Degradation of Bisphenol A by Peroxymonosulfate Catalytically Activated with. Gui-Xiang Huang, Chu-Ya Wang, Chuan-Wang Yang, Pu-Can Guo, Han-Qing Yu*
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1 Supporting Information for Degradation of Bisphenol A by Peroxymonosulfate Catalytically Activated with Mn 1.8 Fe 1.2 O 4 Nanospheres: Synergism between Mn and Fe Gui-Xiang Huang, Chu-Ya Wang, Chuan-Wang Yang, Pu-Can Guo, Han-Qing Yu* CAS Key Laboratory of Urban Pollutant Conversion, Department of Chemistry, University of Science & Technology of China, Hefei, , China This supplementary material contains 24-page document, including 2 tables, 17 figures, references and this cover page. S1
2 Table S1. Comparison between MnFeO and the Previously Reported Mn/Fe-Oxide Catalysts in the Catalytic Performance. catalyst dosage (g L -1 ) PMS dosage (g L -1 ) pollutant (mg L -1 ) removal efficiency (%) initial ph temp. (ºC) ref. nanowires α-mno 2 (0.4) 2.0 phenol (30) (20 min) No data 25 1 β-mno 2 (0.4) 2.0 phenol (25) (50 min) No data 25 2 γ-mno 2 (0.4) 2.0 phenol (25) (30 min) No data 25 2 γ-mn 3 O 4 (0.4) 2.0 phenol (25) 66.4 (120 min) No data 25 3 MnO (0.4) 2.0 phenol (25) 90 (120 min) No data 25 3 α-mn 2 O 3 -cubic (0.4) 2.0 phenol (25) (60 min) No data 25 4 corolla-like MnO 2 (0.2) 2.0 phenol (20) (30 min) PM-S (0.2) 2.0 phenol (40) (30 min) No data 25 6 MnO x /HCAS (1.0) 1.0 acid Red 73 (50) >98 (30 min) Mn 3 O 4 /rgo (0.05) 1.5 orange II (30) (120 min) Mn 3 O 4 /rgo (0.05) 1.5 orange II (30) (90 min) Fe 2 O 3 (1.5) 0.3 RhB (50) (60 min) 6.2 RT 10 DPA-hematite (0.5) 2.0 BPA (15) (120 min) ± 1 11 Fe 3 O 4 (0.8) 0.06 acetaminophen (10) 98 (120 min) ± 1 12 Fe 3 O 4 /MnO 2 (0.2) chlorophenol (50) >95 (30 min) Fe 3 O 2 BBHs (0.3) 6 MB (30) (30 min) Fe 3 O 4 /Mn 3 O 4 / rgo (0.1) 0.3 MB (50) >95 (30 min) S2
3 MnO 2 /ZnFe 2 O 4 (0.2) 2.0 phenol (20) (120 min) No data MnFe 2 O 4 (0.05) 0.5 orange II (20) 77 (120 min) No data MnFe 2 O 4 -rgo (0.05) 0.5 orange II (20) 90 (120 min) No data Mn 2.09 Fe 0.91 O 4 (1.0) 0.06 AO II (35) 64 (480 min) 7.0 RT (~20) 18 Mn 1.8 Fe 1.2 O 4 (0.2) 0.2 BPA (10) (15 min) ± 2 This work S3
4 Table S2. Concentration of the Leaching Metal Ions after the Reaction at Various ph Values and after Different Cycles a ph metal ion metal ion cycle Mn Fe Mn Fe ph= nd run 6.62 UD ph= UD 3rd run 5.76 UD ph= UD regeneration UD a Concentration unit is µg L 1 ; UD = undetectable. S4
5 Figure S1. Nitrogen adsorption-desorption isotherms of the MnFeO nanospheres (a), the synthetic Mn 3 O 4 (b) and commercial Fe 3 O 4 (c). S5
6 Figure S2. XRD patterns of the synthetic Mn 3 O 4 (a) and commercial Fe 3 O 4 (b) and Fe 2 O 3 (c). S6
7 Figure S3. Change of solution ph during BPA degradation in the PMS/MnFeO system without any buffers. Reaction conditions: [BPA] = 10 mg L 1, [MnFeO] = 0.1 g L 1, [PMS] = 0.2 g L 1. S7
