PEI改性CuS活化过硫酸盐去除边坡HA的研究

吕建兵; 邵莹; 陈嘉豪; 樊庆鲁; 姚大游; 林金钧

doi:10.11949/0438-1157.20260086

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PEI改性CuS活化过硫酸盐去除边坡HA的研究

生物化学工程与技术 | 更新时间：2026-04-29

- PEI改性CuS活化过硫酸盐去除边坡HA的研究
- Removal of humic acid from a sloped water body using polyethyleneimime-modified CuS-activated persulfate
- 化工学报 2026年
- 作者机构：
  
  1.广东工业大学土木与交通工程学院，广东广州 510006
  2.新疆农垦科学院，新疆石河子832000
  3.中建三局集团（深圳）有限公司，广东深圳518110
- 作者简介：
  
  吕建兵（1977—），男，博士，教授，ljb@gdut.edu.cn
- 基金信息：
  
  国家自然科学基金项目(52468059)
- DOI：10.11949/0438-1157.20260086
  中图分类号： X 703.1
- 收稿：2026-01-19，
  
  修回：2026-04-26，
  
  录用：2026-04-27，
- 稿件说明：
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吕建兵, 邵莹, 陈嘉豪, 等. PEI改性CuS活化过硫酸盐去除边坡HA的研究[J/OL]. 化工学报, 2026.

LV Jianbing, SHAO Ying, CHEN Jiahao, et al. Removal of humic acid from a sloped water body using polyethyleneimime-modified CuS-activated persulfate[J/OL]. CIESC Journal, 2026.
吕建兵, 邵莹, 陈嘉豪, 等. PEI改性CuS活化过硫酸盐去除边坡HA的研究[J/OL]. 化工学报, 2026. DOI： 10.11949/0438-1157.20260086.

LV Jianbing, SHAO Ying, CHEN Jiahao, et al. Removal of humic acid from a sloped water body using polyethyleneimime-modified CuS-activated persulfate[J/OL]. CIESC Journal, 2026. DOI： 10.11949/0438-1157.20260086.

摘要

边坡或隧道水体中腐殖酸（HA）易产生生物淤堵

也会危害水质安全，需要研发一种新型高效腐殖酸净化技术，基于硫酸根自由基的高级氧化技术是高效去除手段。本研究采用一步原位合成法制备聚乙烯亚胺（PEI）改性硫化铜（CuS@PEI），用于活化过二硫酸盐（PDS）降解HA。结果表明，PEI的引入未改变CuS晶体结构，但通过空间位阻抑制团聚，形成分散性良好的纳米球，且胺基可促进Cu

/Cu

价态循环并减少铜离子浸出。在HA浓度为20mg/L，CuS@PEI浓度为0.2g/L，PDS浓度为3mmol/L，pH值为3~9条件下，60min内HA去除率达88%以上，显著高于未改性CuS体系（52.68%），且具有将HA进一步矿化的潜力。该体系对Cl

、SO

和NO

等常见阴离子表现出优异的抗干扰能力，而HCO

则对HA降解具有抑制作用。CuS@PEI/PDS体系中活性氧包括SO

·、·OH、O

、

，其中O

、

起主导作用，且存在电子转移路径协同降解HA。HA在活性氧的作用下经历芳香族中间体的生成、开环反应、C–C键断裂及最终矿化过程。CuS@PEI循环5次后去除率仍达81.66%，且铜离子浸出量显著降低，该材料为高效去除边坡水体HA提供了新思路。

Abstract

Biological clogging with humic acid (HA) in sloped or tunnel water bodies can degrade water quality

necessitating an innovative and efficient HA purification technology. The sulfate-radical-based advanced oxidation process has been regarded as an effective HA-removal strategy. In this study

polyethyleneimine (PEI)-modified copper sulfide (CuS@PEI) was prepared via a one-step in situ synthesis method and used as a peroxydisulfate (PDS) activator for HA degradation. Results revealed that PEI introduction did not alter the crystal structure of CuS but exerted a steric-hindrance effect that suppressed particle agglomeration and promoted the formation of well-dispersed nanospheres. Moreover

