回收废弃锂电池制备Co3O4-C/ Bi2Fe4O9复合材料活化过一硫酸盐降解丁铵黑药

王亚玮; 柴娜; 刘波; 曹华; 聂倩倩; 杨磊; 俞和胜

doi:10.11949/0438-1157.20251325

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回收废弃锂电池制备Co₃O₄-C/ Bi₂Fe₄O₉复合材料活化过一硫酸盐降解丁铵黑药

更新时间：2026-05-19

- 回收废弃锂电池制备Co₃O₄-C/ Bi₂Fe₄O₉复合材料活化过一硫酸盐降解丁铵黑药
- Recycling Spent Lithium Batteries to Prepare Co₃O₄-C/Bi₂Fe₄O₉ Composites for Peroxymonosulfate Activation in the Degradation of Ammonium Dibutyl Dithiophosphate
- 化工学报 2026年页码：1-15
- 作者机构：
  
  1.中国矿业大学炼焦煤资源绿色开发全国重点实验室，江苏徐州 221116
  2.中国矿业大学孙越崎学院，江苏徐州 221116
  3.中国矿业大学化工学院，江苏徐州 221116
  4.徐州工程学院物理与新能源学院，江苏徐州 221018
  5.新疆工程学院矿业工程与地质学院，新疆乌鲁木齐 830023
- 作者简介：
  
  王亚玮（2003—），男，本科，yaweiwang@cumt.edu.cn
  杨磊（1984—），男，硕士，副研究员，yl14@xjie.edu.cn
  俞和胜（1984—），男，博士，教授，heshengyu@cumt.edu.cn
- 基金信息：
  
  新疆自治区重点研发任务专项—厅地联动项目(2025B04003);智力援疆创新拓展人才计划“小组团”援疆团队人才项目（矿山固废高值化利用援疆团队）;煤炭重大专项(2026ZD1701700);新疆维吾尔自治区中央引导地方科技发展资金项目(ZYYD2024CG08);昌吉州科技支撑产业高质量发展计划项目(2025Z02)
- DOI：10.11949/0438-1157.20251325
  中图分类号： X703;TB333
- 收稿：2025-11-26，
  
  修回：2026-04-03，
  
  网络首发：2026-05-19，
- 稿件说明：
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王亚玮, 柴娜, 刘波, 曹华, 聂倩倩, 杨磊, 俞和胜. 回收废弃锂电池制备Co₃O₄-C/ Bi₂Fe₄O₉复合材料活化过一硫酸盐降解丁铵黑药[J]. 化工学报, DOI: 10.11949/0438-1157.20251325

WANG Yawei, CHAI Na, LIU Bo, CAO Hua, NIE Qianqian, YANG Lei, YU Hesheng. Recycling Spent Lithium Batteries to Prepare Co₃O₄-C/Bi₂Fe₄O₉ Composites for Peroxymonosulfate Activation in the Degradation of Ammonium Dibutyl Dithiophosphate[J]. CIESC Journal, DOI: 10.11949/0438-1157.20251325
王亚玮, 柴娜, 刘波, 曹华, 聂倩倩, 杨磊, 俞和胜. 回收废弃锂电池制备Co₃O₄-C/ Bi₂Fe₄O₉复合材料活化过一硫酸盐降解丁铵黑药[J]. 化工学报, DOI: 10.11949/0438-1157.20251325 DOI：

WANG Yawei, CHAI Na, LIU Bo, CAO Hua, NIE Qianqian, YANG Lei, YU Hesheng. Recycling Spent Lithium Batteries to Prepare Co₃O₄-C/Bi₂Fe₄O₉ Composites for Peroxymonosulfate Activation in the Degradation of Ammonium Dibutyl Dithiophosphate[J]. CIESC Journal, DOI: 10.11949/0438-1157.20251325 DOI：

