Highly Selective Singlet Oxygen Generation via an Asymmetric Co-O-Fe Dual-site for Enhanced Water Treatment: Importance of Switching the Ozone Activation Pathway

Qian Hu; Shanli Wang; Kaixing Fu; Guangpeng Yang; Licong Xu; Wenbin Jiang; Minghua Wu; Wangyang Lu; Xiaomin Zhu; Jinming Luo

doi:10.1016/j.eng.2025.12.016

Engineering ›› :202512016 DOI: 10.1016/j.eng.2025.12.016

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Highly Selective Singlet Oxygen Generation via an Asymmetric Co-O-Fe Dual-site for Enhanced Water Treatment: Importance of Switching the Ozone Activation Pathway

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Abstract

The singlet oxygen (¹O₂)-driven nonradical oxidation pathway has shown great promise for the degradation of organic pollutants with high ionization potentials (IPs) in complex water matrices because of its longer half-life and stronger resistance to environmental interference. However, the symmetric configuration of the active sites (e.g., Fe-O-Fe) in heterogeneous catalysts largely restricts the efficacy of ¹O₂ generation during ozone activation. In this study, we constructed an asymmetric Co-O-Fe dual-site in bimetallic metal organic frameworks (MOFs) with enhanced electron delocalization to switch the ozone activation pathway from radical-dominant to nonradical-dominant. By combining experimental and theoretical analyses, we revealed that breaking the symmetry of iron sites with Co incorporation optimizes the local electronic structure, thereby facilitating ozone adsorption and reducing the O-O bond scission energy barrier to produce ¹O₂. As a result, the constructed asymmetric Co-O-Fe dual-site demonstrates impressive 6.6 and 2.0 fold increases in ¹O₂ selectivity and phenol degradation efficiency, surpassing the performance of the state-of-the-art ozonation catalysts. Furthermore, the Co-O-Fe dual-site/O₃ system could efficiently and stably remove diverse high-IP organic pollutants in complex water matrices, following a positive linear correlation (R² > 0.97) between the kinetic rate constants and theoretical IP values, which further highlights the unique and critical role of ¹O₂. This work advances the understanding and design of efficient dual-site catalysts for selective ¹O₂ generation and sustainable high-IP pollutant degradation.

Keywords

Catalytic ozonation / Asymmetric Co-O-Fe dual-site / Activation pathway / Singlet oxygen / Water treatment

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Qian Hu, Shanli Wang, Kaixing Fu, Guangpeng Yang, Licong Xu, Wenbin Jiang, Minghua Wu, Wangyang Lu, Xiaomin Zhu, Jinming Luo. Highly Selective Singlet Oxygen Generation via an Asymmetric Co-O-Fe Dual-site for Enhanced Water Treatment: Importance of Switching the Ozone Activation Pathway. Engineering 202512016 DOI:10.1016/j.eng.2025.12.016

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References

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[1]	Mekonnen MM, Hoekstra AY. Four billion people facing severe water scarcity. Sci Adv 2016; 2(2):e1500323.

[2]	Eliasson J. The rising pressure of global water shortages. Nature 2015;517:6.

[3]	Chen Z, An F, Zhang Y, Liang Z, Liu W, Xing M. Single-atom Mo-Co catalyst with low biotoxicity for sustainable degradation of high-ionization-potential organic pollutants. Proc Natl Acad Sci USA 2023; 120(29):e2305933120.

[4]	Zhang J, Shan C, Zhang W, Pan B. In situ ligand-modulated activation of inert Ce (III/IV) into ozonation catalyst for efficient water treatment. Proc Natl Acad Sci USA 2023; 120(35):e2305255120.

[5]	Guo Y, Long J, Huang J, Yu G, Wang Y. Can the commonly used quenching method really evaluate the role of reactive oxygen species in pollutant abatement during catalytic ozonation? Water Res 2022;215:118275.

[6]	Wang Y, Duan X, Xie Y, Sun H, Wang S. Nanocarbon-based catalytic ozonation for aqueous oxidation: engineering defects for active sites and tunable reaction pathways. ACS Catal 2020; 10(22):13383-414.

[7]	Zhou Q, Song C, Wang P, Zhao Z, Li Y, Zhan S. Generating dual-active species by triple-atom sites through peroxymonosulfate activation for treating micropollutants in complex water. Proc Natl Acad Sci USA 2023; 120(13): e2300085120.

[8]	Wu Z, Huang B, Wang X, He CS, Liu Y, Du Y, et al. Facilely tuning the first-shell coordination microenvironment in iron single-atom for Fenton-like chemistry toward highly efficient wastewater purification. Environ Sci Technol 2023; 57 (37):14046-57.

