Facile synthesis of Cu-doped manganese oxide octahedral molecular sieve for the efficient degradation of sulfamethoxazole via peroxymonosulfate activation

Abstract

Advanced processes for peroxymonosulfate (PMS)-based oxidation are efficient in eliminating toxic and refractory organic pollutants from sewage. The activation of electron-withdrawing HSO₅⁻ releases reactive species, including sulfate radical (·SO₄⁻), hydroxyl radical (·OH), superoxide radical (·O₂⁻), and singlet oxygen (¹O₂), which can induce the degradation of organic contaminants. In this work, we synthesized a variety of M-OMS-2 nanorods (M = Co, Ni, Cu, Fe) by doping Co²⁺, Ni²⁺, Cu²⁺, or Fe³⁺ into manganese oxide octahedral molecular sieve (OMS-2) to efficiently remove sulfamethoxazole (SMX) via PMS activation. The catalytic performance of M-OMS-2 in SMX elimination via PMS activation was assessed. The nanorods obtained in decreasing order of SMX removal rate were Cu-OMS-2 (96.40%), Co-OMS-2 (88.00%), Ni-OMS-2 (87.20%), Fe-OMS-2 (35.00%), and OMS-2 (33.50%). Then, the kinetics and structure–activity relationship of the M-OMS-2 nanorods during the elimination of SMX were investigated. The feasible mechanism underlying SMX degradation by the Cu-OMS-2/PMS system was further investigated with a quenching experiment, high-resolution mass spectroscopy, and electron paramagnetic resonance. Results showed that SMX degradation efficiency was enhanced in seawater and tap water, demonstrating the potential application of Cu-OMS-2/PMS system in sewage treatment.

Keywords

sulfamethoxazole / manganese oxide octahedral molecular sieve / peroxymonosulfate / sewage treatment / copper

References

[1] Zhou XY, Yin RL, Kang JQ, et al. . Atomic cation-vacancy modulated peroxymonosulfate nonradical oxidation of sulfamethoxazole via high-valent iron-oxo species. Appl. Catal. B. 2023, 330: 122640

[2] Peng JB, Chang Y, Xu L, et al. . Insights into the enhanced removal of sulfamethoxazole via peroxymonosulfate activation catalyzed by bimetallic (Co/Cu) doped graphitic carbon nitride: Reaction kinetics. mechanisms. 2023, andpathwaysChem.Eng.J.476: 146692

[3] Jaafarzadeh N, Ghanbari F, Zahedi A. Coupling electrooxidation and Oxone for degradation of 2,4-Dichlorophenoxyacetic acid (2,4-D) from aqueous solutions. J. Water Process. Eng.. 2018, 22: 203

[4] Li SJ, Zheng XY, Jin HC, et al. . Multivalent cobalt species supported on graphene aerogel for degradation of sulfamethoxazole via high-valent cobalt-oxo species. Chem. Eng. J.. 2023, 463: 142367

[5] Rachna, Rani M, Shanker U. Sunlight assisted degradation of toxic phenols by zinc oxide doped Prussian blue nanocomposite. J. Environ. Chem. Eng.. 2020, 8(4): 104040

[6] Peng YY, Cui MY, Zhang ZY, et al. . Bimetallic composition-promoted electrocatalytic hydrodechlorination reaction on silver—palladium alloy nanoparticles. ACS Catal.. 2019, 9(12): 10803

[7] Kottapurath Vijay A, Marks V, Mizrahi A, et al. . Reaction of Fe_aq^II with peroxymonosulfate and peroxydisulfate in the presence of bicarbonate: Formation of Fe_aq^IV and carbonate radical anions. Environ. Sci. Technol.. 2023, 57(16): 6743

[8] Zhong C, Cao HB, Huang QG, Xie YB, Zhao H. Degradation of sulfamethoxazole by manganese(IV) oxide in the presence of humic acid: Role of stabilized semiquinone radicals. Environ. Sci. Technol.. 2023, 57(36): 13625

[9] Wang ZP, Chen ZB, Li QB, et al. . Non-radical activation of peracetic acid by powdered activated carbon for the degradation of sulfamethoxazole. Environ. Sci. Technol.. 2023, 57(28): 10478

[10] Zhang H, Mei Y, Zhu F, Yu FT, Komarneni S, Ma JF. Efficient activation of persulfate by C@Fe₃O₄ in visible-light for tetracycline degradation. Chemosphere. 2022, 306: 135635

[11] Guan CT, Jiang J, Pang SY, Ma J, Chen X, Lim TT. Nonradical transformation of sulfamethoxazole by carbon nanotube activated peroxydisulfate: Kinetics. mechanism and product toxicity. 2019, Chem.Eng.J.378: 122147