/Cu

cycling was promoted by the amine groups in PEI

which decreased the leaching of copper ions. In the reaction system with HA

CuS@PEI

and PDS concentrations of 20 mg/L

0.2 g/L

and 3 mmol/L

respectively

and pH values of 3-9

the HA-removal rate far exceeded that of the unmodified CuS system within 60 minutes (

88% vs.52.68%)

and the potential mineralization of HA can be further facilitated.The system exhibits excellent resistance to int

erference from common anions such as Cl

、SO

and NO

while HCO

shows an inhibitory effect on HA degradation. Among active oxygen species generated in the CuS@PEI/PDS system (such as SO

·OH

and

)

and

played the dominant role

and synergistic HA degradation was promoted by an electron transfer pathway. HA undergoes the formation of aromatic intermediates

ring-opening reactions

C–C bond cleavage

and ultimately mineralization under the action of reactive oxygen species. After five cycles

CuS@PEI retained a removal rate of 81.66% and copper-ion leaching was significantly reduced compared to the CuS system. Therefore

the as-prepared material can realize the efficient removal of HA from sloped water bodies.

关键词

Keywords

references

Satishkumar P , Isloor A M , Farnood R . High performance 2D molybdenum MXene polyphenylsulfone membranes for boosting water flux and efficient removal of humic acid, antibiotic and dyes from wastewater [J ] . Chemical Engineering Journal , 2025 , 512 : 161920 .

Wang C Q , Huang R , Sun R R , et al . A review on persulfates activation by functional biochar for organic contaminants removal: Synthesis, characterizations, radical determination, and mechanism [J ] . Journal of Environmental Chemical Engineering , 2021 , 9 ( 5 ): 106267 .

Liu Z B , Ren X , Duan X Y , et al . Remediation of environmentally persistent organic pollutants (POPs) by persulfates oxidation system (PS):a review [J ] . Science of The Total Environment , 2023 , 863 : 160818 .

Qiu Y , Zhang Q , Wang Z H , et al . Degradation of anthraquinone dye reactive blue 19 using persulfate activated with Fe/Mn modified biochar: Radical/non-radical mechanisms and fixed-bed reactor study [J ] . Science of the Total Environment , 2021 , 758 : 143584 .

肖鹏飞 , 安璐 , 韩爽 . 炭质材料在活化过硫酸盐高级氧化技术中的应用进展 [J ] . 化工进展 , 2020 , 39 ( 8 ): 3293 - 3306 .

Xiao P F , An L , Han S . Research advances on applying carbon materials to activate persulfate in advanced oxidation technology [J ] . Chemical Industry and Engineering Progress , 2020 , 39 ( 8 ): 3293 - 3306 .

Liu B Z , Huang B R , Wang Z Z , et al . Homogeneous/heterogeneous metal-catalyzed persulfate oxidation technology for organic pollutants elimination: a review [J ] . Journal of Environmental Chemical Engineering , 2023 , 11 ( 3 ): 109586 .

Gao X , Chen Y Q , Kang Z W , et al . Enhanced degradation of aqueous tetracycline hydrochloride by integrating eggshell-derived CaCO 3 /CuS nanocomposite with advanced oxidation process [J ] . Molecular Catalysis , 2021 , 501 : 111380 .

Zhang L H , Xiao C , Li Z M , et al . Degradation of methyl orange using persulfate activated by magnetic CuS/Fe3O4 catalyst: Catalytic performance and mechanisms [J ] . Applied Surface Science , 2023 , 618 : 156595 .

Peng J L , Lu X H , Jiang X , et al . Degradation of atrazine by persulfate activation with copper sulfide (CuS): Kinetics study, degradation pathways and mechanism [J ] . Chemical Engineering Journal , 2018 , 354 : 740 - 752 .

Yang J Y , Hu Z X , Rao W H , et al . Reusable CS-Ca@PEI/CuMnO 2 hydrogel beads for peroxymonosulfate-activated degradation of Congo red [J ] . Langmuir , 2024 , 40 ( 28 ): 14245 - 14256 .

汤亚 , 孙盛睿 , 樊佳 , 等 . 粉煤灰衍生水合硅酸钙PEI改性及吸附去除Cu(Ⅱ)与催化降解有机污染物 [J ] . 无机材料学报 , 2023 , 38 ( 11 ): 1281 - 1291 .

