Synthesis of bimetallic crednerite nanosheet as an efficient heterogeneous catalyst in Fenton-like degradation of bisphenol A

Abstract

Integrating bimetallic oxides into peroxymonosulfate (PMS) based advanced oxidation processes is appealing to span the limited kinetics in view of the interaction between multiple active sites. Herein, the crednerite (CuMnO₂) nanosheet, synthesized through a low-temperature hydrothermal method, has demonstrated significant potential for water remediation. The as-prepared CuMnO₂ sample was characterized by involving morphology, crystal texture, and physicochemical property. The catalytic activity of CuMnO₂ on PMS activation was evaluated, and the influence of PMS concentration, catalyst dosage, and pH value on the removal of bisphenol A (BPA) was investigated. Over an abroad pH range from 4.0 to 10.0, more than 90% BPA could be effectively removed after 60 min reaction with the lower dosages of 0.2 g·L^–1 catalyst and 0.4 mmol·L^–1 oxidant. In terms of reaction pathways, the metal (Cu/Mn)-hydroxyl moiety with cooperative effect and good redox cycle mediate the disaggregation of adsorbed PMS into surface-bound sulfate and hydroxyl radicals, which are mainly responsible for the swift elimination and mineralization of BPA in the CuMnO₂/PMS system. This work provides a constructive paradigm for the development of a cost-effective heterogeneous Fenton-like reaction toward environmental purification.

Graphical abstract

Keywords

bimetallic oxide / bisphenol A / crednerite / nanosheet / persulfate

References

[1] Cai Y , Hu B , Wang X . Defect engineering on constructing surface active sites in catalysts for environment and energy applications. Frontiers of Chemical Science and Engineering, 2024, 18(7): 74

[2] Zhang X , Yan M , Chen P , Li J , Li Y , Li H , Liu X , Chen Z , Yang H , Wang S . . Emerging MOFs, COFs, and their derivatives for energy and environmental applications. The Innovation, 2025, 6(2): 100778

[3] Osuoha J O , Anyanwu B O , Ejileugha C . Pharmaceuticals and personal care products as emerging contaminants: need for combined treatment strategy. Journal of Hazardous Materials Advances, 2023, 9: 100206

[4] Shang Y N , Xu X , Gao B Y , Wang S B , Duan X G . Single-atom catalysis in advanced oxidation processes for environmental remediation. Chemical Society Reviews, 2021, 50(8): 5281–5322

[5] Rahman K O , Aziz K H H . Utilizing scrap printed circuit boards to fabricate efficient Fenton-like catalysts for the removal of pharmaceutical diclofenac and ibuprofen from water. Journal of Environmental Chemical Engineering, 2022, 10(6): 109015

[6] Hama Aziz K H , Miessner H , Mueller S , Kalass D , Moeller D , Khorshid I , Rashid M A M . Degradation of pharmaceutical diclofenac and ibuprofen in aqueous solution, a direct comparison of ozonation, photocatalysis, and non-thermal plasma. Chemical Engineering Journal, 2017, 313: 1033–1041

[7] Hama Aziz K H . Heterogeneous catalytic activation of peroxydisulfate toward degradation of pharmaceuticals diclofenac and ibuprofen using scrap printed circuit board. RSC Advances, 2023, 13(1): 115–128

[8] Wang F L , Sun L , Zhang Z Y , Yang F K , Yang J L , Liu W J . Enhanced activation of persulfate using mesoporous silica spheres augmented Cu-Al bimetallic oxide particles for bisphenol A degradation. Frontiers of Chemical Science and Engineering, 2023, 17(10): 1581–1592

[9] Lan J , Zhang Q , Yang G , Liu Z , Peng F . Removal of tetracycline hydrochloride by N, P co-doped carbon encapsulated Fe₂P activating PMS: a non-radical pathway dominated by singlet oxygen. Journal of Environmental Chemical Engineering, 2023, 11(5): 110481

[10] Ehsan M A , Shah S S , Basha S I , Hakeem A S , Aziz M A . Recent advances in processing and applications of heterobimetallic oxide thin films by aerosol-assisted chemical vapor deposition. The Chemical Record, 2022, 22(7): e202100278

[11] Balaji T E , Tanaya Das H , Maiyalagan T . Recent trends in bimetallic oxides and their composites as electrode materials for supercapacitor applications. ChemElectroChem, 2021, 8(10): 1723–1746

[12] Liang P , Meng D , Liang Y , Wang Z , Zhang C , Wang S , Zhang Z . Cation deficiency tuned LaCoO_3−δ perovskite for peroxymonosulfate activation towards bisphenol A degradation. Chemical Engineering Journal, 2021, 409: 128196

[13] Shi Q , Li J , Ma Y , Zhao R , Li M , Lei X , Sun M , Zhao Y , Ren G , Jia J . Controllable preparation of MnCo₂O₄ spinel and catalytic persulfate activation in organic wastewater treatment: experimental and immobilized evaluation. Progress in Natural Science, 2024, 34(4): 776–786

[14] Fu S , Li L , Jing Y , Zhang Y , Wang X , Fang S , Wang J , Li G . Crystal growth of bimetallic oxides CuMnO₂ with tailored valence states for optimum electrochemical energy storage. Crystal Growth & Design, 2018, 18(10): 6107–6116

[15] Chen H , Zhang X , Zhao Y , Wang S , Ren Y , Wang X . Highly efficient catalyst of crednerite CuMnO₂ for PMS activation: synthesis, performance and mechanism. Surfaces and Interfaces, 2023, 42: 103522

[16] Xiong D , Zhang Q , Du Z , Verma S K , Li H , Zhao X . Low temperature hydrothermal synthesis mechanism and thermal stability of p-type CuMnO₂ nanocrystals. New Journal of Chemistry, 2016, 40(7): 6498–6504

