Reactive oxygen species (ROS) play a critical role in pollutant degradation. However, achieving efficient and sustainable catalytic systems for ROS generation remains a considerable challenge. In this study, we designed a crystalline-amorphous hybrid material (a-FeOOH-Cu0) for water decontamination via molecular oxygen activation. Characterization results indicated that a-FeOOH-Cu0 contained abundant low-valent copper species and exhibited electronic redistribution. These properties facilitated the direct cleavage of O−O bonds while bypassing the formation of *OOH intermediates, ultimately leading to a 1.44-fold and 2.91-fold increase in the concentrations of •OH and 1O2, respectively, compared to bulk Cu0. The abundant ROS significantly enhanced the removal of various organic contaminants (i.e., oxytetracycline, rhodamine B, bisphenol A). Further investigations identified 1O2 as the dominant ROS responsible for oxytetracycline degradation, with low-valent copper species serving as crucial active sites. Moreover, the a-FeOOH-Cu0 composite demonstrated high stability, good reusability, and strong resistance to matrix interference. This study highlights the potential of crystalline-amorphous hybrid materials in enhancing ROS production and provides a promising strategy for aquatic environmental remediation.
| [1] |
Cai Z F , Tang Z X , Zhang Y , Kumar N . (2024). Mechanistic understanding of oxygen activation on bulk Au(111) surface using tip-enhanced Raman spectroscopy. Angewandte Chemie International Edition, 63(19): e202318682
|
| [2] |
Cao G Q , Shen Z R , Cui J S , Yu M Y , Li W Z . (2024). Bifunctional activation of peroxymonosulfate over CuS/g-C3N4 composite for efficient degradation of tetracycline antibiotics. Chemical Engineering Journal, 483: 149082
|
| [3] |
Chen Y Y , Lin Z L , Zhang J F , Liu Y , Liang D L , Li D G , Zhang Y D , Liu H J , Chen P , Lv W Y . et al. (2023). Strategy for improvement of molecular oxygen activation capacity of PPECu by chlorine doping for water decontamination. Journal of Hazardous Materials, 460: 132421
|
| [4] |
Chi J L , Liu K , Wu S Y , Zhang W J , Shi Q T , Fang L P , Li F B . (2024). Dual-ligand-driven dark reactive oxygen species generation on iron oxyhydroxides: implications for environ-mental remediation. Environmental Science & Technology, 58(46): 20751–20760
|
| [5] |
de Almeida J C , Wang Y J , Rodrigues T A , Nunes P H H , De Mendonça V R , Falsetti P H E , Savazi L V , He T , Bardakova A V , Rudakova A V . et al. (2026). Copper-based materials for photo and electrocatalytic process: advancing renewable energy and environmental applications. Advanced Functional Materials, 36(21): 2502901
|
| [6] |
Deng E D , Kralles Z T , Mohamadi S , Das S , Dias R , Dai N , Lin H Q . (2025). Synergistically combining peracetic acid and reduced graphene oxide membranes to degrade trace organic contaminants. Chemical Engineering Journal, 517: 164302
|
| [7] |
Fan W L , Shen X L , Zhu Z L , Liu X C , Zhang H , Qiu Y L , Yin D Q . (2025). Research progress on biochar materials for new pollutants removal in the aquatic environment: a mini-review. Frontiers of Environmental Science & Engineering, 19(3): 33
|
| [8] |
Fan X H , Fu Q , Liu G R , Jia H L , Dong X L , Li Y F , Cui S . (2024). Applying molecular oxygen for organic pollutant degradation: strategies, mechanisms, and perspectives. Environmental Science and Ecotechnology, 22: 100469
|
| [9] |
Fu Y L , Xie L T , Li J , Li X G , Su M S , Liu Y T , Yan L G . (2024). Simultaneous solar-driven interfacial evaporation and phenol degradation using three-dimensional MoS2-melamine foam. Chemical Engineering Journal, 500: 156929
|
| [10] |
Giannakis S , Lin K Y A , Ghanbari F . (2021). A review of the recent advances on the treatment of industrial wastewaters by Sulfate Radical-based Advanced Oxidation Processes (SR-AOPs). Chemical Engineering Journal, 406: 127083
|
| [11] |
Gu C H , Wang S , Zhang A Y , Liu C , Jiang J , Yu H Q . (2024). Tuning electronic structure of metal-free dual-site catalyst enables exclusive singlet oxygen production and in-situ utilization. Nature Communications, 15(1): 5771