[12] Hu Y, Wei XP, Zhu QQ, Li L, Liao CY, Jiang GB. COVID-19 pandemic impacts on humans taking antibiotics in China. Environ. Sci. Technol.. 2022, 56(12): 8338

[13] Qiao M, Ying GG, Singer AC, Zhu YG. Review of antibiotic resistance in China and its environment. Environ. Int.. 2018, 110: 160

[14] Wu LG, Xiao XY, Chen F, et al. . New parameters for the quantitative assessment of the proliferation of antibiotic resistance genes dynamic in the environment and its application: A case of sulfonamides and sulfonamide resistance genes. Sci. Total Environ.. 2020, 726: 138516

[15] Guo YL, Sui MH, Liu S, et al. . Insight into cobalt substitution in LaFeO₃-based catalyst for enhanced activation of peracetic acid: Reactive species and catalytic mechanism. J. Hazard. Mater.. 2024, 461: 132662

[16] Xiao C, Hu YY, Li QT, et al. . Degradation of sulfamethoxazole by super-hydrophilic MoS₂ sponge co-catalytic Fenton: Enhancing Fe²⁺/Fe³⁺ cycle and mass transfer. J. Hazard. Mater.. 2023, 458: 131878

[17] Zheng JL, Lin QT, Liu YX, et al. . Efficient activation of peroxymonosulfate by Fe single-atom: The key role of Fepyrrolic nitrogen coordination in generating singlet oxygen and high-valent Fe species. J. Hazard. Mater.. 2024, 462: 132753

[18] Yang S, Shi Y, Wang XH, et al. . Selective elimination of sulfonamide antibiotics upon periodate/catechol process: Dominance of quinone intermediates. Water Res.. 2023, 242: 120317

[19] Yang T, An LQ, Zeng G, et al. . Enhanced hydroxyl radical generation for micropollutant degradation in the In₂O₃/Vis-LED process through the addition of periodate. Water Res.. 2023, 243: 120401

[20] Li X, Wen X, Lang JY, et al. . CoN₁O₂ single-atom catalyst for efficient peroxymonosulfate activation and selective cobalt(IV) =O generation. Angew. Chem. Int. Ed.. 2023, 62(27): e202303267

[21] Li QY, Fu FY, Yan JY, et al. . Synthesis of N-doped porous biochar from chemical pollutant for efficient sulfadiazine degradation: Performance, mechanism and bio-toxicity assessment. Sep. Purif. Technol.. 2025, 353: 128432

[22] Xiao YN, Hu JH, Li XY, et al. . Constructing zinc singleatom catalysts for the direct electron-transfer mechanism in peroxymonosulfate activation to degrade sulfamethoxazole efficiently. Chem. Eng. J.. 2023, 474: 145973

[23] Moradi M, Kakavandi B, Bahadoran A, Giannakis S, Dehghanifard E. Intensification of persulfate-mediated elimination of bisphenol A by a spinel cobalt ferrite-anchored g-C₃N₄S-scheme photocatalyst: Catalytic synergies and mechanistic interpretation. Sep. Purif. Technol.. 2022, 285: 120313

[24] Ma J, Yang X, Jiang X, et al. . Percarbonate persistence under different water chemistry conditions. Chem. Eng. J.. 2020, 389: 123422

[25] An N, Li SJ, Xu BT, et al. . Role of nitrogen dual reaction sites in N-doped graphene aerogels for synergistic sulfamethoxazole adsorption and peroxymonosulfate activation in Fentonlike process. Chem. Eng. J.. 2023, 475: 146309

[26] Peng LJ, Shang YN, Gao BY, Xu X. Co₃O₄ anchored in N. S heteroatom co-doped porous carbons for degradation of organic contaminant: Role of pyridinic N—Co binding and high tolerance of chloride. 2021, Appl.Catal.B282: 119484

[27] Wang S, Qian JS, Zhang BL, Chen L, Wei S, Pan BC. Unveiling the occurrence and potential ecological risks of organophosphate esters in municipal wastewater treatment plants across China. Environ. Sci. Technol.. 2023, 57(5): 1907

[28] Wang SC, Lin YM, Shao BB, Dong HY, Ma J, Guan XH. Selective removal of emerging organic contaminants from water using electrogenerated Fe(IV) and Fe(V) under nearneutral conditions. Environ. Sci. Technol.. 2023, 57(25): 9332

[29] Shang YN, Xu X, Gao BY, Wang SB, Duan XG. Single-atom catalysis in advanced oxidation processes for environmental remediation. Chem. Soc. Rev.. 2021, 50(8): 5281

