Low-temperature mineral engineering stabilizes anchored cobalt sites for ultrafast antibiotic destruction via electron transfer-driven radical/nonradical synergy

Abstract

Current advanced oxidation technologies face critical limitations in sustainability and efficiency, where conventional transition metal catalysts require energy-intensive synthesis (> 800 °C) and exhibit severe metal leaching. Although carbon supports suffer from pH-dependent deactivation and poor cycling stability, natural silicate minerals present an eco-friendly alternative owing to global abundance, structural robustness, and intrinsic surface functionality. To overcome existing barriers, we engineered cobalt-anchored attapulgite (Co-ATP) through precisely controlled low-temperature synthesis (80 °C), achieving uniform cobalt dispersion. This mineral engineering strategy suppressed cobalt leaching while enabling ultrafast antibiotic degradation (> 99% tetracycline removal in 6 min). Optimized cobalt loading and oxidant dosage minimized chemical consumption and reduced sulfate byproducts. The catalyst demonstrated exceptional environmental resilience, maintaining > 90% efficiency across five reuse cycles under broad pH conditions (4.0–9.0) and in complex matrices, including lake water and wastewater, with < 3% activity loss. Mechanistic investigations revealed electron-transfer-dominated activation, generating radical/nonradical synergy. Through electrochemical analysis, electron paramagnetic resonance, and quenching experiments, it was confirmed that interfacial electron shuttling was the primary degradation pathway. Liquid chromatography-mass spectrometry identified non-toxic degradation intermediates, and Fukui function calculations rationalized selective bond cleavage at high-activity sites. This work establishes a new paradigm for sustainable water remediation, where mineral-anchored cobalt catalysis eliminates energy and toxicity barriers in practical water treatment scenarios, offering a scalable solution for antibiotic-polluted ecosystems.

Graphical abstract

Keywords

Silicate minerals / Peroxymonosulfate / Antibiotics / Advanced oxidation

Highlight

	● Co-ATP was prepared by low-temperature engineering derived from silicate minerals.
	● Electron transfer-driven radical/nonradical synergy.
	● Optimized system reduces oxidant dosage while suppressing sulfate byproducts.
	● Environmental adaptability and cycle stability.

References

[1] Ahmad S , Liu L N , Zhang S C , Tang J C . (2023). Nitrogen-doped biochar (N-doped BC) and iron/nitrogen co-doped biochar (Fe/N co-doped BC) for removal of refractory organic pollutants. Journal of Hazardous Materials, 446: 130727

[2] Chen W , Zhang J K , Hong T , Peng X W , Fu F . (2025). Dual heteroatom-doped porous biochar from chitosan/lignosulfonate gels for enhanced removal of tetracycline by persulfate activation: performance and mechanism. International Journal of Biological Macromolecules, 295: 139690

[3] Dai N , Yang L , Liu X Y , Gao L H , Zheng J S , Zhang K , Song D , Sun T , Luo S Y , Liu X Y . et al. (2023). Enhanced photo-Fenton-like performance of biotemplated manganese-doped cobalt silicate catalysts. Journal of Colloid and Interface Science, 652: 1812–1824

[4] Dou J B , Cheng J , Lu Z J , Tian Z Q , Xu J M , He Y . (2022). Biochar co-doped with nitrogen and boron switching the free radical based peroxydisulfate activation into the electron-transfer dominated nonradical process. Applied Catalysis B: Environmental, 301: 120832

[5] Gu L H , Han J J , Chen M F , Zhou W J , Wang X F , Xu M , Lin H C , Liu H D , Chen H X , Chen J Z . et al. (2022). Enabling robust structural and interfacial stability of micron-Si anode toward high-performance liquid and solid-state lithium-ion batteries. Energy Storage Materials, 52: 547–561

[6] Hu S G , Zhang H Z , Yang Y J , Cui K P , Ao J J , Tong X N , Shi M C , Wang Y , Chen X , Li C X . et al. (2024). Comprehensive insight into the occurrence characteristics, influencing factors and risk assessments of antibiotics in the Chaohu Basin. Frontiers of Environmental Science & Engineering, 18(5): 57

