孔德勇1， 昌晶1， 郑波2， 苗菲1， 马东1，3， 王仲鹏1，3
1. 济南大学 水利与环境学院， 山东 济南 250022； 2.山东省潍坊市科技创新促进中心， 山东 潍坊 261061；3.山东省黄河三角洲生态环境重点实验室， 山东 滨州 256603
引用格式：
孔德勇， 昌晶， 郑波， 等. 氮掺杂与氧空位协同调控InVO4光催化性能及机制［J］. 中国粉体技术， 2026， 32（5）： 1-11.
Citation:Kong Deyong， Chang Jing， Zheng Bo， et al. Synergistic regulation of nitrogen doping and oxygen vacancies on photocatalytic performance and mechanism of InVO4［J］. China Powder Science and Technology， 2026， 32（5）： 1-11.
DOI：10.13732/j.issn.1008-5548.2026.05.011
收稿日期： 2026-05-11， 修回日期： 2026-06-07，上线日期： 2026-07-05。
基金项目： 国家自然科学基金项目，编号：42077120； 济南大学新引进人才科研项目，编号：XRC2506/XRC2532。
第一作者： 孔德勇（2002—），男，硕士生，研究方向为环境催化。E-mail：Kongdy_time@163.com。
通信作者： 郑波（1972—），男，副教授，硕士，研究方向为环境科技管理。E-mail： bo.zheng@pku-iaas.edu.cn。马东（1981—），男，教授，博士，博士生导师，“泰山学者”青年专家，研究方向为环境催化与污染控制。E-mail： stu_mad@ujn.edu.cn。
摘要： 【目的】 研究烷基氢氧化铵调控对钒酸铟（InVO4）粉体光催化性能的影响机制，分析氮掺杂与氧空位协同作用对载流子行为的调控规律，实现材料光催化性能的提升。 【方法】 采用水热法制备InVO4、四乙基氢氧化铵（tetraethylammonium hydroxide， TEAOH）调控InVO4（E-InVO4）以及四丁基氢氧化铵（tetrabutylammonium hydroxide， TBAOH）调控InVO4（B-InVO4）光催化剂，通过表征手段对其结构与电子特性进行表征；以双酚A（bisphenol A， BPA）为目标污染物，开展光催化降解与矿化性能测试。 【结果】 E-InVO4光催化剂带隙为2.48 eV，显著小于InVO4的2.60 eV；60 min内BPA去除率接近100%，总有机碳（total organic carbon， TOC）的去除率约为45%，表观反应速率分别是B-InVO4和InVO4的9.9倍和38.3倍；氧空位浓度最高，载流子复合最弱，明显优于对比样品。 【结论】 烷基氢氧化铵诱导的氮掺杂与氧空位协同作用通过带隙调控与电子捕获机制显著提升载流子分离效率，从而实现InVO4光催化性能的有效提高。
关键词： 光催化； 钒酸铟； 烷基氢氧化铵； 氮掺杂； 氧空位
Abstract
Objective This study aims to investigate the influence of alkylammonium hydroxide regulation on the photocatalytic performance of InVO4 powders. Enhancing photocatalytic activity by tuning crystal growth and defect structures is considered an effective strategy. However， the main challenge lies in clarifying the synergistic roles of nitrogen doping and oxygen vacancies in carrier dynamics. Based on this， their combined effects on charge separation and migration are analyzed to provide guidance for the design of high-efficiency photocatalysts.
Methods In this study， InVO4 photocatalysts were synthesized by a hydrothermal method. Indium nitrate and ammonium metavanadate were dissolved in deionized water， mixed， and then treated with tetraethylammonium hydroxide （TEAOH） or tetrabutylammonium hydroxide （TBAOH） under stirring. The mixture was transferred to a Teflon-lined autoclave and heated at 180 ℃ for 12 h. The obtained precipitate was washed， dried， and denoted as E-InVO4， B-InVO4， and pristine InVO4. Photocatalytic activity was evaluated using bisphenol A （BPA） under visible light. 0.1 g catalyst was dispersed in 100 mL BPA solution， and samples were periodically collected for analysis. BPA concentration was determined by high-performance liquid chromatography （HPLC）， and total organic carbon （TOC） was measured using a TOC analyzer.