[30] Wang JL, Zhuan R. Degradation of antibiotics by advanced oxidation processes: An overview. Sci. Total Environ.. 2020, 701: 135023

[31] Peng YT, Tang HM, Yao B, Gao X, Yang X, Zhou YY. Activation of peroxymonosulfate (PMS) by spinel ferrite and their composites in degradation of organic pollutants: A Review. Chem. Eng. J.. 2021, 414: 128800

[32] Ma CY, Guo YJ, Zhang DF, et al. . Metal-nitrogen-carbon catalysts for peroxymonosulfate activation to degrade aquatic organic contaminants: Rational design. size-effect description. 2023, applicationsandmechanismsChem.Eng.J.454: 140216

[33] Zhou XQ, Zhao QD, Wang J, Chen ZL, Chen ZQ. Nonradical oxidation processes in PMS-based heterogeneous catalytic system: Generation. identification. 2021, oxidationcharacteristicschallengesresponseandapplicationprospectsChem.Eng.J.410: 128312

[34] 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. 2021, Chem.Eng.J.411: 127957

[35] Sun JW, Wu T, Liu ZF, et al. . Peroxymonosulfate activation induced by spinel ferrite nanoparticles and their nanocomposites for organic pollutants removal: A review. J. Clean. Prod.. 2022, 346: 131143

[36] Jin XT, Wang YL, Huang YP, Huang D, Liu X. Percarbonate activation catalyzed by nanoblocks of basic copper molybdate for antibiotics degradation: High performance, degradation pathways and mechanism. Chin. Chem. Lett. 2024, 35(10): 109499

[37] Wang LJ, Xiao K, Zhao HZ. The debatable role of singlet oxygen in persulfate-based advanced oxidation processes. Water Res.. 2023, 235: 119925

[38] Fang C, Yan JY, Wang YL, Zhang NN, Liu X. Facile synthesis of N-doped carbon nanorods for antibiotics degradation via PMS activation: Mechanism insight and biotoxicity assessment. Sep. Purif. Technol.. 2024, 340: 126849

[39] Pang K, Yan JY, Zhang NN, Fang C, Fu FY, Liu X. Spatial confinement of Co nanoparticles in N-doped carbon nanorods for wastewater purification via CaSO₃ activation. Inorg. Chem.. 2024, 63(15): 7071

[40] Pang K, Fang C, Wang YL, Huang YP, Huang D, Liu X. Synthesis of Mo-based/carbon nanocomposistes for water decontamination via percarbonate activation. Catal. Lett.. 2024, 154(6): 2999

[41] Fang C, Wang YL, Huang WK, Huang YP, Huang D, Liu X. Carbon nanosphere as an efficient support for CoOx nanoparticles on water decontamination via sulfite activation. Surf. Interfaces. 2024, 44: 103732

[42] Zhou YH, Fang C, Yang XJ, Wang YL, Yan JY, Liu X. Selective ¹O₂ generation from peroxymonosulfate activation over N-doped carbon nanosponges for pollutant degradation. ACS Appl. Nano Mater.. 2023, 6(19): 18403

[43] Fang C, Hao ZX, Wang YL, Huang YP, Huang D, Liu X. Carbon nanotube as a nanoreactor for efficient degradation of 3-aminophenol over CoO_x/CNT catalyst. J. Clean. Prod.. 2023, 405: 136912

[44] Huang JZ, Zhang HC. Mn-based catalysts for sulfate radical- based advanced oxidation processes: A review. Environ. Int.. 2019, 133: 105141

[45] Hao YX, Li LL, Lu ZM, Yu XF, Zhang XH, Yang XJ. OMS-2 nanorods filled with Co-ion in the tunnels as efficient electron conduits and regulatory substance for oxygen reduction. Appl. Catal. B. 2020, 279: 119373

[46] Iyer A, Galindo H, Sithambaram S, King'ondu C, Chen CH, Suib SL. Nanoscale manganese oxide octahedral molecular sieves (OMS-2) as efficient photocatalysts in 2-propanol oxidation. Appl. Catal. A. 2010, 375(2): 295

[47] Sun M, Yu L, Ye F, et al. . Transition metal doped cryptomelane- type manganese oxide for low-temperature catalytic combustion of dimethyl ether. Chem. Eng. J.. 2013, 220: 320

[48] Yao N, Zhao HY, Liu X, et al. . Synergistic adsorption and oxidative degradation of polyvinyl alcohol by acidified OMS-2: Catalytic mechanism, degradation pathway and toxicity evaluation. Sep. Purif. Technol.. 2022, 302: 122047

[49] Zhang L, Han SC, Wu YJ, et al. . Complete oxidation of formaldehyde at room temperature over Ag-loaded octahedral molecular sieve synthesized from solvent-free route. Appl. Catal. B. 2022, 303: 120875

