Efficient Elerctrochemical oxidation of perfluorooctanoate using a Ti-SnO2-Sb-Bi anode-001

† ‡
Tsinghua University. Shenzhen University.
S1
30 31 32 33 34 35 36 37 38 39 40 41 42 43
S1 Reagents. Perfluorooctanoate (PFOA, C7F15COONa, >97%) was purchased from Tokyo Kasei Kogyo (Japan) and perfluoroheptanoic acid (C6F13COOH, >99%) was obtained from Sigma-Aldrich Co. (product of Switzerland). Undecafluorohexanoic acid (C5F11COOH) and heptafluorobutyric acid (C3F7COOH, 0.5 mol·L-1) were purchased from Tokyo Chemical Industry Co. Ltd. Perfluoropentanoic acid (C4F9COOH, >97%) was bought form Sigma-Aldrich Co. (Steinheim, Germany). Pentafluoropropionic acid (C2F5COOH, >97%) and trifluoroacetic acid (CF3COOH, >99.0%) were obtained from Acro Organics, Geel, Belgium. HPLC-grade methanol was purchased from Fisher Chemical (USA). H218O were purchased from Shanghai Research Institute of Chemical Industry (China). BiCl3 and SbCl3 were purchased from Sinopharm Chemical Reagent Co. Ltd (China). SnCl4 was purchased from XiLong Chemical in Shantou (China). Ethylene glycol was obtained form Beijing Modern Eastern Fine Chemical (China). Isopropanol was supplied by Acros Organics. Citric acid was made by Beijing Chemical Works (China). Other chemicals were analytical reagents.
Table S1. Calibration conditions for F¯ measurement on the ion chromatography. Retention time (min) 4.1
a
Concentration range (mg·L-1) 5-45
Correlation coefficient (R2) 0.999
62 63
First-order kinetic constant (h-1) Initial concentration 1.92 0.174 2.46 5mL) 25 30 600
Fmass balance=(F-in solution,t+∑ Fin C n F2n+1COO - , t ) / Fin PFOA,initial
FOURTEEN PAGES SIX TEXTS EIGHT TABLES ELEVEN FIGURES ONE EQUATION TEN REFERENCES
Corresponding author phone: (+86-10)62787137; fax: (+86-10)62794006;
E-mail: yg-den@.
53 54 55
S3
Flow rate (mL·min-1) 0.30 0.30 0.30 0.30 0.30 0.30 0.30
%A /%B (v/v) 25/75 25/75 85/15 100/0 100/0 25/75 25/75
Curve initial linear linear linear linear linear linear
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29
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Supporting Information
Efficient Electrochemical Oxidation of Perfluorooctanate Using a Ti/SnO2-Sb-Bi Anode
1.10 2.10 2.96 3.59
0-500 0-500 0-500 0-500
Limit of detection (LOD) was calculated from the concentration of each compound that yielded a
signal-to-noise (S/N) ratio of 3.
b
Limit of quantification (LOQ) was calculated from the concentration of each compound that yielded a
signal-to-noise (S/N) ratio of 10.
57 58
TABLE S5. Calibration conditions for the quantification of C7F15COO¯ on the HPLC. Retention time (min) 10.90
59 60
S4
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TABLE S6. First-order kinetic constants for PFOA degradation using different methods. Different methods Electrochemical oxidation UV/KI Sonochemistry
signal-to-noise (S/N) ratio of 3.
b
Limit of quantification (LOQ) was calculated from the concentration of C7F15COO¯ that yielded a
signal-to-noise (S/N) ratio of 10.
b
Limit of quantification (LOQ) was calculated from the concentration of F¯ that yielded a
signal-to-noise (S/N) ratio of 10.
44 45 46 47 48
S2
49
TABLE S2. Calibration conditions for the quantification of CF3COO and C2F5COO on an ion chromatograph. Target compounds CF3COOC2F5COOa
56
TABLE S4. Calibration conditions for the quantification of C3F7COO, C4F9COO, C5F11COO¯, and C6F13COO on the UPLC-MS/MS. Concentration Target m/z compounds time (min) (µg·L-1) C3F7COO C4F9COO C5F11COO C6F13COO
a
Correlation LODa LOQb coefficient (µg·L-1) (µg·L-1) (R2) 0.996 0.991 0.993 0.979 0.21 0.15 0.43 0.071 0.71 1.43 0.68 0.23
Retention range
213 263 313 363
yielded a signal-to-noise (S/N) ratio of 10.
50 51 52
TABLE S3. Gradient conditions in the determination of C3F7COO¯, C4F9COO¯, C5F11COO¯, and C6F13COO¯ on the UPLC-MS/MS. Time (min) 0 0.50 5.0 5.1 7.0 7.1 10
64 65 66
Eq. S1
In Eq.S1, the unit of F was “mg”, n was equal to 1-7, and t represented the time = t.
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FIGURE S1. The electrochemical oxidation reaction system (Reactor I) used in this study
S5
70 71
FIGURE S2. The electrochemical oxidation reaction system (Reactor II) used in this study
0.0035 0.0030 0.0025
Current/1e-3A
Ti/SnO2-Sb-Bi Ti/SnO2-Sb
Retention time (min) 4.07 6.60
Concentration range (mg·L-1) 0-10 0-10
Correlation coefficient (R2) 0.999 0.999