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TRANSCRIPT
Supplementary material for
Rapid degradation of tetracycline hydrochloride by heterogeneous
photocatalysis coupling persulfate oxidation with MIL-53(Fe) under
visible light irradiation
Ying Zhang a, b, Jiabin Zhou a, *, Junhui Chen c, Xiaoqiong Feng c, Weiquan Cai d
a School of Chemistry and Chemical Engineering, Southwest Petroleum University,
Chengdu 610500, China
b School of Resources and Environmental Engineering, Wuhan University of
Technology, Wuhan 430070, China
c Sichuan Academy of Environmental Sciences, Chengdu 610041, China
d School of Chemistry and Chemical Engineering, Guangzhou University, 230 Wai
Huan Xi Road, Guangzhou Higher Education Mega Center, Guangzhou 510006,
China
*Corresponding author. Tel: +86-28-83037306
E-mail: [email protected] (J. Zhou)
Analysis of TC and intermediates
The mobile phase was acetonitrile/methanol/10 mM oxalic acid (16:8:76, v/v)
with a flow rate of 1.0 mL/min; column temperature, 25 °C. The injection volume of
samples was 20 μL. The intermediate products of degradation of TC-HCl were
identified by UHPLC-MS (Thermo Vanquish UHPLC-LTQ XL, USA) with a Thermo
hypersil gold vanquish C18 (2.1 × 100 mm, 1.9 μm). The mobile phase was
acetonitrile/0.1% formic acid (22/78, v/v) with a flow rate of 0.2 mL/min; column
temperature, 25 °C. TC-HCl and the intermediates were estimated in the positive ion
mode using ESI under the following conditions: m/z range, 20-800; DL temperature,
250 °C; heat block temperature, 400 °C; nebulizing gas flow rate, 3 L/min; drying gas
flow rate, 15 L/min. Signals in Q1 Scan and product ion scan (PIS) were detected to
obtain their m/z values.
Table S1 The specific Surface area, pore volume and pore size of the MIL-53(Fe)
using different synthetic methods.
Fe-MILs SBET (m2/g)Pore volume
(cm3/g)Pore size (nm) reference
MIL-53 367.99 0.24 2.81 This work
MIL-53 21.42 0.04 4.60 [31]
MIL-53 89.69 0.12 3.01 [25]
MIL-53 88.64 0.12 3.03 [26]
MIL-53 184.00 - - [3]
MIL-53 19.10 0.05 - [45]
Table S2 Atomic percentage content of TC in the HOMO and LUMO orbital.
Atom HOMO LUMO Atom HOMO LUMO Atom HOMO LUMO
1(O) 0.18% 0.74% 20(C) 0.06% 0.30% 39(H) 0.70% 0.26%
2(O) 0.02% 0.01% 21(C) 0.02% 0.05% 40(C) 14.42% 5.83%
3(H) 0.00% 0.01% 22(C) 0.01% 0.36% 41(C) 10.62% 5.48%
4(O) 0.00% 0.11% 23(C) 0.03% 0.13% 42(C) 1.59% 20.43%
5(O) 0.49% 0.63% 24(H) 0.00% 0.06% 43(C) 4.73% 4.97%
6(H) 0.15% 0.16% 25(C) 0.10% 0.33% 44(C) 3.02% 11.50%
7(O) 14.32% 2.12% 26(H) 0.03% 0.19% 45(C) 0.33% 1.80%
8(H) 0.96% 0.38% 27(C) 0.19% 0.17% 46(C) 0.00% 0.02%
9(O) 0.30% 13.58% 28(H) 0.02% 0.03% 47(H) 0.00% 0.02%
10(O) 2.52% 4.34% 29(H) 0.04% 0.08% 48(H) 0.00% 0.02%
11(H) 0.16% 0.46% 30(C) 0.70% 0.66% 49(H) 0.00% 0.00%
12(O) 0.11% 0.75% 31(H) 0.44% 0.21% 50(C) 0.00% 0.01%
13(H) 0.03% 0.12% 32(C) 0.63% 0.82% 51(H) 0.00% 0.01%
14(N) 0.01% 0.01% 33(C) 6.79% 6.18% 52(H) 0.00% 0.00%
15(H) 0.00% 0.00% 34(C) 19.06% 2.19% 53(H) 0.00% 0.00%
16(H) 0.00% 0.01% 35(H) 1.65% 0.16% 54(C) 0.28% 0.13%
17(N) 0.00% 0.03% 36(C) 4.77% 8.49% 55(H) 0.13% 0.03%
18(H) 0.00% 0.00% 37(H) 0.31% 1.11% 56(H) 0.02% 0.02%
19(C) 0.23% 1.17% 38(C) 9.69% 3.22% 57(H) 0.15% 0.06%
Table S3 Calculated atomic charge distributions of TC.
