Supporting Information

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1 Supporting Information Enhancement of H2O2 Decomposition by the Cocatalytic Effect of WS2 on the Fenton Reaction for the Synchronous Reduction of Cr(VI) and Remediation of Phenol Chencheng Dong, Jiahui Ji, Bin Shen, Mingyang Xing* and Jinlong Zhang* Key Laboratory for Advanced Materials and Institute of Fine Chemicals, School of Chemistry & Molecular Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai , P.R. China Corresponding Author 19 * mingyangxing@ecust.edu.cn; jlzhang@ecust.edu.cn S1

2 22 Table of Contents Table S1 The adsorbent systems for the removal of phenol..s4 Table S2~S4 Apparent Kinetic Modeling....S5 Table S5 Comparison between the past reports and our research on the Fenton reaction for the remediation of pollutants..s6 Figure S1 Sacrificial effect of tert-butyl alcohol (TBA) in WS 2 cocatalytic Fenton oxidation of 10 mg/l phenol..s7 Figure S2 Effects of electron scavenger, hole scavenger and superoxide scavenger on the activity of WS 2 cocatalytic Fenton system.s8 Figure S3 PL spectra of the H 2O 2 mixed with benzoic acid with the increase of the heating time at 90 o C..S9 Figure S4 Mass spectra of intermediates observed in the high performance liquid chromatography (HPLC) that appeared in the degradation process of phenol under different reaction time.s10 Figure S5 XPS spectra of S2p of WS 2 before and after mixing with Fe 3O 4...S11 Figure S6 Raman spectra of Fe 3O 4 (commercial), WS 2 (commercial) and Fe 3O 4+WS 2 through direct mixing in water.s12 Figure S7 Digital image of magnetic separation of WS 2/Fe 3O 4 mixture and WS 2 in aqueous solution..s13 Figure S8 Digital image of magnetic separation of WS 2/Fe 3O 4 mixture and WS 2 in cyclohexane...s14 Figure S9 Activity comparison of WS 2 co-catalytic Fenton reaction before and after N 2-bubbling treatment for the degradation of phenol S15 Figure S10 Digital image of magnetic separation of WS 2/Fe 3O 4 mixture in the presence or absence of H 2O 2..S16 Figure S11 The proposed mechanism of WS 2-cocatalytic Fenton process...s17 Figure S12 Individual effect of H 2O 2 (0.04 mmol/l) towards Cr(VI) reduction and phenol oxidation without addition of catalyst and co-catalyst..s18 Figure S13 TEM images and XRD patterns of the WS 2 before and after the cycle test S19 Figure S14 Various concentration of phenol and chromium for simultaneous oxidation and reduction S20 S2

3 Figure S15 Zeta potentials of WS 2 under various ph values.s21 Figure S16 Simultaneous reduction of Cr(VI) and degradation of phenol over different Fenton reaction...s22 Figure S17 Simultaneous reduction of Cr(VI) and degradation of phenol over different Fenton-like reactions.s23 Figure S18 WS 2 co-catalytic Fenton reaction for the degradation of phenol by different Fenton-like reaction...s24 References.S S3

4 74 75 Table S1. The adsorbent systems for the removal of phenol. Crystalline Removal capacity Adsorbents S BET (m 2 g -1 ) structure (mg g -1 h -1 ) Ref. PHAp 235 poor HAp 55 high FAp 35 high Activated coal high Rattan sawdust based activated carbon 1083 high Commercial activated carbon high Sugarcane bagasse fly ash high Activated carbonlaboratory grade (ACL) high Tectona grandis sawdust activated carbon 585 high Samla coal high Our work(ws 2) 6 high S4