[7] Huang Y H , Zhang J L , Guo Z , Zang H C , Zheng M S , Hao T , Wei J . (2025). Bimetallic Fe-Mo modified N-doped carbon materials activating peroxymonosulfate for acetaminophen degradation: synergistic effects of free radicals and electron transfer process. Environmental Research, 270: 121013

[8] Huang Y X , Zhao S Y , Chen K Y , Huang B C , Jin R C . (2024). A review of persulfate-based advanced oxidation system for decontaminating organic wastewater via non-radical regime. Frontiers of Environmental Science & Engineering, 18(11): 134

[9] Lei X Y , Zhao H H , Bai C , Geng L L , Xu X . (2025). Wood-derived catalysts for green and stable Fenton-like chemistry: from basic mechanisms to catalytic modules and future inspiration. Chinese Chemical Letters, 36(10): 111550

[10] Li P J , Xu D L , Cheng X X , Liu P , Luo X S , Yang J X , Liang H . (2025). Nonradical-dominated nanoconfined iron single-atom catalytic membrane to enhance peroxymonosulfate activation for efficient water decontamination. Water Research, 285: 124106

[11] Li X , Wang S W , Chen P , Xu B K , Zhang X , Xu Y H , Zhou R , Yu Y , Zheng H L , Yu P . et al. (2023). ZIF-derived non-bonding Co/Zn coordinated hollow carbon nitride for enhanced removal of antibiotic contaminants by peroxymonosulfate activation: performance and mechanism. Applied Catalysis B: Environmental, 325: 122401

[12] Liang C , Yin S J , Huang P , Yang S S , Wang Z C , Zheng S L , Li C Q , Sun Z M . (2024). The critical role of minerals in persulfate-based advanced oxidation process: catalytic properties, mechanism, and prospects. Chemical Engineering Journal, 482: 148969

[13] Lu Y S , Wang A Q . (2022). From structure evolution of palygorskite to functional material: a review. Microporous and Mesoporous Materials, 333: 111765

[14] Mao G N , Wang D L , Bai Y H , Qu J H . (2023). Mitigating microbiological risks of potential pathogens carrying antibiotic resistance genes and virulence factors in receiving rivers: benefits of wastewater treatment plant upgrade. Frontiers of Environmental Science & Engineering, 17(7): 82

[15] Mao J S , Yin K X , Zhang Y , Shang Y N , Li Q , Li Y W , Gao B Y , Xu X . (2024). Ultrafast oxidation of refractory organics via PMS activation by Si–O doped biomimetic montmorillonite: simultaneous enhanced radical/electron transfer pathways and efficient catalytic membrane system. Applied Catalysis B: Environmental, 342: 123428

[16] Ren W , Cheng C , Shao P H , Luo X B , Zhang H , Wang S B , Duan X G . (2022). Origins of electron-transfer regime in persulfate-based nonradical oxidation processes. Environmental Science & Technology, 56(1): 78–97

[17] Shi Q Q , Hou Y Q , Zhu Q T , Hao Y M . (2025). MOF-derived CuCo carbon microspheres assembled with nitrogen-doped carbon nanotubes as PMS activator for the efficient degradation of p-nitrophenol. Separation and Purification Technology, 354: 129107

[18] Sun L , Zhang Z Y , Jiang H , Deng X Y . (2021). Facile synthesis of magnetic mesoporous silica spheres for efficient removal of methylene blue via catalytic persulfate activation. Separation and Purification Technology, 256: 117801

[19] Tian M T , Liu Y , Zhang S Z , Yu C , Ostrikov K , Zhang Z H . (2024). Overcoming the permeability-selectivity challenge in water purification using two-dimensional cobalt-functionalized vermiculite membrane. Nature Communications, 15(1): 391

[20] Tian Q B , Chang J L , Peng X M , Geng L L , Gao B Y , Li Q , Gao Y , Xu X . (2025a). Iron single-atom based double-reaction-center catalysis triggers internal-driven and external-driven pathways for green Fenton-like chemistry. Angewandte Chemie International Edition, 64(19): e202503995