Tang Y , Sun S R , Fan J , et al . PEI modified hydrated calcium silicate derived from fly ash and its adsorption for removal of Cu(II)and catalytic degradation of organic pollutants [J ] . Journal of Inorganic Materials , 2023 , 38 ( 11 ): 1281 - 1291 .

Zhang K , Zhang J M , Yang A L . Photoheating effects of CuS@PEI_GQDs nanoshells under near-infrared laser and sunlight irradiation [J ] . Crystal Growth & Design , 2023 , 23 ( 3 ): 1697 - 1708 .

Zhang A , Jiang Z Q , Zhang S D , et al . Coral-shaped Mn-CuS with hierarchical pores and crystalline defects for high-efficiency H 2 O 2 production via electrocatalytic two-electron reduction [J ] . Applied Catalysis B: Environmental , 2023 , 331 : 122721 .

曹振坤 , 张国栋 , 林炜博 , 等 . 超支化聚硅氧烷在四氧化三铁表面改性中的结构调控研究 [J ] . 当代化工研究 , 2025 ( 10 ): 48 - 50 .

Cao Z K , Zhang G D , Lin W B , et al . synthesis and structure regulation of hyperbranched polysiloxane modified Fe 3 O 4 [J ] . Modern Chemical Research , 2025 ( 10 ): 48 - 50 .

Samanta P K . Effect of microstrain on the crystallite size of ZnO nanoparticles: X-ray peak profile and Rietveld analysis [J ] . Next Materials , 2025 , 8 : 100841 .

Liu T , Wang Q , Li C X , et al . Synthesizing and characterizing Fe 3 O 4 embedded in N-doped carbon nanotubes-bridged biochar as a persulfate activator for sulfamethoxazole degradation [J ] . Journal of Cleaner Production , 2022 , 353 : 131669 .

Yang J , Zhai X F , Zhang S Q , et al . Biosynthesis of CuS nanozymes for synergistic antibacterial applications: Biosynthetic parameters optimization and antimicrobial mechanisms elucidation [J ] . Journal of Colloid and Interface Science , 2025 , 700 : 138604 .

Zhang S L , Du Z L , Wang M X , et al . Synthesized CuO-PEI-JE with 3D open-cell structure as an efficient heterogeneous activator of peroxodisulfate for phenol degradation [J ] . Environmental Research , 2025 , 264 : 120308 .

Wang H Y , Li H F . Fe 3 O 4 microplate filled PEI matrix composite with remarkable nonlinear conductive characteristics, dielectric property, and low percolation threshold [J ] . Heliyon , 2023 , 9 ( 11 ): e22514 .

Meng H , Nie C Y , Li W L , et al . Insight into the effect of lignocellulosic biomass source on the performance of biochar as persulfate activator for aqueous organic pollutants remediation: Epicarp and mesocarp of citrus peels as examples [J ] . Journal of Hazardous Materials , 2020 , 399 : 123043 .

Li W H , Nie C Y , Wang X J , et al . Alkaline lignin-derived N-doped biochars as peroxymonosulfate activators for acetaminophen degradation: Performance and catalytic bridging mediated Electron-Transfer mechanism [J ] . Separation and Purification Technology , 2023 , 323 : 124418 .

Zhang T , Yu H L , Han Z L , et al . Remediation of atrazine in environment by persulfate activation via N/B Co-doped Si-rich biochar: Performance, mechanisms, degradation pathways and phytotoxicity [J ] . Chemical Engineering Journal , 2023 , 477 : 147131 .

Wang B , Li Y N , Wang L . Metal-free activation of persulfates by corn stalk biochar for the degradation of antibiotic norfloxacin: Activation factors and degradation mechanism [J ] . Chemosphere , 2019 , 237 : 124454 .

Zhang Z J , Xiao X , Zhou Y H , et al . Bioinspired graphene oxide membranes with pH-responsive nanochannels for high-performance nanofiltration [J ] . ACS Nano , 2021 , 15 ( 8 ): 13178 - 13187 .

陈思良 , 孙雯 , 洪耀良 . 氮掺杂生物炭负载CuS活化过硫酸盐去除橙黄G [J ] . 中国环境科学 , 2024 , 44 ( 05 ): 2483 - 2494 .