5 Table S2. The data corresponding to the fitting line between lg(dc/dt) and lg[fe 2+ ]0 under the visible light irradiation. Condition FeSO 4 (g/l) Fitting Equation R 2 -lg(dc/dt) C/C 0= e -t/ Vis 0.04 C/C 0= e -t/ C/C 0= e -t/ C/C 0= e -t/ Table S3. The data corresponding to the fitting line between lg(dc/dt) and lg[h2o2]0 under the visible light irradiation. Condition H2O2(mmol/L) Fitting Equation R 2 -lg(dc/dt)0 0.1 C/C 0= e -t/ C/C 0= e -t/ Vis 0.4 C/C 0= e -t/ C/C 0= e -t/ C/C 0= e -t/ Table S4. The data corresponding to the fitting line between lg(dc/dt) and lg[ws2]0 under the visible light irradiation. Condition WS2(g/L) Fitting Equation R 2 -lg(dc/dt)0 3 C/C 0= e -t/ Vis 4 C/C 0= e -t/ C/C 0= e -t/ C/C 0= e -t/ S5

6 Table S5. Comparison between the past reports and our research on the Fenton reaction for the remediation of pollutants. Pollutant Fe 2+ usage Reaction Degradation ph Ref concentration H2O2 usage time rate 100 mg/l phenol [Fe 2+ ] = 10 mg/l [H 2O 2] = 500 mg/l 100 mg/l phenol [Fe 2+ ] = 10 mg/l [H 2O 2] = 358 mg/l 1000 mg/l phenol [Fe 2+ ] = 10 mg/l [H 2O 2] = 500 mg/l 1128 mg/l phenol [Fe 2+ ] = 28 mg/l [H 2O 2] = 6800 mg/l 200 mg/l phenol [Fe 2+ ] = 45 mg/l [H 2O 2] = 1020 mg/l 20 mg/l phenol 30 mg Fe-Al, [H 2O 2] = 136 mg/l 0.53 mmol phenol [Fe 2+ ] = 30 mg/l [H 2O 2] = 165 mg/l 200 mg/l phenol [Fe 2+ ] = 45 mg/l 10min ~ 18% min ~ 90% min 40% min ~ 30% min ~ 70% min 5% min ~ 80% min ~ 25% [H 2O 2] =800 mg/l H 2O mg/l phenol [Fe 2+ ] = 500 mg/l [H 2O 2] = 1000 mg/l 25 min 90% [Cr(VI)] 0 = 10 mg/ L, [4-CP] 0 = 100 mg/l nzvi = 0.4 g/l, [H 2O 2] 0 = 333 mg/l 5min [4-CP] ~ 5% Cr(VI) ~70% CP = 13 mg/l Cr(VI) = 5.2 mg/l [Fe 3+ ] = 5.6 mg/l 30min [4-CP] ~ 45% Cr(VI) ~ 90% mg/l phenol Cr(VI) = 40 mg/l [Fe 2+ ] = 1.47 mg/l [H2O2] = 13.6 mg/l 1min [Phenol]~80% Cr(VI) ~90% 3.8 This work S6

7 Figure S1. Sacrificial effect of tert-butyl alcohol (TBA) in WS 2 cocatalytic Fenton oxidation of 10 mg/l phenol (100 ml solution including 0.04 g/l Fe(SO 4) 7H 2O, 4.0 g/l WS 2, 0.4 mmol/l H 2O 2, ph= 3.8, 100 mg/l tert-butyl alcohol (TBA), Vis: under visible light (λ> 420 nm) illumination) S7

8 Figure S2. Effects of electron scavenger (AgNO3), hole scavenger (CH3OH) and superoxide scavenger (1,4-benzoquinone) on the activity of WS 2 cocatalytic Fenton system S8

9 Figure S3. PL spectra of the H2O2 mixed with benzoic acid with the increase of the heating time at 90 o C. 4.0 µl H2O2 can be completely decomposed in 100 ml aqueous solution by heating it at 90 o C for 120 min S9

10 Figure S4. Mass spectra of intermediates observed in the high performance liquid chromatography (HPLC) that appeared in the degradation process of phenol under different reaction time S10