[17] Rajah Z , Guiza M , Solís R R , Becheikh N , Rivas F J , Ouederni A . Clopyralid degradation using solar-photocatalytic/ozone process with olive stone activated carbon. Journal of Environmental Chemical Engineering, 2019, 7(1): 102900

[18] Liang C , Huang C F , Mohanty N , Kurakalva R M . A rapid spectrophotometric determination of persulfate anion in ISCO. Chemosphere, 2008, 73(9): 1540–1543

[19] Mustafa F S , Hama Aziz K H . Heterogeneous catalytic activation of persulfate for the removal of rhodamine B and diclofenac pollutants from water using iron-impregnated biochar derived from the waste of black seed pomace. Process Safety and Environmental Protection, 2023, 170: 436–448

[20] Jin Y Y , Wang X N , Sun S P , Dong W B , Wu Z X , Bian G Q , Wu W D , Chen X D . Hydroxyl and sulfate radicals formation in UVA/Fe^III-NTA/S₂O₈²⁻ system: mechanism and effectiveness in carbamazepine degradation at initial neutral pH. Chemical Engineering Journal, 2019, 368: 541–552

[21] Zhang T , Li C , Ma J , Tian H , Qiang Z . Surface hydroxyl groups of synthetic α-FeOOH in promoting OH generation from aqueous ozone: property and activity relationship. Applied Catalysis B: Environmental, 2008, 82(1-2): 131–137

[22] Huang G X , Wang C Y , Yang C W , Guo P C , Yu H Q . Degradation of bisphenol A by peroxymonosulfate catalytically activated with Mn_1.8Fe_1.2O₄ nanospheres: synergism between Mn and Fe. Environmental Science & Technology, 2017, 51(21): 12611–12618

[23] Hama Aziz K H , Miessner H , Mueller S , Mahyar A , Kalass D , Moeller D , Khorshid I , Rashid M A M . Comparative study on 2,4-dichlorophenoxyacetic acid and 2,4-dichlorophenol removal from aqueous solutions via ozonation, photocatalysis and non-thermal plasma using a planar falling film reactor. Journal of Hazardous Materials, 2018, 343: 107–115

[24] Shukla P , Sun H , Wang S , Ang H M , Tadé M O . Co-SBA-15 for heterogeneous oxidation of phenol with sulfate radical for wastewater treatment. Catalysis Today, 2011, 175(1): 380–385

[25] Guan Y H , Ma J , Li X C , Fang J Y , Chen L W . Influence of pH on the formation of sulfate and hydroxyl radicals in the UV/peroxymonosulfate system. Environmental Science & Technology, 2011, 45(21): 9308–9314

[26] Zhang T , Zhu H , Croué J P . Production of sulfate radical from peroxymonosulfate induced by a magnetically separable CuFe₂O₄ spinel in water: efficiency, stability, and mechanism. Environmental Science & Technology, 2013, 47(6): 2784–2791

[27] Genuino H C , Meng Y , Horvath D T , Kuo C H , Seraji M S , Morey A M , Joesten R L , Suib S L . Enhancement of catalytic activities of octahedral molecular sieve manganese oxide for total and preferential CO oxidation through vanadium ion framework substitution. ChemCatChem, 2013, 5(8): 2306–2317

[28] Anipsitakis G P , Dionysiou D D . Radical generation by the interaction of transition metals with common oxidants. Environmental Science & Technology, 2004, 38(13): 3705–3712

[29] Huang Z , Bao H , Yao Y , Lu W , Chen W . Novel green activation processes and mechanism of peroxymonosulfate based on supported cobalt phthalocyanine catalyst. Applied Catalysis B: Environmental, 2014, 154–155: 36–43

[30] Yang S , Xiao T , Zhang J , Chen Y , Li L . Activated carbon fiber as heterogeneous catalyst of peroxymonosulfate activation for efficient degradation of Acid Orange 7 in aqueous solution. Separation and Purification Technology, 2015, 143: 19–26

[31] Liang H Y , Zhang Y Q , Huang S B , Hussain I . Oxidative degradation of p-chloroaniline by copper oxidate activated persulfate. Chemical Engineering Journal, 2013, 218: 384–391

[32] Yan S , Xiong W , Xing S , Shao Y , Guo R , Zhang H . Oxidation of organic contaminant in a self-driven electro/natural maghemite/peroxydisulfate system: efficiency and mechanism. Science of the Total Environment, 2017, 599–600: 1181–1190

[33] Zhou L , Song W , Chen Z , Yin G . Degradation of organic pollutants in wastewater by bicarbonate-activated hydrogen peroxide with a supported cobalt catalyst. Environmental Science & Technology, 2013, 47(8): 3833–3839

[34] Zhou Y , Jiang J , Gao Y , Ma J , Pang S Y , Li J , Lu X T , Yuan L P . Activation of peroxymonosulfate by benzoquinone: a novel nonradical oxidation process. Environmental Science & Technology, 2015, 49(21): 12941–12950

[35] Yuan Y , Wang Y , Ding W , Li J , Wu F . Solid surface photochemistry of montmorillonite: mechanisms for the arsenite oxidation under UV-A irradiation. Environmental Science and Pollution Research International, 2016, 23(2): 1035–1043

[36] Lu X , Zhao H , Feng W , Ji P . A non-precious metal promoting the synthesis of 5-hydroxymethylfurfural. Catalysts, 2017, 7(11): 330

Competing interests

The authors declare that they have no competing interests.

Acknowledgements

This study was supported by the National Natural Science Foundation of China (Grant No. 21806125).

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-025-2546-1 and is accessible for authorized users.

RIGHTS & PERMISSIONS

2025 Higher Education Press