Atom Mulliken Hirshfeld ADCH Atom Mulliken Hirshfeld ADCH
1(O) -0.3009 -0.2628 -0.3126 29(H) 0.2476 0.0347 0.08022(O) -0.3597 -0.3110 -0.3984 30(C) -0.0003 -0.0174 -0.07713(H) 0.3959 0.1646 0.2848 31(H) 0.2137 0.0444 0.11674(O) -0.4275 -0.1412 -0.2563 32(C) 0.2152 0.0849 0.12245(O) -0.4862 -0.2278 -0.4413 33(C) -0.0325 0.0026 -0.03606(H) 0.3520 0.1660 0.3387 34(C) -0.1841 -0.0552 -0.14237(O) -0.4505 -0.2043 -0.3894 35(H) 0.1807 0.0487 0.13478(H) 0.3821 0.1301 0.3368 36(C) -0.1368 -0.0170 -0.09309(O) -0.5924 -0.2181 -0.3607 37(H) 0.1737 0.0603 0.156410(O) -0.4569 -0.1682 -0.3966 38(C) -0.2644 -0.0576 -0.142711(H) 0.3874 0.1374 0.3834 39(H) 0.1708 0.0551 0.144912(O) -0.4866 -0.1976 -0.3593 40(C) 0.2541 0.0928 0.122413(H) 0.3673 0.1635 0.3317 41(C) -0.0536 -0.0472 -0.069014(N) -0.5819 -0.1149 -0.3600 42(C) 0.3219 0.1444 0.171615(H) 0.3274 0.1534 0.3026 43(C) -0.0841 -0.0570 -0.066916(H) 0.2888 0.1504 0.2781 44(C) 0.1669 0.1019 0.128217(N) -0.0827 0.0827 -0.0156 45(C) 0.3757 0.0667 0.110418(H) 0.3247 0.1660 0.2592 46(C) -0.3328 0.0024 -0.211419(C) 0.1507 0.1438 0.1488 47(H) 0.2086 0.0598 0.112820(C) -0.0500 -0.0568 -0.0500 48(H) 0.2019 0.0588 0.115721(C) 0.2750 0.1813 0.2458 49(H) 0.2069 0.0772 0.194622(C) 0.1815 0.1204 0.1017 50(C) -0.3204 0.0159 -0.203223(C) -0.1201 0.0540 -0.0410 51(H) 0.2028 0.0778 0.162724(H) 0.2650 0.0752 0.1518 52(H) 0.2056 0.0718 0.137025(C) -0.3588 -0.0137 -0.0857 53(H) 0.2041 0.0809 0.176226(H) 0.2411 0.0518 0.1175 54(C) -0.5487 -0.0866 -0.267027(C) -0.5519 -0.0426 -0.1518 55(H) 0.1749 0.0422 0.109428(H) 0.2188 0.0487 0.1277 56(H) 0.1858 0.0403 0.1085
Table S4 Calculated atomic charge of CFF for TC.
Atom Mulliken Hirshfeld ADCH Atom Mulliken Hirshfeld ADCH
1(O) -0.3009 -0.2628 -0.3126 29(H) 0.2476 0.0347 0.08022(O) -0.3597 -0.3110 -0.3984 30(C) -0.0003 -0.0174 -0.07713(H) 0.3959 0.1646 0.2848 31(H) 0.2137 0.0444 0.11674(O) -0.4275 -0.1412 -0.2563 32(C) 0.2152 0.0849 0.12245(O) -0.4862 -0.2278 -0.4413 33(C) -0.0325 0.0026 -0.03606(H) 0.3520 0.1660 0.3387 34(C) -0.1841 -0.0552 -0.14237(O) -0.4505 -0.2043 -0.3894 35(H) 0.1807 0.0487 0.13478(H) 0.3821 0.1301 0.3368 36(C) -0.1368 -0.0170 -0.09309(O) -0.5924 -0.2181 -0.3607 37(H) 0.1737 0.0603 0.156410(O) -0.4569 -0.1682 -0.3966 38(C) -0.2644 -0.0576 -0.142711(H) 0.3874 0.1374 0.3834 39(H) 0.1708 0.0551 0.144912(O) -0.4866 -0.1976 -0.3593 40(C) 0.2541 0.0928 0.122413(H) 0.3673 0.1635 0.3317 41(C) -0.0536 -0.0472 -0.069014(N) -0.5819 -0.1149 -0.3600 42(C) 0.3219 0.1444 0.171615(H) 0.3274 0.1534 0.3026 43(C) -0.0841 -0.0570 -0.066916(H) 0.2888 0.1504 0.2781 44(C) 0.1669 0.1019 0.128217(N) -0.0827 0.0827 -0.0156 45(C) 0.3757 0.0667 0.110418(H) 0.3247 0.1660 0.2592 46(C) -0.3328 0.0024 -0.211419(C) 0.1507 0.1438 0.1488 47(H) 0.2086 0.0598 0.112820(C) -0.0500 -0.0568 -0.0500 48(H) 0.2019 0.0588 0.115721(C) 0.2750 0.1813 0.2458 49(H) 0.2069 0.0772 0.194622(C) 0.1815 0.1204 0.1017 50(C) -0.3204 0.0159 -0.203223(C) -0.1201 0.0540 -0.0410 51(H) 0.2028 0.0778 0.162724(H) 0.2650 0.0752 0.1518 52(H) 0.2056 0.0718 0.137025(C) -0.3588 -0.0137 -0.0857 53(H) 0.2041 0.0809 0.176226(H) 0.2411 0.0518 0.1175 54(C) -0.5487 -0.0866 -0.267027(C) -0.5519 -0.0426 -0.1518 55(H) 0.1749 0.0422 0.109428(H) 0.2188 0.0487 0.1277 56(H) 0.1858 0.0403 0.1085
N: The electron density of the system in its original state.N+1: The electron density of the system in an electron ionized state.N-1: The electron density of the system in an electron bounded state.f-: CFF value in electrophilic reaction.f+: CFF value in nucleophilic reaction.
