Supplementary data for:
Phosphorus-rich microorganism-enabled synthesis of cobalt phosphide/carbon
composite for bisphenol A degradation through activation of peroxymonosulfate
Wenhua Tong, Yi Xie, Haiqiong Luo, Jinye Niu, Wenyi Ran, Wanrong Hu, Luyao Wang, Changhong
Yao, Wenbin Liu, Yongkui Zhang, Yabo Wang*
School of Chemical Engineering, Sichuan University, Chengdu 610065, China
Corresponding author:
Yabo Wang
School of Chemical Engineering, Sichuan University, Chengdu 610065, China
Tel.: +86-28-85405221; Fax: +86-28-85405221
Email: [email protected] (Y. Wang)
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Fig. S1 N2 adsorption-desorption isotherms of various samples.
Fig. S2 XPS spectra of C 1s for CP-700 (below) and CP-900 (above) samples.
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Fig. S3 Effect of initial solution pH on BPA degradation using CP-900 as catalyst. Reaction
conditions: [BPA] = 0.1 mmol L-1, [catalyst] = 0.4 g L-1, [PMS] = 0.4 g L-1. Data are presented as
mean values (n = 3) ± SD.
Fig. S4 Residual concentration of PMS in solution as a function of time. Reaction conditions: [BPA]
= 0.1 mmol L-1, [CP-900] = 0.4 g L-1, [PMS] = 0.4 g L-1. Data are presented as mean values (n = 3) ±
SD.
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Fig. S5 The relationship between BPA concentration and its inhibition rate on Tetraselmis
subcordiformis. Data are presented as mean values (n = 3) ± SD.
Fig. S6 Growth situation of Tetraselmis subcordiformis cells observed under an optical microscope.
(a) The cells grew normally without BPA. (b) Chlorophyll breakdown and dead autolysis occurred in
cells exposed to 50 mg L-1 BPA. (c) The cells grew well in the degraded BPA solution.
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Text S1: GC-MS and LC-MS analysis of BPA degradation intermediates
(1) GC−MS Analysis. The BPA degradation intermediates were extracted by using dichloromethane.
GC/MS analysis was performed with an Agilent 7890-5977 B system equipped with capillary
column (HP-5MS, 30 m × 0.25 mm × 0.25 μm). Chromatographic conditions: the temperature of
injection port was 250 °C, the temperature program of column was 80-250 (8 °C min‒1) and 250 °C
(2 min). The interface was kept at 250 °C. Qualitative analysis was performed in the electron-impact
(EI) mode, at 70-eV potential using 30-450 msu for qualitative analysis.
(2) LC−MS Analysis. Identification of the intermediates were performed with an Agilent 1200
HPLC system equipped with a C-18 column (250 × 4.6 mm, 5 μm, Grace Davison Discovery
Sciences., Maryland, USA) at 25 °C. MS (Thermo TSQ quantum ultra) was fitted with an ESI
(electrospray ionization) mode. The mobile phase is a mixture of 50% acetonitrile and 50% ultrapure
water running at a flow rate of 1 mL min-1.
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Fig. S7 GC-MS chromatogram and mass spectra for BPA in water reaction for 10 min. (a) total ions
chromatogram (TIC) from GC-MS; (b), (c), (d), (e), (f), (g), (h) and (i) mass spectra of the main
peaks. Reaction conditions: [BPA]0 = 0.1 mmol L−1, [catalyst] = 0.4 g L−1, [PMS] = 0.4 g L−1 and
reaction time = 10 min.
Fig. S8 LC-MS chromatogram and mass spectra for BPA in water reaction for 10 min. (a) total ions chromatogram (TIC) from LC-MS; (b) UV-vis spectra of intermediates at 254 nm; (c) mass spectra of the main peaks. Reaction conditions:
[BPA]0 = 0.1 mmol L−1, [catalyst] = 0.4 g L−1, [PMS]= 0.4 g L−1 and reaction time = 10 min.
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Text S2: Digestion process of dry biomass
Typically, 20 mg of dry biomass was suspended in 25 mL de-ionized water. After adding 2 mL
concentrated HNO3, the suspension was concentrated to ca. 10 mL by heating. This step was repeated
for one time. Then, 3 mL of perchloric acid was added into the cooled suspension, which was further
concentrated to ca. 3 mL by heating. 10 mL of de-ionized water was added into the concentrated
solution, which was titrated by NaOH solution and H2SO4 solution to near neutral. Finally, the
solution was quantified to 50 mL with a volumetric flask for further analysis.
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Table S1 Comparison of BPA degradation over various catalytic systems for
AOPs.
Type of AOP[BPA]
(mg L-1)
[catalyst]
(g L-1)
Reaction
time (min)
BPA degradation
rate (%)
k
(min−1)Reference
VUV/H2O2 100 - 7 100 0.528 [1]
magnetite nanoparticles supported
on carbon/UV/US/PMS30 0.20 60 100 0.150 [2]
Iron functionalized biochar/PMS 20 0.15 5 100 - [3]
manganese/magnetite/graphene
oxide hybrid catalyst/PMS91 0.50 30 95 0.113 [4]
Co3O4/MXene (CMs)
composite/PMS20 0.3 7 95 0.398 [5]
magnetic MnFe2O4/PMS 5 0.20 30 88 0.113 [6]
MnO2 of different structures/PMS 1.4 0.05 10 92 - [7]
perylene imide-modified g-
C3N4/visible light10 1.00 60 96 0.0501 [8]
sulfur-doped carbon nitride/PMS 50 0.60 120 95 0.0225 [9]
vanadium-titanium magnetite/PMS 50 12 120 90 - [10]
cobalt phosphide/carbon
composite/PMS23 0.4 30 98 0.149 This work
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Table S2 Possible intermediates of BPA degradation
No. Compound nameMolecular
weight (m/z)Tentative structure Detected
Reported in/by
1 Bisphenol A 228 HO OH - [4, 11]
2Dihydroxylated BPA
(DHBPA)260 √ [4, 12, 13]
3Quinone of
monohydroxylated BPA243 √ [4, 14]
4Quinone of dihydroxylated
BPA258 √ [5]
5Quinone of dihydroxylated
BPA258 √ [5, 14]
6 4-isopropylphenol 136 √[9, 11, 14,
15]
72-(4-hydroxyphenyl)-
propanol-2-ol152 HO OH √ [13, 16]
8 Styrene 104 √ [8, 9]
91,2-dimethyl-4-(prop-1-en-
2-yl)benzene146 √ [17]
10 Phenol 94OH
√ [17, 18]
11 Benzaldehyde 152 √ [17]
12 m-xylene 106 √ [19]
13 1,5-hexadien-3-ol 98OH
√ [15]
14 Penta-1,4-dien-3-one 82 √ [9]
15 3-methylbutanone 86 √ [12]
16 Acetone 58 √ [12]
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