8 Figure S4. Change of solution ph during BPA degradation in the PMS/MnFeO system. Reaction conditions: [BPA] = 10 mg L 1, [MnFeO] = 0.1 g L 1, [PMS] = 0.2 g L 1 and the solution phs (except ph 4.2) were buffered with 20 mm borate. S8
9 Figure S5. Effect of borate-buffered solution (BBS) on the BPA degradation in the PMS/MnFeO system. Reaction conditions: [BPA] = 10 mg L 1, [MnFeO] = 0.1 g L 1, [PMS] = 0.2 g L 1, and initial ph = 7.5. S9
10 Figure S6. BET surface area and specific-surface-area normalized BPA removal efficiency of the MnFeO nanospheres, the synthetic Mn 3 O 4 and commercial Fe 3 O 4. S10
11 Figure S7. BPA removal efficiency in homogeneous reactions with 20 µg L 1 Mn 2+ and the leaching solution. To obtain the leaching solution, the BPA solution with 0.1 g L 1 MnFeO nanospheres was incubated at ph 7.5 for 30 min and then the nanoparticles were removed by centrifugation. Reaction conditions: [BPA] = 10 mg L 1, [PMS] = 0.2 g L 1, ph = 7.5 and buffered with 20 mm borate. S11
12 Figure S8. TOC removal efficiency in the BPA degradation within 30 min in the PMS/MnFeO system. Reaction conditions: [MnFeO] = 0.1 g L 1, [PMS] = 0.2 g L 1, [BPA] = 10 mg L 1, and initial ph = 6.2. S12
13 Figure S9. BPA removal efficiency in the repeated batch catalytic reactions over the MnFeO nanospheres (regeneration means the thermal treatment at 400 C for 1 h in air). Reaction conditions: [MnFeO] = 0.1 g L 1, [PMS] = 0.2 g L 1, [BPA] = 10 mg L 1, and initial ph = 6.2. S13
14 Figure S10. Raman spectra of the MnFeO samples before and after reaction. Reaction conditions: [MnFeO] = 0.1 g L 1, [PMS] = 0.2 g L 1, [BPA] = 10 mg L 1, and initial ph = 6.2. S14
15 Figure S11. FTIR spectra of the MnFeO samples before and after reaction. Reaction conditions: [MnFeO] = 0.1 g L 1, [PMS] = 0.2 g L 1, [BPA] = 10 mg L 1, and initial ph = 6.2. S15
16 Figure S12. SEM images of Mn 3 O 4 (a, b), Fe 3 O 4 (c) and the mixture of Mn 3 O 4 /Fe 3 O 4 (d). S16
17 Figure S13. EPR spectra in the activation of PMS with/without ethanol (EtOH). Reaction conditions: [DMPO] = 5 mm, [PMS] = 0.02 g L 1, [MnFeO] = 0.01 g L 1, [BPA] = 1 mg L 1, and ph = 7.2. S17
18 Figure S14. Mn 2p (a) and Fe 2p (b) regions of the XPS spectra of the MnFeO samples before and after the reaction. Reaction conditions: [BPA] = 10 mg L 1, [PMS] = 0.2 g L 1, [MnFeO] = 0.1 g L 1, and initial ph = 6.2. S18
19 Figure S15. GC-MS chromatogram for the BPA degradation in the PMS/MnFeO system. S19
20 Figure S16. GC-MS spectra of the intermediates from the BPA degradation in the PMS/MnFeO system. S20
21 Figure S17. Proposed pathways for the BPA degradation in the PMS/MnFeO system. S21
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