[9]	Ren T, Yin M, Chen S, Ouyang C, Huang X, Zhang X. Single-atom Fe-N₄ sites for catalytic ozonation to selectively induce a nonradical pathway toward wastewater purification. Environ Sci Technol 2023; 57(9):3623-33.

[10]	Yu G, Wang Y, Cao H, Zhao H, Xie Y. Reactive oxygen species and catalytic active sites in heterogeneous catalytic ozonation for water purification. Environ Sci Technol 2020; 54(10):5931-46.

[11]	Hu Q, Zhang M, Xu L, Wang S, Yang T, Wu M, et al. Unraveling timescale-dependent Fe-MOFs crystal evolution for catalytic ozonation reactivity modulation. J Hazard Mater 2022;431:128575.

[12]	Wei K, Cao X, Gu W, Liang P, Huang X, Zhang X. Ni-induced C-Al₂O₃-framework (Ni CAF) supported core-multishell catalysts for efficient catalytic ozonation: a structure-to-performance study. Environ Sci Technol 2019; 53(12):6917-26.

[13]	Wang Y, Chen L, Cao H, Chi Z, Chen C, Duan X, et al. Role of oxygen vacancies and Mn sites in hierarchical Mn₂O₃/LaMnO_3-δ perovskite composites for aqueous organic pollutants decontamination. Appl Catal B 2019;245:546-54.

[14]	Li X, Liu L, Ren X, Gao J, Huang Y, Liu B. Microenvironment modulation of single-atom catalysts and their roles in electrochemical energy conversion. Sci Adv 2020; 6(39):eabb6833.

[15]	Xiao M, Chen Y, Zhu J, Zhang H, Zhao X, Gao L, et al. Climbing the apex of the ORR volcano plot via binuclear site construction: electronic and geometric engineering. J Am Chem Soc 2019; 141(44):17763-70.

[16]	Zhou W, Su H, Cheng W, Li Y, Jiang J, Liu M, et al. Regulating the scaling relationship for high catalytic kinetics and selectivity of the oxygen reduction reaction. Nat Commun 2022; 13(1):6414.

[17]	Wang Z, Yi Z, Wong LW, Tang X, Wang H, Wang H, et al. Oxygen doping cooperated with Co-N-Fe dual-catalytic sites: synergistic mechanism for catalytic water purification within nanoconfined membrane. Adv Mater 2024; 36(30):2404278.

[18]	Zhao Z, Wang P, Song C, Zhang T, Zhan S, Li Y. Enhanced interfacial electron transfer by asymmetric Cu-O_v-in sites on In₂O₃ for efficient peroxymonosulfate activation. Angew Chem Int Ed 2023; 62(11):e202216403.

[19]	Gu CH, Wang S, Zhang AY, Liu C, Jiang J, Yu HQ. Tuning electronic structure of metal-free dual-site catalyst enables exclusive singlet oxygen production and in-situ utilization. Nat Commun 2024; 15(1):5771.

[20]	Song J, Hou N, Liu X, Antonietti M, Zhang P, Ding R, et al. Asymmetrically coordinated CoB₁N₃ moieties for selective generation of high-valence Co-oxo species via coupled electron-proton transfer in Fenton-like reactions. Adv Mater 2023; 35(23):2209552.

[21]	Yao Y, Wang C, Yang Y, Zhang S, Yan X, Xiao C, et al. Mn-Co dual sites relay activation of peroxymonosulfate for accelerated decontamination. Appl Catal B 2023;330:122656.

[22]	Cai G, Yan P, Zhang L, Zhou HC, Jiang HL. Metal-organic framework-based hierarchically porous materials: synthesis and applications. Chem Rev 2021; 121(20):12278-326.

[23]	Islamoglu T, Chen Z, Wasson MC, Buru CT, Kirlikovali KO, Afrin U, et al. Metal-organic frameworks against toxic chemicals. Chem Rev 2020; 120 (16):8130-60.

[24]	Sanati S, Morsali A, García H. First-row transition metal-based materials derived from bimetallic metal-organic frameworks as highly efficient electrocatalysts for electrochemical water splitting. Energy Environ Sci 2022; 15(8):3119-51.

[25]	Liu L, Corma A. Bimetallic sites for catalysis: from binuclear metal sites to bimetallic nanoclusters and nanoparticles. Chem Rev 2023; 123(8):4855-933.

[26]	Yu D, Wang L, Yang T, Yang G, Wang D, Ni H, et al. Tuning Lewis acidity of iron-based metal-organic frameworks for enhanced catalytic ozonation. Chem Eng J 2021;404:127075.

[27]	Yu D, Wu M, Hu Q, Wang L, Lv C, Zhang L. Iron-based metal-organic frameworks as novel platforms for catalytic ozonation of organic pollutant: efficiency and mechanism. J Hazard Mater 2019;367:456-64.