摘要

利用柿子皮-草酸协同体系从废弃钴酸锂正极材料中回收钴，

并制备Co

-C/Bi

（Co

-C/BFO）复合催化剂用于活化过一硫酸盐（PMS）以高效降解丁铵黑药（ADD）。实验结果表明，Co

-C/BFO催化剂对黑药的降解效率高于Co

和Bi

（BFO）单体材料，以及未掺杂生物炭的Co

/BFO复合材料。在催化剂投加量为0.4 g/L，PMS浓度为0.8 mM的条件下，反应1 h后，Co

-C/BFO对丁铵黑药（160 mg/L）的降解效率超过99%。5次循环使用后，Co

-C/BFO仍保持97%以上的降解效率，具有优异的稳定性。该复合材料亦可高效去除乙基和丁基黄药捕收剂（降解率

88%）。Co

-C/BFO复合材料优异的催化性能归因于Fe（II）/Fe（III）与Co（II）/Co（III）的氧化还原循环及生物炭载体增强的界面电子传输能力，这两种机制协同活化PMS并诱导关键活性物种

的生成，最终实现黑药高效降解。

Abstract

With a persimmon peel–oxalic acid synergistic system

cobalt was directly recovered from spent lithium cobalt oxide cathode materials and used as a transition-metal precursor to prepare Co

-C/Bi

(Co

-C /BFO) composite catalysts for peroxymonosulfate (PMS) activation in the efficient degradation of ammonium dibutyl dithiophosphate (ADD). Experimental results show that the Co

-C/BFO catalyst exhibits significantly higher degradation efficiency of ADD than individual Co

and Bi₂Fe₄O₉ (BFO) materials

as well as the Co

/BFO composite without biochar doping. Under the conditions of catalyst dosage of 0.4 g/L and PMS concentration of 0.8 mM

-C/BFO achieved over 99% degradation of ADD (160 mg·L⁻¹) within 1 h. After 5 cycles of use

-C/BFO still maintained a high degradation efficiency above 97%

demonstrating excellent stability. Furthermore

it shows high removal rates (

88%) for sodium ethyl and sodium butyl xanthate collectors. The outstanding catalytic activity of the Co₃O₄-C/BFO composite is attributed to the synergistic PMS activation driven by the Fe(II)/Fe(II

I) and Co(II)/Co(III) redox cycles

along with the biochar-enhanced interfacial electron-transfer capability. These two mechanisms together promote the generation of key reactive species

and ultimately enable efficient ADD degradation.

关键词

Keywords

references

Yuan J Q , Li Y M , DingZ , et al . Heterogeneous activation of peroxymonosulfate by natural chalcopyrite for degradation of ammonium dibutyl dithiophosphate from mineral processing wastewater [J ] . Separation and Purification Technology , 2024 , 341 : 126741 .

Zhu L , Yang Z K , Liu X J , et al . Hydrothermal preparation of NiO/La–NaTaO 3 composite photocatalyst for degradation of ammonium dibutyl dithiophosphate wastewater [J ] . Environmental Pollution , 2023 , 334 : 122139 .

Xin Z M , Wang S G , He Q Q , et al . Preparation of a novel photocatalytic catalyst PW 9 @ZnO/Ag and the photocatalytic degradation of butyl xanthate under visible light [J ] . Environmental Research , 2022 , 214 : 113776 .

顾杰 , 李双硕 , 崔天伊 , 等 . 生物质炭掺杂BiOBr的制备及其光催化性能研究 [J ] . 聊城大学学报(自然科学版) , 2025 , 38 ( 1 ): 68 - 75 .

Gu J , Li S S , Cui T Y , et al . Preparation of biomass charcoal doped BiOBr and its photocatalytic performance [J ] . Journal of Liaocheng University(Natural Science Edition) , 2025 , 38 ( 1 ): 68 - 75 .

Nie Q Q , Liu L F , Liu J Y , et al . Photodegradation of xanthate using a Bi 2 Fe 4 O 9 /ZnIn 2 S 4 heterojunction: experimental and DFT studies [J ] . Industrial & Engineering Chemistry Research , 2024 , 63 ( 1 ): 184 - 199 .

Chen S H , Gong W Q , Mei G J , et al . Primary biodegradation of sulfide mineral flotation collectors [J ] . Minerals Engineering , 2011 , 24 ( 8 ): 953 - 955 .

Sun S H , Ren M Z , Pan F S , et al . Degradation of potassium alkyl xanthogenate in wet air oxidation: Enhancement method, degradation mechanism and structure impact [J ] . Journal of Environmental Chemical Engineering , 2022 , 10 ( 2 ): 107349 .

Premnath N , Mohanrasu K , Guru Raj Rao R , et al . A crucial review on polycyclic aromatic Hydrocarbons - Environmental occurrence and strategies for microbial degradation [J ] . Chemosphere , 2021 , 280 : 130608 .