11 Figure S5. XPS spectra of S2p of WS2 before and after mixing with Fe3O S11

12 Figure S6. Raman spectra of Fe3O4 (commercial), WS2 (commercial) and Fe3O4+WS2 through direct mixing in water S12

13 Figure S7. Digital image of magnetic separation of WS2/Fe3O4 mixture and WS2 in aqueous solution S13

14 Figure S8. Digital image of magnetic separation of WS2/Fe3O4 mixture and WS2 in cyclohexane S14

15 Figure S9. Activity comparison of WS2 co-catalytic Fenton reaction before and after N2-bubbling treatment for the degradation of phenol (10 mg/l). (100 ml solution including 0.04 g/l Fe(SO4) 7H2O, 4.0 g/l WS2, 0.4 mmol/l H2O2, ph= 3.8, Vis: under visible light illumination (λ> 420 nm) S15

16 Figure S10. Digital image of magnetic separation of WS2/Fe3O4 mixture in the presence or absence of H2O S16

17 Figure S11. The proposed mechanism of WS2-cocatalytic Fenton process S17

18 Figure S12. Individual effect of H2O2 (0.04 mmol/l) towards Cr(VI) reduction and phenol oxidation without addition of catalyst and co-catalyst S18

19 Figure S13. (a) TEM images of the WS2 before and after the cycle test for the degradation of phenol. (b) HRTEM images of the WS2 after the cycle test. (c) XRD patterns of the WS2 before and after the cycle test S19

20 Figure S14. Various concentration of phenol (a: 5 mg/l, b: 10 mg/l, c: 20 mg/l and d: 40 mg/l) and chromium (40 mg/l, 60 mg/l and 80 mg/l) for simultaneous oxidation and reduction S20

21 Figure S15. Zeta potentials of WS2 under various ph values S21

22 Figure S16. Simultaneous reduction of Cr(VI) and degradation of phenol over different Fenton reaction (100 ml solution including 0.04 g/l Fe(SO4) 7H2O, 0.4 mmol/l H2O2, 10 mg/l phenol, and 40 mg/l Cr(VI), ph= 3.8, Vis: under visible light illumination (λ> 420 nm)) S22

23 Figure S17. Simultaneous reduction of Cr(VI) (a) and degradation of phenol (b) over different Fenton-like reactions (100 ml solution including 0.04 g/l Fe(SO4) 7H2O, 400 or 500 mg WS2, 0.4 mmol/l H2O2, 10 mg/l phenol, and 40 mg/l Cr(VI), ph= 3.8, under visible light illumination: λ> 420 nm) S23

24 Figure S18. WS2 co-catalytic Fenton reaction for the degradation of phenol (10 mg/l) by different Fenton-like reaction: (a) Fe(III)/H2O2 and (b) Ni(II)/H2O2. (100 ml solution including 0.04 g/l metal salts, 4.0 g/l WS2, 0.4 mmol/l H2O2, ph= 3.8, under visible light illumination: λ> 420 nm). 284 References: Bahdod, A.; El Asri, S.; Saoiabi, A.; Coradin, T.; Laghzizil, A., Adsorption of phenol from an aqueous solution by selected apatite adsorbents: Kinetic process and impact of the surface properties. Water Res. 2009, 43, (2), Vázquez, I.; Rodríguez-Iglesias, J.; Marañón, E.; Castrillón, L.; Álvarez, M., Removal of residual phenols from coke wastewater by adsorption. J. Hazard. Mater. 2007, 147, (1), Özkaya, B., Adsorption and desorption of phenol on activated carbon and a comparison of isotherm models. J. Hazard. Mater. 2006, 129, (1), Srivastava, V. C.; Swamy, M. M.; Mall, I. D.; Prasad, B.; Mishra, I. M., Adsorptive removal of phenol by bagasse fly ash and activated carbon: Equilibrium, kinetics and thermodynamics. Colloids Surf. A: Physicochem. Eng. Aspects 2006, 272, (1), Mohanty, K.; Das, D.; Biswas, M. N., Adsorption of phenol from aqueous solutions using activated carbons prepared from Tectona grandis sawdust by ZnCl 2 activation. Chem. Eng. J. 2005, 115, (1), Ahmaruzzaman, M.; Sharma, D. K., Adsorption of phenols from wastewater. J. Colloid Interf. Sci. 2005, 287, (1), S24

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