Chen S L , Sun W , Hong Y L . Removal of Orange G by nitrogen-doped biochar loaded with CuS activated persulfate [J ] . China Environmental Science , 2024 , 44 ( 5 ): 2483 - 2494 .

Wang M M , Wang Y F , Li Y C , et al . Persulfate oxidation of tetracycline, antibiotic resistant bacteria, and resistance genes activated by Fe doped biochar catalysts: Synergy of radical and non-radical processes [J ] . Chemical Engineering Journal , 2023 , 464 : 142558 .

张佳颖 , 王聪 , 王雅君 . CNT-Co/Bi 2 O 3 催化剂光催化协同过硫酸盐活化高效降解四环素 [J ] . 化工学报 , 2024 , 75 ( 9 ): 3163 - 3175 .

Zhang J Y , Wang C , Wang Y J . CNT-Co/Bi 2 O 3 catalyst photocatalytic synergistic activation of persulfate for efficient degradation of tetracycline [J ] . CIESC Journal , 2024 , 75 ( 9 ): 3163 - 3175 .

冯竹青 . 秸秆成分差异驱动生物炭基催化剂活化过硫酸盐降解磺胺嘧啶的机制研究 [D ] . 北京：北京科技大学 , 2025 .

Feng Z Q . Mechanisms of sulfadiazine degradation by activation of persulfate over biochar-based catalysts driven with differences in straw composition [D ] . Beijing ： University of Science and Technology Beijing , 2025 .

Peng H N , Hong F Q , Chen P , et al . Preparation of organic solvent-resistant nanofiltration membranes through copper sulfate (CuSO 4 )/hydrogen peroxide (H 2 O 2 ) oxidation triggered polydopamine (PDA)/polyethyleneimine (PEI) deposition interlayer [J ] . Separation and Purification Technology , 2025 , 369 : 133090 .

Jiang M X , Sun Y , Zhu J W , et al . Confinement synthesis via pH-responsive polyethyleneimine-glutaraldehyde cross-linked networks for Cu@Ag with enhanced conductivity and oxidation resistance for electronic applications [J ] . Chemical Engineering Journal , 2025 , 522 : 166931 .

Nguyen D K , Bui M Q , Le D T , et al . One-step synthesis of dual-functional PEI/SiO 2 nanoparticles for simultaneous Cu(II) ion adsorption and fluorescence sensing [J ] . Solid State Communications , 2025 , 404 : 116041 .

Pei C C , Aryee A A , Zhu K K , et al . Adsorption and catalytic degradation of Light green SF by magnetic PEI-modified carbon nanotubes composites [J ] . Separation and Purification Technology , 2025 , 355 : 129625 .

Kannivelan S , Rajappan K . Fe-HNT@PVP/PEI membranes for enhanced dye removal and water purification [J ] . Materials Science and Engineering: B , 2025 , 317 : 118213 .

Huang K Z , Xu J J , Qu W , et al . Self-supply activation Fenton-like system for water purification using polyethyleneimine-driven electron pumps in polymeric carbon nitride [J ] . Journal of Colloid and Interface Science , 2025 , 700 : 138408 .

Zheng J B , Monfort O , Xu J Y , et al . A novel CuS/persulfate/ percarbonate dual-oxidant process for synergistic degradation of BPA: Crucial role of CO 3 2- [J ] . Process Safety and Environmental Protection , 2025 , 198 : 107116 .

He J H , Yuan S , Gao P , et al . Probing the interfacial adsorption mechanism of an ammonium salt of N-nitroso-N-phenylhydroxylamine in bastnaesite flotation by FT-IR, XPS and DFT [J ] . Applied Surface Science , 2026 , 719 : 165103 .

Bai C B , Guo W J , Liu Q , et al . Cu 2 O/BiVO 4 heterostructure controllably triggers radical and non- radical persulfate activation via light “on-off” for efficient organic contaminants degradation [J ] . Applied Catalysis B: Environment and Energy , 2024 , 344 : 123606 .