Shen M W , Zhang G Q , Liu J Y , et al . Visible-light-driven photodegradation of xanthate in a continuous fixed-bed photoreactor: Experimental study and modeling [J ] . Chemical Engineering Journal , 2023 , 461 : 141833 .

庞尔楠 , 李世嘉 , 雒志利 , 等 . 可见光下碳点介导Cu 2+ /Cu + 氧化还原循环促进过硫酸盐活化降解四环素 [J ] . 化工学报 , 2026 , 77 ( 2 ): 922 - 932 .

Pang E N , Li S J , Luo Z L , et al . Boosting persulfate activation via carbon dots-mediated Cu 2+ /Cu + redox cycling under visible light for efficient tetracycline removal [J ] . CIESC Journal , 2026 , 77 ( 2 ): 922 - 932 .

Dewil R , Mantzavinos D , Poulios I , et al . New perspectives for advanced oxidation processes [J ] . Journal of Environmental Management , 2017 , 195 : 93 - 99 .

张林 , 张子怡 , 李勇 , 等 . Fe-MOF-74前体制备铁-碳/氮复合材料及其活化过硫酸盐性能 [J ] . 化工学报 , 2024 , 75 ( 5 ): 1882 - 1889 .

Zhang L , Zhang Z Y , Li Y , et al . Preparation of Fe-carbon/nitrogen composites from Fe-MOF-74 precusor and its performance in activating peroxymonosulfate [J ] . CIESC Journal , 2024 , 75 ( 5 ): 1882 - 1889 .

Ding J , Yin H S , Li X X , et al . Room-temperature induction of oxygen vacancies in Bi 2 Fe 4 O 9 for PMS activation and dimethyl phthalate degradation: Mechanism and toxicity evaluation [J ] . Chemical Engineering Journal , 2025 , 507 : 160497 .

Rao Y F , Zhou C Y , Wu P Q , et al . Molecular structure-dependent contribution of reactive species to organic pollutant degradation using nanosheet Bi 2 Fe 4 O 9 activated peroxymonosulfate [J ] . Journal of Hazardous Materials , 2023 , 452 : 131240 .

Dong X Y , Wang J X , Wang X , et al . Prussian blue analogue-derived bimetallic CoFe@NC as effective and extremely stable oxygen reduction electrocatalysts for Mg-air battery [J ] . ACS Applied Energy Materials , 2022 , 5 ( 10 ): 12272 - 12282 .

Kohantorabi M , Moussavi G , Giannakis S . A review of the innovations in metal- and carbon-based catalysts explored for heterogeneous peroxymonosulfate (PMS) activation, with focus on radical vs. non-radical degradation pathways of organic contaminants [J ] . Chemical Engineering Journal , 2021 , 411 : 127957 .

Zhu G M , Tan W J , Gu T T , et al . Influence of Co 3 O 4 crystal planes on peroxymonosulfate activation: Reactive oxygen species generation and pollutant degradation [J ] . Applied Surface Science , 2025 , 709 : 163742 .

Wang L , Wang Y Y , Zhang L L , et al . CoO anchored on boron nitride nanobelts for efficient removal of water contaminants by peroxymonosulfate activation [J ] . Chemical Engineering Journal , 2022 , 430 : 132915 .

Wang X T , Gu Z Y , Cao J M , et al . Dual-loop upcycling of spent LiFePO 4 : defect inheritance enables durable and fast-charging sodium-ion batteries [J ] . National Science Review , 2025 , 12 ( 9 ): nwaf321 .

Jacoby M . It's time to recycle lithium-ion batteries [J ] . C&EN Global Enterprise , 2019 , 97 ( 28 ): 29 - 32 .

Zhou F Y , Li X Y , Wang S Y , et al . Recovery of valuable metals from spent lithium-ion batteries through biomass pyrolysis gas-induced reduction [J ] . Journal of Hazardous Materials , 2023 , 459 : 132150 .

Hu Z Y , Su G , Long S J , et al . Synthesis of X@DRHC (X=Co, Ni, Mn) catalyst from comprehensive utilization of waste rice husk and spent lithium-ion batteries for efficient peroxymonosulfate (PMS) activation [J ] . Environmental Research , 2024 , 245 : 118078 .