|
| [12] |
Guo H , Niu C G , Feng C Y , Liang C , Zhang L , Wen X J , Yang Y , Liu H Y , Li L , Lin L S . (2020). Steering exciton dissociation and charge migration in green synthetic oxygen-substituted ultrathin porous graphitic carbon nitride for boosted photocatalytic reactive oxygen species generation. Chemical Engineering Journal, 385: 123919
|
| [13] |
Guo H , Niu C G , Liang C , Niu H Y , Yang Y Y , Liu H Y , Tang N , Fang H X . (2021). Highly crystalline porous carbon nitride with electron accumulation capacity: promoting exciton dissociation and charge carrier generation for photocatalytic molecular oxygen activation. Chemical Engineering Journal, 409: 128030
|
| [14] |
Guo Y, Long J F, Huang J, Yu G, Wang Y J (2022). Can the commonly used quenching method really evaluate the role of reactive oxygen species in pollutant abatement during catalytic ozonation? Water Research, 215: 118275
|
| [15] |
Han H S , Choi H , Mhin S , Hong Y R , Kim K M , Kwon J , Ali G , Chung K Y , Je M , Umh H N . et al. (2019). Advantageous crystalline-amorphous phase boundary for enhanced electro-chemical water oxidation. Energy & Environmental Science, 12(8): 2443–2454
|
| [16] |
Hu X N , Zhu M S . (2024). Were persulfate-based advanced oxidation processes really understood? Basic concepts, cognitive biases, and experimental details. Environmental Science & Technology, 58(24): 10415–10444
|
| [17] |
Hu Y , Zhou Y , Ding R J , Ye X C , Chu C , Liu L L , Tian L , Jiang X H , Zhang L S , Zou J P . et al. (2025). Sustainable Fe and Cu sites double redox cycle boosting Fenton-like degradation of organic pollutants. Environmental Science & Technology, 59(31): 16812–16821
|
| [18] |
Huang D Y , Chen N , Zhu C Y , Sun H T , Fang G D , Zhou D M . (2023). Dynamic production of hydroxyl radicals during the flooding-drainage process of paddy soil: an in situ column study. Environmental Science & Technology, 57(43): 16340–16347
|
| [19] |
Lan H , Wang J W , Cheng L W , Yu D D , Wang H , Guo L . (2024). The synthesis and application of crystalline–amorphous hybrid materials. Chemical Society Reviews, 53(2): 684–713
|
| [20] |
Li T , Zhong W , Jing C Y , Li X G , Zhang T , Jiang C J , Chen W . (2020). Enhanced hydrolysis of p-Nitrophenyl phosphate by iron (Hydr)oxide nanoparticles: roles of exposed facets. Environmental Science & Technology, 54(14): 8658–8667
|
| [21] |
Ling C C , Li M Q , Li H , Liu X F , Guo F R , Liu Y , Zhang R , Zhao J C , Zhang L Z . (2025). High-spin surface FeIV = O synthesis with molecular oxygen and pyrite for selective methane oxidation. Nature Communications, 16(1): 7642
|
| [22] |
Liu Y H , Deng W X , Wu X J , Hu C , Lyu L . (2024a). Enhanced Fenton-like process over Cu/L(+)-ascorbic acid co-doping mesoporous silica for toxicity reduction of emerging contami-nants. Frontiers of Environmental Science & Engineering, 18(4): 44
|
| [23] |
Liu Y J , Wang R T , Liu S H , Xu Y S , Zhang Z R , Song Y , Yao Z P . (2024b). Nitrogen-doped carbon-coated Cu0 activates molecular oxygen for norfloxacin degradation over a wide pH range. Journal of Colloid and Interface Science, 665: 945–957
|
| [24] |
Norris K E , Leresche F , Vialykh E A , Mezyk S P , Rosario-Ortiz F L . (2025). Mechanisms of hydroxylating species production by dissolved organic matter model photosensitizers. Environmental Science & Technology, 59(41): 22122–22132
|
| [25] |
Qi W N , Long J , Feng C Q , Feng Y , Cheng D M , Liu Y W , Xue J M , Li Z J . (2019). Fe3+ enhanced degradation of oxytetracycline in water by pseudomonas. Water Research, 160: 361–370
|
| [26] |
Qin H N , Guo M N , Zhou C L , Li J R , Jing X Q , Wan Y H , Song W J , Yu H D , Peng G , Yao Z W . et al. (2024). Enhancing singlet oxygen production of dioxygen activation on the carbon-supported rare-earth oxide nanocluster and rare-earth single atom catalyst to remove antibiotics. Water Research, 252: 121184
|
| [27] |
