Supporting Information for

Efficient peroxymonosulfate activation and bisphenol A degradation derived

from mineral-carbon materials: key role of double mineral-templates

Shanshan Yanga,b, Xiaodi Duanb, Junqin Liua, Pingxiao Wua,c*, Chunquan Lid, Xiongbo Dongb,d,

Nengwu Zhua,c, Dionysios D. Dionysioub,*a College of Environment and Energy, South China University of Technology, Guangzhou

510006, P.R. Chinab Environmental Engineering and Science Program, Department of Chemical and Environmental

Engineering, University of Cincinnati, Cincinnati, OH 45221-0012, USAc The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of

Education, Guangzhou 510006, P.R. Chinad School of Chemical and Environmental Engineering, China University of Mining and

Technology (Beijing), Beijing 100083, P.R. China

The SI contains 21 pages with 6 texts, 3 tables and 13 figures.

S 1 Materials and reagents

S 1.1 Preparation of minerals

Montmorillonite (Mt) was purchased from Nanhai, Guangdong province, China. The

chemical composition is 30.4% of Si, 52.8% of O, 1.78% of Mg, 6.83% of Al, 0.08% of K, 1.5%

of Ca, 2.26% of Fe, and 0.72% of Na. Synthesis of FeOOH was conducted by hydrothermal

method under alkaline condition. For the synthesis, 50 g of Fe(NO3)3·9H2O were dissolved in

825 mL of deionized water followed by vigorous stirring with a magnetic stirrer. Then 2.5 M

KOH was added at a rate of 5 mL·min-1 with continuous stirring for 0.5 h until the pH reached

12. The suspension was aged at 60 °C in water bath for 24 h and then centrifuged. The

precipitate was washed with deionized water and 95% alcohol until the conductivity was less

than 20 S·cm-1, then dried at 65 °C. After grinding the suspension was passed through 200-mesh

sieve for further use. The preparation of FeOOH-Mt was conducted according to our previous

study.

S 1.2 Reagents

TC (96% purity), BPA (98% purity), PMS, 5,5-dimethyl-1-pyrrolidine N-oxide (DMPO),

2,2,6,6-tetramethyl-4-piperidone (TEMP), and dimethyl sulfoxide (DMSO) were purchased from

Aladdin Chemistry Co., Ltd. Chemical reagents, including ferric chloride hexahydrate

(FeCl3·6H2O), sodium carbonate (Na2CO3), methanol (MeOH), phenol, tert-Butanol (TBA),

furfulyl alcohol (FFA), and p-benzoquinone (p-BQ) were obtained from Guangzhou Chemical

Reagent Factory (Guangzhou, PRC). All the chemicals were used without further purification.

S 2 Detailed information of etching experiments

The mineral-carbon composites were etched by 20 wt% HF and 18 wt% HCl for 2 h,

respectively, and the process was repeated for three times to completely liberate carbon materials

from the mineral, followed by filtration and drying.

S 3 Detailed information of degradation experiments and radical scavenger

experiments

Typically, a 100 ml aqueous solution containing 20 mg∙L-1 BPA and 0.05 g∙L-1 catalyst was

added into a 200 ml glass reactor and magnetically stirred at the room temperature for 180 min to

obtain adsorption-desorption equilibrium. Then, the degradation reaction was initiated by the

addition of 1 mM PMS. At given time intervals of reaction, 1 mL samples were withdrawn,

filtered with a 0.45 μm filter membrane and quenched with 0.5 ml menthol for high performance

liquid chromatography (HPLC) analysis. Radical scavenger experiments were performed under

the same experiment procedures described above while all kinds of quenching agents would be

added along with PMS.

S 4 Detailed information of UPLC-Q-TOF/MS

The degradation products of BPA were analyzed by UPLC-Q-TOF/MS with an Eclips plus

C18 column (diameter, 2.1x100 mm, Agilent) with an auto-sampler. A gradient elution with

acetonitrile (A)-water (containing 10 mM ammonium formate, B) was used. The gradient

program was as follows: 0-5 min, 0-90% A; 5-6 min 90% A; 6-7 min, 90%-20% A; 7-10 min,

20% A. The flow rate was set to 0.4 mL∙min-1. The auto-sampler was conditioned at 25 °C and

the injection volume was 20 μL for analysis. The MS data were obtained by a full scan mass

from m/z 50 to 600 under negative ion mode. The cone voltage and capillary temperature were

30 kV and 600 °C, respectively.

S 5 Detailed information about the reactivation of the reused NPC-FeOOH/Mt

(1) Dichloromethane desorption: The reused NPC-FeOOH/Mt were added into a brown bottle

with 10 ml dichloromethane. Then the mixed solution was shaken horizontally at 180 rpm for 6

hours. Subsequently, NPC-FeOOH/Mt was separated from solution by filtration. The above

procedures were repeated for three times to completely remove the adsorbed intermediates on

NPC-FeOOH/Mt.