Wu L T , Liu Y Y , Shi T Y , et al . Bimetallic MOFs-derived CuS/FeMn-C composite materials efficiently activate persulfate for catalytic degradation of ciprofloxacin [J ] . Journal of the Taiwan Institute of Chemical Engineers , 2025 , 174 : 106236 .

Ben Hamou A , Amjlef A , Nouj N , et al . Persulfate activation by Fe-rich biochar from sewage sludge digestate for organic pollutants removal: performance and superoxide radical role [J ] . Journal of Environmental Management , 2025 , 390 : 126331 .

Cai S , Wang T S , Wu C Y , et al . Efficient degradation of norfloxacin using a novel biochar-supported CuO/Fe 3 O 2 combined with peroxydisulfate: Insights into enhanced contribution of nonradical pathway [J ] . Chemosphere , 2023 , 329 : 138589 .

Huang T T , Wang S , Deng L , et al . In-situ complexation of Cu(II) with polyethyleneimine (PEI) triggers the enhanced formation of halonitromethanes, dichloroacetonitrile, and dichloroacetamide during UV/chlorine disinfection: Cu(I) contribution and Cl· sustainable production [J ] . Chemical Engineering Journal , 2024 , 497 : 154412 .

周凌风 , 李腾 , 张娱 , 等 . 铜氮共掺杂生物炭活化过一硫酸盐降解盐酸四环素的研究 [J ] . 能源环境保护 , 2025 , 39 ( 2 ): 95 - 108 .

Zhou L F , Li T , Zhang Y , et al . Degradation of tetracycline hydrochloride by peroxymonosulfate activation using Cu/N Co-doped biochar [J ] . Energy Environmental Protection , 2025 , 39 ( 2 ): 95 - 108 .

Zhang Y F , Zhang X J , Huang J J , et al . Lamellar COF solid-state electrolytes for robust ambient-temperature lithium-ion transfer enhanced by PEI-driven channel alignment [J ] . Green Energy & Environment , 2025 , 10 ( 5 ): 982 - 993 .

Zhao Q M , Ni X H , Wang Z . Biochar matrix composites for persulfate-based advanced oxidation process: Preparation, performance and activation mechanism [J ] . Journal of Industrial and Engineering Chemistry , 2025 , 152 : 1 - 17 .

Ma D R , Mei J , Liang Q W , et al . Recent advances in nanomaterial-enhanced persulfate activation for organic pollutants removal: Electron transfer, surface reactions, and radical generation [J ] . Journal of Environmental Chemical Engineering , 2023 , 11 ( 6 ): 111511 .

Zhang M X , Liao C C , Dong B , et al . Construction of SnO 2 /Bi 2 O 2 CO 3 Z-type heterojunction for photocatalytic degradation of humic acid under sunlight [J ] . Environmental Research , 2026 , 297 : 124219 .

Cai J B , Li H , Feng K , et al . Low-temperature degradation of humic acid via titanium zirconium oxide@copper single-atom activating oxygen: Mechanism and pathways [J ] . Chemical Engineering Journal , 2022 , 450 : 138239 .

Wang Q , Luo W , Huang K , et al . Unveiling the impact of initial pH on humic acid degradation using ultraviolet light-activated peroxydisulfate in landfill leachate treatment [J ] . Journal of Environmental Chemical Engineering , 2025 , 13 ( 5 ): 119062 .

Ma Q L , Tan X Q , Fang M , et al . Built-in electric field of Ag 2 Se thermoelectric effect activated persulfate for humic acid decomposition in water: Molecular transformation mechanism [J ] . Water Research , 2025 , 281 : 123717 .

Cao F , Wu J L , Dai G L , et al . Electrospun porous polyacrylonitrile nanofibrous membrane grafted with branched polyethyleneimine for efficient adsorption of Cu 2+ and Pb 2+ from polluted water [J ] . Journal of Environmental Chemical Engineering , 2024 , 12 ( 6 ): 114424 .

Song S Y , Pham N N T , Moon G-H , et al . Unveiling the unforeseen role of manganese constituent in creating a carbon-based composite as a high-efficiency persulfate activator: Catalyzing carbon phase graphitization and promoting persulfate binding affinity [J ] . Applied Catalysis B: Environment and Energy , 2025 , 378 : 125598 .

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