ S型异质结。密度泛函理论(DFT)计算、振动样品磁强计(VSM)与开尔文探针力显微镜(KPFM)表征共同证实，Co掺杂使BOC费米能级附近呈现自旋极化电子态的不对称占据，窄化带隙并促进电荷转移。功函数差异驱动界面电子由Co₃O₄向0.5Co-BOC定向转移，形成内建电场。该内建电场驱动光生载流子空间定向分离，而自旋极化通过调控载流子自旋态、抑制自旋匹配复合，二者协同实现“空间分离+自旋禁阻”双重调控，显著增强载流子分离效率与界面传输动力学。最佳条件下，80 min内环丙沙星(CIP)降解率达95.4%，分别为纯BOC和Co₃O₄的1.50倍与4.79倍。液相色谱-质谱联用技术(LC-MS)与毒性评估软件工具(T.E.S.T.)评估表明，CIP经多条路径逐步降解，中间产物毒性显著降低。本研究阐明了自旋极化与内建电场协同强化载流子分离的机制，为设计高效光催化体系提供了新思路。

关键词: 自旋极化, Co-掺杂, S型异质结, 光催化降解, 内建电场

Abstract: Spin polarization control can suppress the recombination of photogenerated carriers at the intrinsic electron spin level, significantly enhancing charge separation efficiency. This study proposes a synergistic strategy combining spin polarization with an S-scheme heterojunction. Specifically, Co doping is introduced into BiOCl (BOC) nanosheets via a coupled hydrothermal-calcination method to induce spin polarization. Meanwhile, the material is coupled with cubic Co₃O₄ to construct a 0.5Co-BOC/Co₃O₄ Sscheme heterojunction. Characterization results from density functional theory (DFT) calculations, vibrating sample magnetometer (VSM), and Kelvin probe force microscopy (KPFM) collectively confirm that Co doping induces asymmetric occupation of spin-polarized electronic states near the Fermi level of BOC. This narrows the bandgap and promotes charge transfer. The work function difference drives interfacial electrons to transfer directionally from Co₃O₄ to 0.5Co-BOC, forming a built-in electric field. This built-in electric field drives the spatial directional separation of photogenerated carriers. Meanwhile, spin polarization regulates the spin states of carriers and suppresses spinmatched recombination. Their synergy achieves dual regulation of “spatial separation + spin-forbidden effect”, significantly enhancing carrier separation efficiency and interfacial transport kinetics. Under optimal conditions, the degradation rate of ciprofloxacin (CIP) reaches 95.4% within 80 min. This is 1.50 times that of pristine BOC and 4.79 times that of pristine Co₃O₄. Liquid chromatography-mass spectrometry (LC-MS) and toxicity estimation software tool (T.E.S.T.) assessments indicate that CIP is degraded stepwise via multiple pathways, with significantly reduced toxicity of the intermediate products. This study elucidates the mechanism of synergistic enhancement of carrier separation by spin polarization and the built-in electric field, providing new insights for designing efficient photocatalytic systems.

Key words: Spin polarization, Co-doping, S-scheme heterojunction, Photodegradation, Built-in electric field

黎影, 黄志凌, 虞田慧, 孟跃, 倪哲明, 夏盛杰. S型0.5Co-BiOCl/Co₃O₄：异质结与自旋极化协同调控电荷分离增强光降解性能[J]. 物理化学学报 2026, (), 100401. doi: 10.1016/j.actphy.2026.100401

Ying Li, Zhiling Huang, Tianhui Yu, Yue Meng, Zheming Ni, Shengjie Xia. S-scheme 0.5Co-BiOCl/Co₃O₄: synergistic regulation of charge separation by heterojunction and spin polarization for enhanced photodegradation performance[J]. Acta Phys. -Chim. Sin. 2026, (), 100401. doi: 10.1016/j.actphy.2026.100401

链接本文: https://www.whxb.pku.edu.cn/CN/10.1016/j.actphy.2026.100401

https://www.whxb.pku.edu.cn/CN/Y2026/V/I/100401

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S型0.5Co-BiOCl/Co₃O₄：异质结与自旋极化协同调控电荷分离增强光降解性能

S-scheme 0.5Co-BiOCl/Co₃O₄: synergistic regulation of charge separation by heterojunction and spin polarization for enhanced photodegradation performance

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