Li B , Ma B , Wei M Y , et al . Synthesis of Co-NC catalysts from spent lithium-ion batteries for Fenton-like reaction: Generation of singlet oxygen with ∼100% selectivity [J ] . Carbon , 2022 , 197 : 76 - 86 .

Zhou F Y , Liu M J , Li X Y , et al . Preparation of CoO-C catalysts from spent lithium-ion batteries and waste biomass for eff icient degradation of ciprofloxacin via peroxymonosulfate activation [J ] . Chemical Engineering Journal , 2023 , 471 : 144469 .

Zhou D X , Tang R , Min Y L , et al . External electric field-assisted electronic restructuring of transition metal oxides derived from spent lithium-ion batteries to enhance persulfate activation [J ] . Applied Surface Science , 2023 , 625 : 157120 .

Lou X X , Li Z Y , Yan P L , et al . Repurposing spent LiFePO 4 batteries for sustainable photothermal-upcycling of polyesters [J ] . Science China Chemistry , 2026 , 69 ( 3 ): 1358 - 1366 .

Tang S J , Feng J L , Su R C , et al . New bifunctional deep-eutectic solvent for in situ selective extraction of valuable metals from spent lithium batteries [J ] . ACS Sustainable Chemistry & Engineering , 2022 , 10 ( 26 ): 8423 - 8432 .

Wu D T , Deng W , Li J , et al . Ultrasound-assisted deep eutectic solvent extraction of phenolic compounds from thinned young kiwifruits and their beneficial effects [J ] . Antioxidants , 2023 , 12 ( 7 ): 1475 .

Wang Y W , Wang L J , Zhang S A , et al . Green strategy for recovering cathode materials from end-of-life lithium-ion batteries using grape pomace [J ] . Separation and Purification Technology , 2025 , 354 : 129184 .

陈亮 , 唐新村 , 张阳 , 等 . 以废旧锂离子电池为原料制备棒状草酸钴粉末 [J ] . 中南大学学报(自然科学版) , 2012 , 43 ( 8 ): 2921 - 2925 .

Chen L , Tang X C , Zhang Y , et al . Preparation of rod-like cobalt oxalate powder from spent lithium-ion batteries [J ] . Journal of Central South University , 2012 , 43 ( 8 ): 2921 - 2925 .

Zhou J P , Yang X L , Wei Q Q , et al . Co 3 O 4 anchored on biochar derived from chitosan (Co 3 O 4 @BCC) as a catalyst to efficiently activate peroxymonosulfate (PMS) for degradation of phenacetin [J ] . Journal of Environmental Management , 2023 , 327 : 116895 .

Liu Y P , Zhong J J , Liu Z Y , et al . Single unit-cell layered Bi 2 Fe 4 O 9 nanosheets: synthesis, formation mechanism, and anisotropic thermal expansion [J ] . Small , 2023 , 19 ( 15 ): 2207202 .

Shen M W , Wang T , Wang Y W , et al . Synergy of bismuth and tungsten in Bi 2 WO 6 for PMS activation to enhance degradation of ammonium dibutyl dithiophosphate in flotation wastewater [J ] . Journal of Water Process Engineering , 2025 , 74 : 107845 .

Zhang Y Y , Zhou C Y , Long H M , et al . Efficient oxidation of ibuprofen by nano-plate Bi 2 Fe 4 O 9 activated peroxymonosulfate [J ] . Separation and Purification Technology , 2023 , 319 : 124044 .

Chen J J , Yu S N , Jiang X L , et al . High-efficiency PMS activation by difunctional Co-Fe PBA/g-C 3 N 4 S-scheme heterojunction for oxytetracycline degradation: Performance evaluation and mechanism insight [J ] . Science of the Total Environment , 2024 , 957 : 177326 .

Wang W H , Liu X D , Jing J F , et al . Photoelectrocatalytic peroxymonosulfate activation over CoFe 2 O 4 -BiVO 4 photoanode for environmental purification: Unveiling of multi-active sites, interfacial engineering and degradation pathways [J ] . Journal of Colloid and Interface Science , 2023 , 644 : 519 - 532 .

