Intramolecular Electron Transfer Mechanism of pH-Mediated Cupric Complexes Activated Peroxymonosulfate Selective Oxidation of Aqueous Tetracycline

doi:10.7503/cjcu20240337

Abstract

Abstract:

Although aqueous dissociative Cu（Ⅱ） could not effectively activate peroxymonosulfate（PMS）， the cupric complexes formed by complexing with tetracycline（TC） could activate PMS and realize self-catalytic degradation of TC. The generation of cupric complexes was verified by UV-Vis and high performance liquid chromatography（HPLC）， and the reaction pathways， molecular structure model， free energy variation， density of states（DOS）， and complexation interaction of cupric complexes were revealed by density functional theory（DFT） calculation. It was found that the d orbital of Cu in Cu(H₂O)₄^{2 +} was complexed by accepting the lone pair electrons of p orbital from hydroxyl， carbonyl， and amide group O in TC， and there were five possible complexation models constructed， all of them showed a stable bidenate ligands and hexatomic-ring coordination structure， in which the free energy of complex M 1 became the smallest and its structure was the most stable. The interaction of cupric complexes formation mainly included van der Waals force， weak interaction， covalent bond， steric hindrance， coordination bond， etc. Cu（II）/PMS system had significant self-catalytic degradation of TC， which could be completely degraded within 240 min（degradation efficiency was greater than 99%）. Furthermore， under alkaline conditions（pH=10）， the activation of peroxymonosulfate by cupric complexes coupling Cu（III） complexes generation in situ promoted an intramolecular electron transfer（IET） process dominating the selective oxidation of TC. The pH-mediated IET mechanism of cupric complexes activated peroxymonosulfate selective oxidation of aqueous tetracycline was further elucidated through DFT calculations from dynamic and microscopic perspectives. The new findings in this paper further verified the self-catalytic selective oxidation performance and mechanism by aqueous cupric complexes activated PMS system， which provided a potential solution for the synergistic decontamination of actual wastewater contaminated heavy metals and antibiotics.

Key words: Cupric complex, Peroxymonosulfate, Tetracycline, Selective oxidation

CLC Number:

O611.2

TrendMD:

ZENG Xiangchu, YE Yuting, WU Zhe, WEI Ruisong, LIU Huan. Intramolecular Electron Transfer Mechanism of pH-Mediated Cupric Complexes Activated Peroxymonosulfate Selective Oxidation of Aqueous Tetracycline[J]. Chem. J. Chinese Universities, 2024, 45(12): 20240337.

Figures/Tables 13

References 40

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Species	Electron energy/a.u.	Free energy correction/a.u.		Free energy/a.u.
Species	Electron energy/a.u.	303 K	353 K	303 K	353 K
H₂O	-76.3859	0.002584	-0.00118	-76.3803	-76.3840
H ⁺	0	-0.0102	-0.01231	-0.44141	-0.44352
Cu⁃4H₂O	-502.587	0.067376	0.059214	-502.517	-502.525
TC	-1602.18	0.420748	0.405165	-1601.75	-1601.77
M1	-1951.56	0.456565	0.438817	-1951.10	-1951.12
M2	-1951.98	0.466724	0.448389	-1951.51	-1951.53
M3	-1951.54	0.456971	0.439220	-1951.08	-1951.10
M4	-1951.56	0.456087	0.438193	-1951.10	-1951.12
M5	-1951.53	0.452588	0.434274	-1951.08	-1951.10

Species	Electron energy/a.u.	Free energy correction/a.u.		Free energy/a.u.
Species	Electron energy/a.u.	303 K	353 K	303 K	353 K
H₂O	-76.3859	0.002584	-0.00118	-76.3803	-76.3840
H ⁺	0	-0.0102	-0.01231	-0.44141	-0.44352
Cu⁃4H₂O	-502.587	0.067376	0.059214	-502.517	-502.525
TC	-1602.18	0.420748	0.405165	-1601.75	-1601.77
M1	-1951.56	0.456565	0.438817	-1951.10	-1951.12
M2	-1951.98	0.466724	0.448389	-1951.51	-1951.53
M3	-1951.54	0.456971	0.439220	-1951.08	-1951.10
M4	-1951.56	0.456087	0.438193	-1951.10	-1951.12
M5	-1951.53	0.452588	0.434274	-1951.08	-1951.10

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