杨林超,刘穗君,刘磊,等.金属离子掺杂ɑ-Fe₂O₃的形貌调控与光降解研究[J].河南理工大学学报(自然科学版)，doi:10.16186/j.cnki.1673-9787.2026010059.

YANG L C, LIU H J, LIU L, et al． Study on structural regulation and photodegradation performance of metal ion-doped α-Fe₂O₃[J]. Journal of Henan Polytechnic University( Natural Science) ， doi: 10.16186/j.cnki.1673-9787.2026010059.

金属离子掺杂ɑ-Fe₂O₃的形貌调控与光降解研究(网络首发)

杨林超1，刘穗君1，刘磊1，朱陈2，柳宾1，李章纪1，张桂铭1，王聪慧2

1.河南中烟工业有限责任公司,河南 南阳 473007；2.河南工业大学 化学化工学院,河南 郑州 450001

摘要: 目的 通过金属离子掺杂优化α-Fe₂O₃的光降解性能，解析各金属离子调控光降解活性的主导机制。方法 以具有规则形貌的α-Fe₂O₃类立方体为基准，通过在其生长过程中引入不同的金属离子（Al³⁺、Cr³⁺、Mn²⁺、Cu²⁺），构筑不同金属离子掺杂的α-Fe₂O₃光催化剂，并采用X射线衍射分析、扫描电子显微镜、透射电子显微镜、傅里叶变换红外光谱和X射线光电子能谱研究掺杂对形貌和结构的影响。通过研究各掺杂金属对光降解罗丹明B的影响，筛选出最优的掺杂元素及其最佳掺杂量。进一步采用自由基捕获实验和电子顺磁共振谱确定反应的活性自由基，采用紫外-可见吸收光谱表征和Mott-Schottky测试确定各催化剂的带隙结构，采用光电流测试、阻抗测试和荧光光谱研究光生载流子的分离和迁移，最终阐明各掺杂金属对光降解反应的调控机制。结果 Al³⁺掺杂使α-Fe₂O₃类立方体转变为大尺寸纺锤体，光降解速率常数由0.01327 min^-1降为0.00816 min^-1；Cr³⁺掺杂和Mn³⁺掺杂获得小尺寸的α-Fe₂O₃类立方体，光降解速率常数分别提升至0.04409min^-1和0.01567 min^-1；Cu²⁺掺杂对形貌和尺寸无明显影响，光降解速率常数提升至0.06579 min^-1，是α-Fe₂O₃类立方体的4.95倍。结论 对α-Fe₂O₃类立方体，Al³⁺掺杂和Mn²⁺掺杂主要通过形貌效应影响光催化活性，Cr³⁺掺杂通过电子效应与形貌效应共同调控光催化活性，Cu²⁺掺杂则主要通过电子效应调控光催化活性。Cu²⁺掺杂通过促进光生电荷的生成和分离，强化界面电荷转移和抑制光生电荷复合，生成更多活性自由基，实现优异的光催化脱色降污。

关键词:形貌调控；金属离子掺杂；光芬顿反应；高色度难降解废水

doi: 10.16186/j.cnki.1673-9787.2026010059.

基金项目:国家自然科学基金资助项目（22408087，21802114）；河南省自然科学基金资助项目（252300423112）；河南中烟工业有限责任公司科研项目（BWR202412）

收稿日期：2026-01-27

修回日期：2026-03-30

网络首发日期：2026-07-06

Study on structural regulation and photodegradation performance of metal ion-doped α-Fe₂O₃

Yang Linchao1, Liu Huijun1, Liu Lei1, Zhu Chen2,  Liu Bin1, Li Zhangji1, Zhang Guiming1, Wang Conghui2

1. China Tobacco Henan Industrial Co., Ltd., Nanyang 473007, Henan, China; 2. College of Chemistry and Chemical Engineering, Henan University of Technology, Zhengzhou 450001, Henan, China

Abstract: Objectives Constructing high-performance α-Fe₂O₃ photocatalysts through metal ion doping and elucidating the dominant regulatory mechanisms of metal ion doping on α-Fe₂O₃ photocatalytic activity. Methods Different metal ion-doped α-Fe₂O₃ photocatalysts were constructed by introducing various metal ions (Al³⁺, Cr³⁺, Mn²⁺, Cu²⁺) during the growth process of cubic-like α-Fe₂O₃. The effects of doping on morphology and structure were investigated by X-ray diffraction analysis, scanning electron microscopy, transmission electron microscopy, fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The optimal doping element and its corresponding doping concentration were screened by evaluating the influence of each doped metal on the photocatalytic degradation of Rhodamine B. The active radicals involved in the reaction were identified via free radical trapping experiments and electron paramagnetic resonance, The band gap structures of the catalysts were determined using UV-visible absorption spectroscopy and Mott-Schottky measurements. The separation and migration of photogenerated carriers were studied by photocurrent response, electrochemical impedance spectroscopy, and photoluminescence spectroscopy.. Finally, the regulation mechanism of each doped metal on the photocatalytic reaction was systematically elucidated. Results Al³⁺ doping transformed the cubic-like α-Fe₂O₃ to large-sized spindles, and the photodegradation rate constant decreased from 0.01327 min^-1 to 0.00816 min^-1. Cr³⁺ doping and Mn²⁺ doping yielded small-sized cubic-like α-Fe₂O₃, and the photodegradation rate constants increased to 0.04409 min^-1 and 0.01567 min^-1, respectively. Cu²⁺ doping had no obvious effect on morphology and size, but enhanced the photodegradation rate constant to 0.06579 min^-1, which was 4.95 times that of the pristine cubic-like α-Fe₂O₃. Conclusions For cubic-like α-Fe₂O₃, Al³⁺ and Mn²⁺ doping regulated the photocatalytic activity through the morphology effects, while Cr³⁺ doping functioned via a combination of electronic and morphology effects. In contrast, Cu²⁺ doping modulated photocatalytic activity primarily through the electronic effect. Cu²⁺ doping promoted the generation and separation of photogenerated charge carriers, enhanced interfacial charge transfer, suppressed charge recombination, and generated more reactive radicals, ,thereby achieving highly efficient photocatalytic decolorization and pollutant degradation.

Keywords: morphology control; metal ion doping; photo-Fenton reaction; high-chroma refractory wastewater