[28]	Luo YR. Comprehensive handbook of chemical bond energies. Boca Raton, FL: CRC Press; 2007.

[29]	Horcajada P, Serre C, Maurin G, Ramsahye NA, Balas F, Vallet-Regí M, et al. Flexible porous metal-organic frameworks for a controlled drug delivery. J Am Chem Soc 2008; 130(21):6774-80.

[30]	Hou J, Ashling CW, Collins SM, Krajnc A, Zhou C, Longley L, et al. Metal-organic framework crystal-glass composites. Nat Commun 2019; 10(1):2580.

[31]	Zhu Y, Ren B, Qiu Y, Zhou Q, Chang J, Lin Z, et al. Nanoporous cerium-doped MIL-53(Fe)-NH₂ for effective and selective removal of phosphate from wastewater. ACS Appl Nano Mater 2024; 7(17):20700-13.

[32]	Wu Q, Siddique MS, Guo Y, Wu M, Yang Y, Yang H. Low-crystalline bimetallic metal-organic frameworks as an excellent platform for photo-Fenton degradation of organic contaminants: intensified synergism between hetero-metal nodes. Appl Catal B 2021;286:119950.

[33]	Yang T, Yu D, Wang D, Yang T, Li Z, Wu M, et al. Accelerating Fe(III)/Fe(II) cycle via Fe(II) substitution for enhancing Fenton-like performance of Fe-MOFs. Appl Catal B 2021;286:119859.

[34]	Roy D, Neogi S, De S. Visible light assisted activation of peroxymonosulfate by bimetallic MOF based heterojunction MIL-53(Fe/Co)/CeO₂ for atrazine degradation: pivotal roles of dual redox cycle for reactive species generation. Chem Eng J 2022;430:133069.

[35]	Liu Y, Wang C, Ju S, Li M, Yuan A, Zhu G. FeCo-based hybrid MOF derived active species for effective oxygen evolution. Prog Nat Sci Mater Intern 2020; 30 (2):185-91.

[36]	Breeze MI, Clet G, Campo BC, Vimont A, Daturi M, Grenèche JM, et al. Isomorphous substitution in a flexible metal-organic framework: mixed-metal, mixed-valent MIL-53(Fe) type materials. Inorg Chem 2013; 52 (14):8171-82.

[37]	Liu K, Wang X, Wang N, Zhang R, Yang M, Hou B, et al. Effective electrochemical water oxidation to H₂O₂ based on a bimetallic Fe/Co metal-organic framework. Energy Adv 2024; 3(11):2842-50.

[38]	Abuzalat O, Tantawy H, Mokhtar M, Baraka A. Nano-porous bimetallic organic frameworks (Fe/Co)-BDC, a breathing MOF for rapid and capacitive removal of Cr-oxyanions from water. J Water Process Eng 2022;46:102537.

[39]	Sunil J, Narayana C, Kumari G, Jayaramulu K. Raman spectroscopy, an ideal tool for studying the physical properties and applications of metal-organic frameworks (MOFs). Chem Soc Rev 2023; 52(10):3397-437.

[40]	Shen P, Hou K, Chen F, Pi Z, He L, Chen S, et al. Ultra-rapid and long-lasting activation of peracetic acid by Cu-Co spinel oxides for eliminating organic contamination: role of radical and non-radical catalytic oxidation. Chem Eng J 2023;463:142344.

[41]	Wang Q, Lu J, Jiang Y, Yang S, Yang Y, Wang Z. FeCo bimetallic metal organic framework nanosheets as peroxymonosulfate activator for selective oxidation of organic pollutants. Chem Eng J 2022;443:136483.

[42]	Zheng Y, Liu Q, Shan C, Su Y, Fu K, Lu S, et al. Defective ultrafine MnO_x nanoparticles confined within a carbon matrix for low-temperature oxidation of volatile organic compounds. Environ Sci Technol 2021; 55(8):5403-11.

[43]	Deng L, Hung SF, Liu S, Zhao S, Lin ZY, Zhang C, et al. Accelerated proton transfer in asymmetric active units for sustainable acidic oxygen evolution reaction. J Am Chem Soc 2024; 146(33):23146-57.

[44]	Ha M, Kim DY, Umer M, Gladkikh V, Myung CW, Kim KS. Tuning metal single atoms embedded in N_xC_y moieties toward high-performance electrocatalysis. Energy Environ Sci 2021; 14(6):3455-68.

[45]	Zhang XY, Li FT, Dong YW, Dong B, Dai FN, Liu CG, et al. Dynamic anion regulation to construct S-doped FeOOH realizing 1000 mA cm^-2-level-current-density oxygen evolution over 1000 h. Appl Catal B 2022;315:121571.