Results and Discussion From a structural perspective， the introduction of organic auxiliaries significantly regulated the morphology and particle size distribution of the powders. In particular， the short-chain TEAOH promoted the formation of smaller and more uniformly distributed nanoparticles， which not only improved the utilization of active sites but also provided a favorable basis for the uniform introduction of defects. From the viewpoint of electronic structure， nitrogen doping effectively narrowed the band gap of InVO4 and enhanced its visible-light absorption. The band gap of E-InVO4 was reduced to 2.48 eV， which was significantly lower than that of pristine InVO4 （2.60 eV）. Meanwhile， the introduction of defect structures increased the concentration of oxygen vacancies and effectively suppressed the recombination of photogenerated electron–hole pairs. The short-chain organic auxiliary was more conducive to constructing a synergistic defect structure with high nitrogen doping and abundant oxygen vacancies， leading to nearly complete removal of BPA within 60 min and a TOC removal of approximately 45%， which was markedly superior to the control samples.
Conclusion The synergistic effects of nitrogen doping and oxygen vacancies induced by TEAOH significantly enhance charge carrier separation efficiency and effectively improve the photocatalytic performance of InVO4. The apparent rate constant of E-InVO4 is 9.9 and 38.3 times higher than those of B-InVO4 and pristine InVO4， respectively. This study provides theoretical insights and technical guidance for the design of InVO4 powder photocatalysts based on defect engineering.
Keywords： photocatalysis； indium vanadate； alkylammonium hydroxides； nitrogen doping； oxygen vacancies
参考文献（References）
［1］Hassani A， Eghbali P， Mahdipour F， et al. Insights into the synergistic role of photocatalytic activation of peroxymonosulfate by UVA-LED irradiation over CoFe2O4-rGO nanocomposite towards effective bisphenol a degradation： performance， mineralization， and activation mechanism［J］. Chemical Engineering Journal， 2023， 453： 139556.
［2］雷学博， 刘慧景， 丁赫宇， 等. 用于降解印染废水中有机污染物的光催化剂的研究进展［J］. 应用化学， 2023， 40（5）：681-696.
Lei Xuebo， Liu Huijing， Ding Heyu， et al. Research progress on photocatalysts for degradation of organic pollutantsin printing and dying wastewater［J］. Applied Chemistry， 2023， 40（5）： 681-696.
［3］Sinha R， Ghosal P S. A comprehensive appraisal on status and management of remediation of DBPs by TiO2 based-photocat-alysts： insights of technology， performance and energy efficiency［J］.Journal of Environmental Management，2023，328：117011.
［4］Chauhan A， Negi A， Dogra A， et al. Recent advancements in the role of biopolymers as photocatalytic materials for waste-water treatment［J］. Advances in Colloid and Interface Science， 2025， 344： 103591.
［5］Yang Ruijie， Zhang Yuefeng， Fan Yingying， et al. InVO4-based photocatalysts for energy and environmental applications［J］.Chemical Engineering Journal， 2022， 428： 131145.
［6］Zhao Guoqing， Zhang Qie， Hu Chuchu， et al. Recent intensification strategies of indium vanadate-based materials for photocatalytic application［J］. Separation and Purification Technology， 2024， 346： 127462.
［7］Liu Jue， Li Shiwen， Meng Can， et al. Visible-light induced tetracycline degradation catalyzed by dual Z-scheme InVO4/CuBi2O4/BiVO4 composites： the roles of oxygen vacancies and interfacial chemical bonds［J］. Chemical Engineering Journal， 2023， 473： 145278.
［8］Dhivya J， Gopalakrishnan L， Deivasigamani P， et al. Engineered Cu3P-ZnWO4 heterojunction integrated with porous polymer monolithic template for enhanced photocatalytic degradation of organic pollutants［J］. Scientific Reports， 2025， 16（1）：389.
［9］Liu Deyu， Kuang Yongbo. Particle-based photoelectrodes for PEC water splitting： concepts and perspectives［J］. Advanced Materials， 2024， 36（37）： 2311692.