[50] Liu WB, Yang Y, Li YH, et al. . Oxygen vacancies enhanced natural manganese sand activation by PMS for CBZ degradation: Intermediate toxicity and DFT calculations. Sep. Purif. Technol.. 2024, 329: 125015

[51] Yang X, Wei GL, Wu PQ, Liu P, Liang XL, Chu W. Controlling oxygen vacancies of CoMn₂O₄ by loading on planar and tubular clay minerals and its application for boosted PMS activation. J. Hazard. Mater.. 2022, 436: 129060

[52] Wang JL, Wang SZ. Effect of inorganic anions on the performance of advanced oxidation processes for degradation of organic contaminants. Chem. Eng. J.. 2021, 411: 128392

[53] Chen CL, Xie J, Chen X, Zhang WX, Chen J, Jia AP. Cu species-modified OMS-2 materials for enhancing ozone catalytic decomposition under humid conditions. ACS Omega. 2023, 8(22): 19632

[54] Liu X, Hao ZX, Fang C, et al. . Using waste to treat waste: Facile synthesis of hollow carbon nanospheres from lignin for water decontamination. Chem. Sci.. 2024, 15(1): 204

[55] Li QY, Ruan JY, Zhang XY, et al. . Spatial confinement of Co—N—C catalyst in carbon nanocuboid for water decontamination: High performance. mechanism and biotoxicity assessment. 2024, Chem.Eng.J.479: 147555

[56] Chen ZH, Lin BF, Huang YP, et al. . Pyrolysis temperature affects the physiochemical characteristics of lanthanum-modified biochar derived from orange peels: Insights into the mechanisms of tetracycline adsorption by spectroscopic analysis and theoretical calculations. Sci. Total Environ.. 2023, 862: 160860

[57] Wang JL, Wang SZ. Reactive species in advanced oxidation processes: Formation. identification and reaction mechanism. 2020, Chem.Eng.J.401: 126158

[58] Wu SH, Yang ZW, Zhou ZY, et al. . Catalytic activity and reaction mechanisms of single-atom metals anchored on nitrogen- doped carbons for peroxymonosulfate activation. J. Hazard. Mater.. 2023, 459: 132133

[59] Kong LS, Fang GD, Chen YF, et al. . Efficient activation of persulfate decomposition by Cu₂FeSnS₄ nanomaterial for bisphenol A degradation: Kinetics, performance and mechanism studies. Appl. Catal. B. 2019, 253: 278

[60] Shi YB, Wang XB, Liu XF, Ling CC, Shen WJ, Zhang LZ. Visible light promoted Fe₃S₄ Fenton oxidation of atrazine. Appl. Catal. B. 2020, 277: 119229

[61] Wu JM, Sun YG, Chang WE, Lee JT. Piezoelectricity induced water splitting and formation of hydroxyl radical from active edge sites of MoS₂ nanoflowers. Nano Energy. 2018, 46: 372

[62] Shi YB, Yang ZP, Shi LJ, et al. . Surface boronizing can weaken the excitonic effects of BiOBr nanosheets for efficient O2 activation and selective NO oxidation under visible light irradiation. Environ. Sci. Technol.. 2022, 56(20): 14478

[63] Shi YB, Zhang CC, Yang ZP, et al. . Interfacial electrostatic field boosted exciton dissociation of phosphorylated BiOBr for efficient O₂ activation and chlorobenzene degradation. J. Phys. Chem. C. 2022, 126(51): 21847

[64] Oyekunle DT, Gendy EA, Ifthikar J, Chen ZQ. Heterogeneous activation of persulfate by metal and non-metal catalyst for the degradation of sulfamethoxazole: A review. Chem. Eng. J.. 2022, 437: 135277

[65] Wang M, Tang YW, Wang JD, et al. . Promoted peroxydisulfate activation by nitrogen-doped carbon embedding iron on a nickel foam cathode: Performance, mechanism and relationship between CO and ¹O₂ generation. Chem. Eng. J.. 2023, 460: 141638

[66] Zeng HX, Deng L, Zhang HJ, Zhou C, Shi Z. Development of oxygen vacancies enriched CoAl hydroxide@hydroxysulfide hollow flowers for peroxymonosulfate activation: A highly efficient singlet oxygen-dominated oxidation process for sulfamethoxazole degradation. J. Hazard. Mater.. 2020, 400: 123297

[67] Wang AN, Zhu BZ, Huang CH, et al. . Generation mechanism of singlet oxygen from the interaction of peroxymonosulfate and chloride in aqueous systems. Water Res.. 2023, 235: 119904