[46]	Zhang C, Qi Q, Mei Y, Hu J, Sun M, Zhang Y, et al. Rationally reconstructed metal-organic frameworks as robust oxygen evolution electrocatalysts. Adv Mater 2023; 35(8):2208904.

[47]	Zhang B, Shen Y, Liu B, Ji J, Dai W, Huang P, et al. Boosting ozone catalytic oxidation of toluene at room temperature by using hydroxyl-mediated MnO_x/Al₂O₃ catalysts. Environ Sci Technol 2023; 57(17):7041-50.

[48]	Huang M, Li YS, Zhang CQ, Cui C, Huang QQ, Li M, et al. Facilely tuning the intrinsic catalytic sites of the spinel oxide for peroxymonosulfate activation: from fundamental investigation to pilot-scale demonstration. Proc Natl Acad Sci USA 2022; 119(30):e2202682119.

[49]	Zhao Z, Tan H, Zhang P, Liang X, Li T, Gao Y, et al. Turning the inert element zinc into an active single-atom catalyst for efficient Fenton-like chemistry. Angew Chem Int Ed 2023; 62(18):e202219178.

[50]	Foley S, Rotureau P, Pin S, Baldacchino G, Renault JP, Mialocq JC. Radiolysis of confined water: production and reactivity of hydroxyl radicals. Angew Chem Int Ed 2005; 44(1):110-2.

[51]	Gao Y, Chen Z, Zhu Y, Li T, Hu C. New insights into the generation of singlet oxygen in the metal-free peroxymonosulfate activation process: important role of electron-deficient carbon atoms. Environ Sci Technol 2020; 54 (2):1232-41.

[52]	Guo Y, Zhang Y, Yu G, Wang Y. Revisiting the role of reactive oxygen species for pollutant abatement during catalytic ozonation: the probe approach versus the scavenger approach. Appl Catal B 2021;280:119418.

[53]	Guo Y, Zhan J, Yu G, Wang Y. Evaluation of the concentration and contribution of superoxide radical for micropollutant abatement during ozonation. Water Res 2021;194:116927.

[54]	Zhou Y, Zhou Q, Liu H, Xu W, Wang Z, Qiao S, et al. Asymmetric dinitrogen-coordinated nickel single-atomic sites for efficient CO₂ electroreduction. Nat Commun 2023; 14(1):3776.

[55]	Zeng Y, Zhao J, Wang S, Ren X, Tan Y, Lu YR, et al. Unraveling the electronic structure and dynamics of the atomically dispersed iron sites in electrochemical CO₂ reduction. J Am Chem Soc 2023; 145(28):15600-10.

[56]	Qu W, Luo M, Tang Z, Zhong T, Zhao H, Hu L, et al. Accelerated catalytic ozonation in a mesoporous carbon-supported atomic Fe-N₄ sites nanoreactor: confinement effect and resistance to poisoning. Environ Sci Technol 2023; 57 (35):13205-16.

[57]	Qu W, Tang Z, Tang S, Zhong T, Zhao H, Tian S, et al. Precisely constructing orbital coupling-modulated iron dinuclear site for enhanced catalytic ozonation performance. Proc Natl Acad Sci USA 2024; 121(16):e2319119121.

[58]	Ma D, Lian Q, Zhang Y, Huang Y, Guan X, Liang Q, et al. Catalytic ozonation mechanism over M₁-N₃C₁ active sites. Nat Commun 2023; 14(1):7011.

[59]	Yu G, Wu Y, Cao H, Ge Q, Dai Q, Sun S, et al. Insights into the mechanism of ozone activation and singlet oxygen generation on N-doped defective nanocarbons: a DFT and machine learning study. Environ Sci Technol 2022; 56(12):7853-63.

[60]	Liang L, Cao J, Zhang Y, Liu X, Li J, Yang B, et al. Selective adsorption of high ionization potential value organic pollutants in wastewater. Proc Natl Acad Sci USA 2024; 121(29):e2403766121.

[61]	Thommes M, Kaneko K, Neimark AV, Olivier JP, Rodriguez-Reinoso F, Rouquerol J, et al. Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC technical report). Pure Appl Chem 2015; 87(9-10):1051-69.

[62]	Hu P, Su H, Chen Z, Yu C, Li Q, Zhou B, et al. Selective degradation of organic pollutants using an efficient metal-free catalyst derived from carbonized polypyrrole via peroxymonosulfate activation. Environ Sci Technol 2017; 51(19):11288-96.

[63]	Liu X, Qin H, Xing S, Liu Y, Chu C, Yang D, et al. Selective removal of organic pollutants in groundwater and surface water by persulfate-assisted advanced oxidation: the role of electron-donating capacity. Environ Sci Technol 2023; 57 (36):13710-20.