［10］Wei Hainan， Meng Fanming， Zhang Han， et al. Novel oxygen vacancy-rich Bi2MoO6-SOVs/MgFe2O4 S-scheme heterojunction piezo-photocatalytic for efficient degradation of norfloxacin and theoretical calculations［J］. Chemical Engineering Journal， 2024， 479： 147738.
［11］Lin Xi， Xia Shuhui， Zhang Liang， et al. Fabrication of flexible mesoporous black Nb2O5 nanofiber films for visible-light-driven photocatalytic CO2 reduction into CH4［J］. Advanced Materials， 2022， 34（16）： 2200756.
［12］Wang Wenchao， Du Lili， Xia Ruiqin， et al. In situ protonated-phosphorus interstitial doping induces long-lived shallow charge trapping in porous C3-xN4 photocatalysts for highly efficient H2 generation［J］. Energy & Environmental Science， 2023， 16（2）： 460-472.
［13］Liu Fuyu， Li Honglei， Gao Zixiang， et al. Steering charge transfer in CuInS2/BiOCl composites to enable sunlight-driven C—F bond cleavage of PFAS in water［J］. Nature Water， 2026， 4： 334-347.
［14］Sun Long， Li Lingling， Yang Juan， et al. Fabricating covalent organic framework/CdS S-scheme heterojunctions for improved solar hydrogen generation［J］. Chinese Journal of Catalysis， 2022， 43（2）： 350-358.
［15］Zhang Xiao， Yang Ping. Role of graphitic carbon in g-C3N4 nanoarchitectonics towards efficient photocatalytic reaction kinetics： a review［J］. Carbon， 2024， 216： 118584.
［16］Liu Tian， Zhu Wei， Wang Ning， et al. Preparation of structure vacancy defect modified diatomic-layered g-C3N4 nanosheet with enhanced photocatalytic performance［J］. Advanced Science， 2023， 10（24）： 2302503.
［17］Mushtaq M A， Kumar A， Yasin G， et al. 3D interconnected porous Mo-doped WO3@CdS hierarchical hollow heterostructures for efficient photoelectrochemical nitrogen reduction to ammonia［J］. Applied Catalysis B： Environmental， 2022， 317： 121711.
［18］Bao Yunfeng， Zou Hai， Du Shiwen， et al. Metallic powder promotes nitridation kinetics for facile synthesis of （oxy）nitride photocatalysts［J］. Advanced Materials， 2023， 35（32）： 2302276.
［19］Zhang Yangpeng， Han Wei， Yang Yan， et al. S-scheme heterojunction of black TiO2 and covalent-organic framework for enhanced photocatalytic hydrogen evolution［J］. Chemical Engineering Journal， 2022， 446： 137213.
［20］Gul I， Sayed M， Rehman F， et al. Z-scheme Ti3C2@Bi2O3 based MXene with multifaceted （001） and （101） TiO2 and Ti3+/oxygen vacancies： photocatalytic degradation of dichlorophen via peroxymonosulfate activation， energy utilization and antibacterial activities［J］. Chemical Engineering Journal， 2025， 506： 159992.
［21］Esmat M， El-Hosainy H， Tahawy R， et al. Nitrogen doping-mediated oxygen vacancies enhancing co-catalyst-free solar photocatalytic H2 production activity in anatase TiO2 nanosheet assembly［J］. Applied Catalysis B： Environmental， 2021， 285： 119755.
［22］Yang Bin， Li Xiaolong， Zhang Qian， et al. Ultrathin porous carbon nitride nanosheets with well-tuned band structures via carbon vacancies and oxygen doping for significantly boosting H2 production［J］. Applied Catalysis B： Environmental， 2022， 314： 121521.
［23］Qi Lanyue， Zhang Hao， Yang Yue， et al. Coupled electron delocalization and multi-dimensional porosity engineering in TiO2 hollow spheres-embedded carbon nanofiber aerogels for efficient photocatalytic aniline degradation［J］. Chemical Engineering Journal， 2025， 515： 163690.