闫新龙 , 黄志刚 , 胡清勋 , 等 . Cu/Co掺杂多孔炭活化过硫酸盐降解水中硝基酚研究 [J ] . 化工学报 , 2023 , 74 ( 3 ): 1102 - 1112

Yan X L , Huang Z G , Hu Q X , et al . Catalytic nitrophenol degradation via peroxymonosulfate activation over Cu/Co doped porous carbon [J ] . CIESC Journal , 2023 , 74 ( 3 ): 1102 - 1112 .

Oh W D , Dong Z L , Lim T T . Generation of sulfate radical through heterogeneous catalysis for organic contaminants removal: Current development, challenges and prospects [J ] . Applied Catalysis B: Environmental , 2016 , 194 : 169 - 201 .

Ren X C , Yang Z Y , Pang X C , et al . The preparation and characterization of WS 2 nanomaterials with different morphologies and the mechan istic study of peroxymonosulfate activation for phenol degradation [J ] . Journal of Environmental Chemical Engineering , 2024 , 12 ( 5 ): 114082 .

张振飞 , 曾婷 , 聂云妮 , 等 . 赣南地区选矿药剂自然光解及光催化降解特性 [J ] . 有色金属工程 , 2018 , 8 ( 5 ): 50 - 56 .

Zhang Z F , Zeng T , Nie Y N , et al . Natural photolysis and photocatalytic degradation characteristics of reagent for beneficiation in Gannan Region [J ] . Nonferrous Metals Engineering , 2018 , 8 ( 5 ): 50 - 56 .

Liu X , Zhang J G , Wang S J , et al . Coordination dependent photocatalytic peroxymonosulfate activation on biomass derived Fe single atom catalysts for atrazine degradation [J ] . Chemical Engineering Journal , 2024 , 499 : 156625 .

韩雪 , 高生旺 , 王国英 , 等 . 铈掺杂强化碳纳米管活化过一硫酸盐实验研究 [J ] . 化工学报 , 2022 , 73 ( 4 ): 1743 - 1753 .

Han X , Gao S W , Wang G Y , et al . Research of enhanced carbon nanotubes activated peroxymonosulfate by cerium doping [J ] . CIESC Journal , 2022 , 73 ( 4 ): 1743 - 1753 .

刘波 , 聂倩倩 , 左霜霜 , 等 . 天然磁赤铁矿赋磁的Bi 2 WO 6 材料制备及其光催化降解异丁基黄药的研究 [J ] . 中国环境科学 , 2025 , 45 ( 10 ): 5459 - 5470 .

Liu B , Nie Q Q , Zuo S S , et al . Magnetization of Bi 2 WO 6 composite by using natural maghemite and its application in photocatalytic degradation of isobutyl xanthate [J ] . China Environmental Science , 2025 , 45 ( 10 ): 5459 - 5470 .

Liu Z C , Chen L , Song Y R , et al . Highly efficient PMS activation by synergistic effects of FeS 2 /CoS 2 for rapid diuron degradation: Advanced oxidation and mechanism [J ] . Environmental Research , 2025 , 270 : 121015 .

张仪杰 , 袁加巧 , 余安美 , 等 . 氧化锌矿物浮选药剂研究进展 [J ] . 有色金属(中英文) , 2025 , 15 ( 4 ): 629 - 642 .

Zhang Y J , Yuan J Q , Yu A M , et al . Research progress on flotation reagents for zinc oxide minerals [J ] . Nonferrous Metals , 2025 , 15 ( 4 ): 629 - 642 .

Nandi A , Chatterjee I B . Scavenging of superoxide radical by ascorbic acid [J ] . Journal of Biosciences , 1987 , 11 ( 1 ): 435 - 441 .

Li P , Lin Y N , Zhao S E , et al . Defect-engineered Co 3 O 4 with porous multishelled hollow architecture enables boosted advanced oxidation processes [J ] . Applied Catalysis B: Environmental , 2021 , 298 : 120596 .

王俊辉 , 张菁玮 , 孙静 , 等 . 铁酸镍负载杉木屑生物炭活化过一硫酸盐降解磷酸氯喹 [J ] . 复合材料学报 , 2024 , 41 ( 8 ): 4310 - 4323 .

Wang J H , Zhang J W , Sun J , et al . Preparation of nickel ferrite loaded fir sawdust biochar to activate peroxymonosulfate for chloroquine phosphate degradation [J ] . Acta Materiae Compositae Sinica , 2024 , 41 ( 8 ): 4310 - 4323 .

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