[21] Tian Q B , Yu B L , Li Z H , Hong W , Li Q , Xu X . (2025b). Versatile catalytic membranes anchored with metal-nitrogen based metal oxides for ultrafast Fenton-like oxidation. Chinese Chemical Letters, 36(6): 110322

[22] Vinayagam V , Palani K N , Ganesh S , Rajesh S , Akula V V , Avoodaiappan R , Kushwaha O S , Pugazhendhi A . (2024). Recent developments on advanced oxidation processes for degradation of pollutants from wastewater with focus on antibiotics and organic dyes. Environmental Research, 240: 117500

[23] Wang Z , Meng C C , Zhang W , Zhang S Z , Yang B , Zhang Z H . (2022). Honeycomb-like holey Co₃O₄ membrane triggered peroxymonosulfate activation for rapid degradation of organic contaminants. Science of the Total Environment, 814: 152698

[24] Wen S Q , Lin W L , He Q , Xu Y Q , Shi X Y , Guo J M , Gao Y , Xue W J . (2024). Evaluation of a novel attapulgite loaded sulfidized nanoscale zero-valent iron for immobilization of Pb in sediment: performance, microenvironmental response, and mechanisms. Chemical Engineering Journal, 498: 155676

[25] Wu Q Y , Yang Z W , Wang Z W , Wang W L . (2023). Oxygen doping of cobalt-single-atom coordination enhances peroxymonosulfate activation and high-valent cobalt-oxo species formation. Proceedings of the National Academy of Sciences, 120(16): e2219923120

[26] Xiong Y , Zhou Y T , Liu Y Y , Zhou X , Du Z J , Men R , Wang J J . (2025). Peroxymonosulfate activation by iron-cluster-modified Mn single atom catalyst for ciprofloxacin removal: non-radical pathway dominated by ¹O₂ and high-valent metal-oxygen species. Separation and Purification Technology, 366: 132730

[27] Xu Y Y , Shen W Q . (2023). Flocculation synergistic with nano zero-valent iron augmented attapulgite @chitosan as Fenton-like catalyst for the treatment of landfill leachate. Environmental Technology, 44(23): 3605–3613

[28] Yu Y Q , Ji Y F , Lu J H , Yin X M , Zhou Q S . (2021). Degradation of sulfamethoxazole by Co₃O₄-palygorskite composites activated peroxymonosulfate oxidation. Chemical Engineering Journal, 406: 126759

[29] Zhai S , Chen Y W , Ge M Q . (2023). Efficient polyvinyl alcohol degradation via peroxymonosulfate activated by natural illite supported CoNi₃O₄ nanosheets. Chemical Engineering Journal, 452: 139155

[30] Zhang D Y , Shi L , Dawolo E H , Chen B F , Ding N , Liu H . (2024a). Synthesis of Fe-loaded biochar obtained from rape straw for enhanced degradation of emerging contaminant antibiotic metronidazole. Water, 16(13): 1822

[31] Zhang P P , Yang Y Y , Duan X G , Wang S B . (2024b). Oxidative polymerization versus degradation of organic pollutants in heterogeneous catalytic persulfate chemistry. Water Research, 255: 121485

[32] Zhang Y J , Liu S Y , Chen D D , Xu X . (2024c). Iron single-atom/clusters catalysts derived from iron-rich Enteromorpha after urea-saturation for Fenton-like reaction. Chinese Chemical Letters, 35(3): 108666

[33] Zhou K Q , Lai L F , Zhen Y C , Hong Z S , Guo J H , Huang Z G . (2017). Rational design of Co₃O₄/Co/carbon nanocages composites from metal organic frameworks as an advanced lithium-ion battery anode. Chemical Engineering Journal, 316: 137–145

[34] Zhou L , Yan Y B , Mao H Y , Zhou S Y , Hui J Y , Li H D , Li M S , Zhao Y J , Zhang Q , Xia S S . (2023). Development of attapulgite based catalytic membrane for activation of peroxymonosulfate: a singlet oxygen-dominated catalytic oxidation process for sulfamethoxazole degradation. Separation and Purification Technology, 312: 123382

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