Fig. S1 TG-DSC image of MIL-53 (Fe).
0 200 400 600 800-2
0
2
4
6
8
TG
DSC
Temperature (oC)
DSC
(mW
/mg)
Wei
ght l
oss
(%)
20
40
60
80
100
Fig. S2 N2 adsorption/desorption isotherms of MIL-53 (Fe). The inset shows the pore-
size distribution of the sample.
0 5 10 15 20
0.00
0.05
0.10
0.15
dV/d
D (c
m3 g-1
)
Pore Diameter (nm)0.0 0.2 0.4 0.6 0.8 1.0
80
100
120
140
160
Ads
orbe
d Vo
lum
e (c
m3 g-1
)
Relative Pressure (P/P0)
Fig. S3 (a) The variation of adsorption capacity with adsorption time for TC-HCl on
MIL-53(Fe); Adsorption kinetics of TC-HCl on MIL-53(Fe): (b) pseudo-first-order
kinetics; (c) second-order kinetics for adsorption of TC-HCl on MIL-53(Fe).
(initial concentration = 300 mg/L; adsorbents: 0.2 g/L)
Fig. S4 Recycling test on the degradation rate of TC by MIL-53 (Fe).0 100
0.0
0.2
0.4
0.6
0.8
1.04 th3 rd1 st
(C0-C
)/C0
Time (min)
2 nd
0 100
0 100
0 100
0 100
5 th
Fig. S5 Structure and atomic numbering of TC
(The red color atom is O, the gray color atom is C, the blue color
atom is N and the white color atom is H.)
Fig. S6 (a) HOMO and (b) LUMO of TC.
Fig. S7 Electron density map of TC
Fig. S8 Analysis of Q1 intermediate of TC with m/z=445: (a) MS spectra; (b)
MS/MS spectra
Fig. S9 Analysis of Q2 intermediate of TC with m/z=461: (a-d) MS spectra; (e)
MS/MS spectra of Q2a.
Fig. S10 Analysis of Q3 intermediate of TC with m/z=431: (a) MS spectra; (b)
MS/MS spectra
Fig. S11 Analysis of Q4 intermediate of TC with m/z=427: (a) MS spectra; (b)
MS/MS spectra
Fig. S12 Analysis of Q5 intermediate of TC with m/z=459: (a) and (b) MS spectra; (c)
MS/MS spectra of Q5a.
Fig. S13 Analysis of Q6 intermediate of TC with m/z=417: (a) MS spectra; (b)
MS/MS spectra
Fig. S14 Analysis of Q7 intermediate of TC with m/z=477: (a) MS spectra; (b)
MS/MS spectra
Fig. S11 Analysis of Q8 intermediate of TC with m/z=448: (a) MS spectra; (b)
MS/MS spectra
Fig. S15 Analysis of Q9 intermediate of TC with m/z=432: (a) MS spectra; (b)
MS/MS spectra
Fig. S16 Analysis of Q10 intermediate of TC with m/z=509: (a) MS spectra; (b)
MS/MS spectra
Fig. S17 Analysis of Q11 intermediate of TC with m/z=480: (a) MS spectra; (b)
MS/MS spectra
Fig. S18 Analysis of Q12 intermediate of TC with m/z=496: (a) MS spectra; (b)
MS/MS spectra
Fig. S19 Analysis of Q13 intermediate of TC with m/z=525: (a) MS spectra; (b)
MS/MS spectra