(2) Recalcination in N2 atmosphere: The recalcination of reused NPC-FeOOH/Mt was

performed by tube furnace with a predetermined temperature program under N2 atmosphere. The

initial temperature of the tube furnace was set at 30 , then increased to 500 at a heating rate℃ ℃

of 5 °C∙min-1 and held at 500 °C for 60 min.

Table S1 Composition, degree of graphitization and textural properties of the formed carbon materialsElement analysis ICP-OES Raman BET

C,

at.%

N,

at. %

H,

at.%

Fe,

mg∙g-1

Si,

mg∙g-1ID/IG

SSA,

m2 g-1

Average pore

volume, cm2 g-1

Average pore

size, nm

NC 74.99 2.33 1.42 - - 0.96 17.68 0.03 5.55

NPC-Mt 79.21 3.05 2.4 0.523 0.687 0.89 333.72 0.38 4.23

NPC-FeOOH 78.45 4.12 1.75 2.734 - 0.95 480.64 0.73 8.91

NPC-FeOOH/Mt 75.3 4.25 1.81 2.065 1.664 0.96 763.52 1.99 10.45

Table S2 The parameters of XPS fitting spectra for all samplesC 1s N 1s

C-C C-O-C/C-N

C=O π-πshake-up

pyridinic N

graphitic N

NC 1.13 1.71 ‒ 4.13 1.33 2.98NPC-Mt 1.15 1.82 ‒ 4.23 1.25 2.78

NPC-FeOOH 1.09 1.56 2.09 4.19 1.28 2.88NPC-FeOOH/Mt 1.13 1.63 2.11 4.15 1.17 2.98

Fifth used NPC-FeOOH/Mt 1.07 1.58 ‒ ‒ 1.36 2.78DCM- NPC-FeOOH/Mt 1.08 1.60 ‒ ‒ 1.18 2.69

Recalcination NPC-FeOOH/Mt 1.11 1.76 ‒ 4.35 1.48 2.51

Table S3 Water parameters of water samples from Pearl RiverWater parameters

pH 7.36TOC 2.31

Electrical conductivity (μS∙cm-1) 435Cl- (mg∙L-1) 66.19

NO3- (mg∙L-1) 12.38

PO43- (mg∙L-1) -

SO42- (mg∙L-1) 30.21

Fig. S1 Adsorption of TC on different minerals

Fig. S2 HRTEM image (a) and AFM images (b and c) of NPC-FeOOH/Mt

Fig. S3 XRD patterns of NC, NPC-Mt, NPC-FeOOH and NPC-FeOOH/Mt

Fig. S4 Raman spectra of NC, NPC-Mt, NPC-FeOOH and NPC-FeOOH/Mt

Fig. S5 FT-IR spectra of NPC-Mt, NPC-FeOOH and NPC-FeOOH/Mt

Fig. S6 XPS spectra of NC (a), NPC-Mt (b), NPC-FeOOH (c) and NPC-FeOOH/Mt (d)

Fig. S7 Pseudo first order kinetic curves of BPA degradation with the addition of different kinds of scavengers in PMS/NPC-FeOOH/Mt system (a); removal of BPA in PMS/NPC-FeOOH/Mt system in D2O/H2O mix solution and H2O, respectively. Conditions of PMS-based system: dosage of NPC-FeOOH/Mt: 0.05 g∙L-1;

BPA: 20 mg∙L-1; PMS: 1mM; pH: 6.0; Temperature: 30 ℃.

Fig. S8 XPS spectra of fresh NPC-FeOOH/Mt, five times reused NPC-FeOOH/Mt, reused after DCM desorption and reused after N2 recalcination (a); high-resolution C1s (b) and N 1s (c) XPS spectra of five times reused NPC-FeOOH/Mt; high-resolution C1s (d) and N 1s (e) of reused after DCM desorption; high-resolution

C1s (f) and N 1s (g) of reused after N2 recalcination

Fig.S9 Nyquist plots of NPC-FeOOH/Mt, five timed reused NPC-FeOOH/Mt and reused after N2 recalcination

Fig. S10 Effects of catalyst dosages (a and b), PMS dosages (c and d), and initial pH values (e and f) on the BPA degradation in PMS/ NPC-FeOOH/Mt system.(General conditions: BPA = 20 mg·L-1, Temperature: 30

, ℃ pH = 6.0 ; for a and b: [PMS]0 = 0.5 mM; for c and d: [Catalyst]0=0.05 g·L-1; for e and f: [PMS]0 = 0.5 mM, [Catalyst]0=0.05 g·L-1).

Fig. S11 LC chromatograms for BPA degradation in PMS/ NPC-FeOOH/Mt system (a); UPLC-Q-TOF/MS spectra of the intermediates from the BPA degradation in PMS/ NPC-FeOOH/Mt system (b-e)

Fig. S12 GC diagrams for BPA degradation in PMS/NPC-FeOOH/Mt system (a); Mass spectra and possible ion fragment assignment of the identified products or intermediates from the BPA degradation in

PMS/ NPC-FeOOH/Mt system (b-e).

Fig. S13 Proposed pathway of BPA degradation in PMS/NPC-FeOOH/Mt system