［24］Sun Siwei， Wang Chao， Wang Qinchao， et al. Three-in-one oxygen-deficient titanium dioxide in a pomegranate-inspired design for improved lithium storage［J］. Journal of Colloid and Interface Science， 2023， 633： 546-554.
［25］Zhou Li， Zhang Xue， Cai Min， et al. New insights into the efficient charge transfer of the modified-TiO2/Ag3PO4 composite for enhanced photocatalytic destruction of algal cells under visible light［J］. Applied Catalysis B： Environmental， 2022， 302： 120868.
［26］Mei Feifei， Dai Kai， Zhang Jinfeng， et al. Ultrathin indium vanadate/cadmium selenide-amine step-scheme heterojunction with interfacial chemical bonding for promotion of visible-light-driven carbon dioxide reduction［J］. Journal of Colloid and Interface Science， 2022， 608： 1846-1856.
［27］Cao Kaipeng， Chen Wei， Fan Dong， et al. MOR nanosheets with tunable c-axis thickness and their catalytic performance in DME carbonylation［J］. Chemical Engineering Journal， 2024， 487： 150344.
［28］Zeng Bojun， Wu Siming， Gao Mingbin， et al. Directional transport in hierarchically aligned ZSM-5 zeolites with high cataytic activity［J］. Journal of the American Chemical Society， 2024， 146（49）： 33423-33433.
［29］Yu Qiang， Li Junjie， Liu Wen， et al. Rational design of a novel silica-based material with abundant open micropores for efficient VOC removal［J］. Chemical Engineering Journal， 2023， 454： 140077.
［30］Wang Xiaoyi， Xue Sikang， Huang Meirong， et al. Pressure-induced engineering of surface oxygen vacancies on metal oxides for heterogeneous photocatalysis［J］. Journal of the American Chemical Society， 2025， 147（6）： 4945-4951.
［31］宋相海， 刘晓颖， 任智祥， 等. 氮掺杂显著提升BiOBr光催化还原CO2性能研究［J］. 物理化学学报， 2025， 41（6）：84-96.
Song Xianghai， Liu Xiaoying， Ren Zhixiang， et al. Insights into the greatly improved catalytic performance of N-doped BiOBr for CO2 photoreduction［J］. Acta Physico-Chimica Sinica， 2025， 41（6）： 84-96.
［32］Hailili R， Ji Hongwei， Wang Kaiwen， et al. ZnO with controllable oxygen vacancies for photocatalytic nitrogen oxide removal［J］. ACS Catalysis， 2022， 12（16）： 10004-10017.
［33］马德运， 梁凤兰， 薛清泉， 等. 界面工程与氧空位协同策略促进Cd0.5Zn0.5S/BiOBr S型异质结高效光催化去除抗生素［J］. 物理化学学报， 2025， 41（12）： 164-174.
Ma Deyun， Liang Fenglan， Xue Qingquan， et al. Interfacial engineering of Cd0.5Zn0.5S/BiOBr S-scheme heterojunction with oxygen vacancies for effective photocatalytic antibiotic removal［J］. Acta Physico-Chimica Sinica， 2025， 41（12）： 100190.
［34］Wang Yinghui， Yu Wenying， Wang Chunyang， et al. Defects in photoreduction reactions： fundamentals， classification， and catalytic energy conversion［J］. eScience， 2024， 4（3）： 100228.
［35］Wu Xinlin， Liu Shiang， Li Yu， et al. Directional and ultrafast charge transfer in oxygen-vacancy-rich ZnO@single-atom cobalt core-shell junction for photo-fenton-like reaction［J］. Angewandte Chemie International Edition， 2023， 62（30）： e202305639.
［36］Guo Congcong， Li Yuyou， Gu Jiyan， et al. Unraveling the co-catalytic mechanism in fenton-like reaction with diatomic Fe/Mo catalysts： accelerating the Fe（Ⅱ）/Fe（Ⅲ） conversion and PAA efficient activation［J］. Water Research， 2025， 287： 124473.
［37］Xia Xiaoyong， Feng Jie， Zhong Zhaocan， et al. Reconstruction of D-Π-A polymer accelerating photocatalytic degradation of BPA and production of H2O2［J］. Advanced Functional Materials， 2024， 34（13）： 2311987.