Shi L J , Huang G X , Wang Z H , Duan Y H , Zhang Y J , Chen J J , Li W W , Yu H Q , Elimelech M . (2025). Dual-substrate synergistic catalysis for highly efficient water purification. Nature Water, 3(3): 345–353
|
| [28] |
Song W , Yang Y W , Li X G , Yan L G , Qi H Q , Xu X , Zhang Y H , Zhao Y X . (2026). Oxalate-tailored microenvironment engineering of zero-valent copper for enhanced molecular oxygen activation. Water Research, 288: 124789
|
| [29] |
Song W , Yu Z H , Li H , Ji Y Q , Cao L L , Ren L Y , Li X G , Li Y F , Xu X , Yan L G . (2024). Insights into the factors influencing the oxidation of antibiotic pollutants in nitrogen-doped biochar/PMS system: the roles of physicochemical properties and reaction pathways. Chemical Engineering Journal, 498: 155601
|
| [30] |
Sun Y M , Tang Y B , Chen F Y , Huang P , Sun W Q , Song Y H . (2024). Amorphous FeOOH shell decorated Bi2O4 for the boosted photocatalytic degradation of tetracycline under visible irradiation. Journal of Environmental Chemical Engineering, 12(2): 112181
|
| [31] |
Tan M X , Zheng X S , Yu W C , Chen B L , Chu C H . (2024). Facet-dependent productions of reactive oxygen species from pyrite oxidation. Environmental Science & Technology, 58(1): 432–439
|
| [32] |
Tian Q B , Xu X , Duan X G . (2025). Application-oriented advanced oxidation processes: research priorities for upscaling and deployment. Environmental Science & Technology, 59(32): 16823–16826
|
| [33] |
Wang K Y , Dai J , Zhan G M , Zhao L , Wang R Z , Zou X Y , Wang J X , Zheng Q , Zhou B , Zhao R . et al. (2024a). Superior singlet oxygen electrosynthesis via neighboring dual molecular oxygen coactivation for selective tetracycline detoxification. Angewandte Chemie International Edition, 63(47): e202412209
|
| [34] |
Wang M Y , Feng X F , Li S , Ma Y X , Peng Y X , Yang S J , Liu Y N , Lei H T , Dang J S , Zhang W . et al. (2024b). Spinel-type metal oxides with tailored amorphous/crystalline heterointerfaces for enhanced electrocatalytic water splitting. Advanced Functional Materials, 34(51): 2410439
|
| [35] |
Wang S H , Zhu J Y , Li T , Ge F , Zhang Z H , Zhu R L , Xie H J , Xu Y . (2022a). Oxygen vacancy-mediated CuCoFe/Tartrate-LDH catalyst directly activates oxygen to produce superoxide radicals: transformation of active species and implication for nitrobenzene degradation. Environmental Science & Technology, 56(12): 7924–7934
|
| [36] |
Wang Z W , Wang W L , Wang J , Yuan Y , Wu Q Y , Hu H Y . (2022b). High-valent iron-oxo species mediated cyclic oxidation through single-atom -Fe-N6 sites with high peroxymonosulfate utilization rate. Applied Catalysis B: Environmental, 305: 121049
|
| [37] |
Xu J , Yu C Z , Chen F J , Li F F , Yu W C , Wang S L , Xiong L , Geng F L , Lv J T , Wang X W . et al. (2025). Unexpected spontaneous generation of superoxide radicals: water-solid collision as an atypical source. Angewandte Chemie International Edition, 64(42): e202511594
|
| [38] |
Zhang C W , Kong C P , Tratnyek P G , Qin C Y , Zhao Y S , Piao Y . (2024a). Effect of interfacial action on the generation and transformation of reactive oxygen species in tripolyphosphate-enhanced heterogeneous Fe3O4/O2 systems. Environmental Science & Technology, 58(2): 1378–1389
|
| [39] |
Zhang P , Sun M L , Zhou C Y , He C S , Liu Y , Zhang H , Xiong Z K , Liu W , Zhou P , Lai B . (2024b). Origins of selective oxidation in carbon-based nonradical oxidation processes toward organic pollutants: quantitative structure-activity relationships (QSARs). Environmental Science & Technology, 58(10): 4781–4791
|
| [40] |
Zhang P P , Yang Y Y , Duan X G , Wang S B . (2024c). Oxidative polymerization versus degradation of organic pollutants in heterogeneous catalytic persulfate chemistry. Water Research, 255: 121485
|
| [41] |
Zhang Q , Zheng D , Bai B , Ma Z Y , Zong S C . (2024d). Insight into antibiotic removal by advanced oxidation processes (AOPs): performance, mechanism, degradation pathways, and ecotoxicity assessment. Chemical Engineering Journal, 500: 157134
|
| [42] |
Zhang T , Liu Y Q , Zhang Y H , Wang P F , Yue S , Fu T , Zhao Z Y , Zhan S H . (2025a). Zn-Bi catalytic pair enables selective superoxide radical generation for simultaneous removal of organic pollutants and heavy metals. Advanced Materials, 37(45): e12489
|
| [43] |
Zhang X , Gang D D , Lei X B , Wang T J , Lian Q Y , Holmes W E , Fei L , Zappi M E , Yao H . (2022). Surface-bound hydroxyl radical-dominated degradation of sulfamethoxazole in the amorphous FeOOH/ peroxymonosulfate system: the key role of amorphous structure enhancing electron transfer. Environmental Research, 214: 113964
|
| [44] |
Zhang X F , Xie H H , Ma J X , Zhan J H , Yang Z H , Zhang Y , Yang Z F . (2024e). Intraplanar heterostructure-mediated activation of peroxydisulfate for singular-electron-transfer degradation of organic pollutants. Chemical Engineering Journal, 499: 155973
|
| [45] |
Zhang X F , Zhan J H , Jia X B , Ma J X , Han B , Wang Z L , Li F L , Wang Y T , Zhang Y . (2025b). Enhanced peroxymonosulfate activation by V2O5/g-C3N4 heterojunction for rapid degradation of chloramphenicol: role of the built-in electric field. Separation and Purification Technology, 361: 131506
|
| [46] |
Zhang Y , Wu Y L , Zhang Z Q , Xu D D , Zhang X F , Yang Z H , Han B , Zhan J H , Wang Y T . (2025c). Low-power LED lamp-driven dual-defect carbon nitride activated peroxydisulfate for bisphenol S degradation: performance, DFT calculations, and mechanism. Journal of Environmental Chemical Engineering, 13(1): 115123
|
| [47] |
Zhang Y J , Tao J S , Yu H Q . (2025d). Optimizing compatibility between oxidants and catalysts for heterogeneous catalytic water purification. Environmental Science & Technology, 59(23): 11935–11944
|
| [48] |
Zhang Y P , Gao F , Wang D Q , Li Z L , Wang X M , Wang C Q , Zhang K W , Du Y K . (2023). Amorphous/crystalline heterostructure transition-metal-based catalysts for high-performance water splitting. Coordination Chemistry Reviews, 475: 214916
|
| [49] |
Zhao G Q , Tan M X , Wu B B , Zheng X S , Xiong R X , Chen B L , Kappler A , Chu C H . (2023). Redox oscillations activate thermodynamically stable iron minerals for enhanced reactive oxygen species production. Environmental Science & Technology, 57(23): 8628–8637
|
| [50] |
Zhao H H , Xu X , Cui W Q , Geng L L , Peng X M , Yang J R , Shao X Z , Liu Y B . (2025a). Synchronization strategy for activity and stability in Fenton-Like single-atom catalysis. Advanced Materials, 37(30): 2503217
|
| [51] |
Zhao X H , Tong J T , Bai S , Qian J . (2025b). Dual-metal-catalyzed Fenton-like reaction on CdxZn1–xS @biochar: mechanistic insights into sulfide-metal interactions for water purification. Applied Catalysis B: Environment and Energy, 379: 125654
|
| [52] |
Zheng N C , He X , Hu R T , Wang R L , Zhou Q , Lian Y K , Hu Z F . (2022). In-situ production of singlet oxygen by dioxygen activation on iron phosphide for advanced oxidation processes. Applied Catalysis B: Environment and Energy, 307: 121157
|
| [53] |
Zheng N C , Tang X H , Lian Y K , Ou Z S , Zhou Q , Wang R L , Hu Z F . (2023). Low-valent copper on molybdenum triggers molecular oxygen activation to selectively generate singlet oxygen for advanced oxidation processes. Journal of Hazardous Materials, 452: 131210
|
| [54] |
Zheng X Y , Yang Y W , Yan L G , Song W , Li Y F , Li X G . (2025). Efficient production of singlet oxygen via dioxygen activation on Cu0 decorated MoS2 facilitates the elimination of oxytetracycline. Journal of Colloid and Interface Science, 679: 656–669
|
| [55] |
Zhou L L , Liu Y T , Shi H , Qing Y , Chen C , Shen L G , Zhou M Z , Li B S , Lin H J . (2024). Molecular oxygen activation: innovative techniques for environmental remediation. Water Research, 250: 121075
|
| [56] |
Zhu J D , Ji Q Y , Lu P P , Zhou W D , Zhong Q , Zhang K , Liu Y Z , Zuo G C , Xu Z , Yang S G . et al. (2025). Crystalline-amorphous hybrid of MoS2 for enhanced piezo-catalytic activation of peroxomonosulfate toward organic pollutants degradation. Advanced Functional Materials, 35(15): 2419597
|
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