*Corresponding author. Phone, x2920; Fax +34. Vicente del Raspeig, Alicante, Spain

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1 Green synthesis of thin shell carbon-encapsulated iron nanoparticles via hydrothermal carbonization B. Calderon a,*, F. Smith a, I. Aracil a, A. Fullana a a Chemical Engineering Department, University of Alicante, San Vicente del Raspeig Road, s/n San Vicente del Raspeig, Alicante, Spain *Corresponding author. blanca.calderon@ua.es; Phone, x2920; Fax Number of pages: 11 Number of tables: 3 Number of figures: 16 S1

2 Table S1. Physical-chemical characteristics of OMW given by several authors This work [22] [25] Solid residue (%) Density (g/ml) TC 1 (g/l) ph IC 2 (g/l) TOC 3 (g/l) N (%) C (%) H (%) S (%) Total carbon; 2 Inorganic carbon; 3 Total organic carbon Table S2. ICP-OES analysis of OMW. mg/kg K 6260,4 Ca 210,5 Mg 174,5 S 93,8 Na 50,9 Si 30,1 Fe 23,8 Al 5,3 B 4,8 Zn 3,6 Mn 3,6 Sr 0,8 Ni 0,7 Ba 0,5 Cu 0,2 S2

3 Figure S1. FE-SEM images of: a) OMW-CE-nFe with secondary electrons, b) OMW-CE-nFe with backscattered electrons, c) G-CE-nFe with backscattered electrons. Reaction conditions: 200ºC, nfe/nci = 0.05, 3 h. Figure S2. Microscopy images of sample P4 in which the sphere-like supra-structure of the OMWCE-nFe particles is observed, performed with: a) FE-SEM; b) TEM. Reaction conditions of sample P4: 200ºC, nfe/nci = 0.05, 3 h. S3

4 Figure S3. Nitrogen adsorption-desorption isotherms and pore size distributions of the samples: a) G-CE-nFe (sample P3); b) OMW-CE-nFe (sample P4). The pore size distribution of the samples were calculated by the BJH method using the desorption branch of the isotherm. S4

5 Figure S4. Pore size distribution of OMW-CE-nFe (sample P4) obtained by the QSDFT model using a kernel of nitrogen adsorption in slit pores in activated carbon using the desorption branch of the isotherm. Reaction conditions of sample P4: 200ºC, nfe/nc i 0.05, 3h γ-fe 2 O 3 C 2 H 5 NO 4 H 2 O Fe 2 O 3 Fe 2 C x (C 5 H 9 NO 4 ) n Intensity (a.u.) OMW-CE-nZVI Glucose-CE-nZVI β θ (degrees) Figure S5. XRD patterns of G-CE-nFe and OMW-CE-nFe. Reaction conditions: 200ºC, nfe/nc i = 0.05; 3 h. S5

6 Figure S6. Pore size distribution calculated by the BJH model of the OMW-CE-nFe synthesized at different HTC reaction temperatures. Reaction conditions: nfe/nc i = 0.05, 3 h. BJH model was applied to the desorption branch of the isotherm. Figure S7. XRD patterns of OMW-CE-nFe synthesized at various temperatures. Reaction conditions: nfe/nc i = 0.05, 3 h. S6

7 Figure S8. Pore volume and pore size distribution calculated by the BJH model of the OMW-CEnFe synthesized at different HTC reaction times. Reaction conditions: 200ºC, nfe/nc i = BJH model was applied to the desorption branch of the isotherm. Figure S9. XRD patterns of OMW-CE-nFe synthesized at various reaction times. Reaction conditions: 200ºC, nfe/nc i = S7

8 Figure S10. TEM images of OMW-CE-nFe at different Fe/C initial molar ratios. Reaction conditions: 200ºC, 3 h. S8

9 Figure S11. FE-SEM images of OMW-CE-nFe at different Fe/C initial molar ratios. Reaction conditions: 200ºC, 3 h. S9

10 Element Weight (%) C 2.64 O Fe Figure S12. TEM image and EDS analysis of the sample P17 (200ºC, nfe/nc i = 0.25, 3 h). Figure S13. Pore volume and pore size distribution calculated by the BJH model of the OMW-CEnFe synthesized at different Fe/C initial molar ratios. Reaction conditions: 200ºC, 3 h. BJH model was applied to the desorption branch of the isotherm Weight loss (%) T ( C) Figure S14. TG profile of the sample P4 (200ºC, nfe/nc i = 0.05, 3h) under nitrogen atmosphere. S10

11 γ-fe 2 O 3 Fe 3 C C0.14Fe1.86 bcc Fe(0) x C(lonsdaleite) Post-treatment 800ºC Counts Post-treatment 600ºC Before post.treatment Theta Figure S15. XRD pattern of the sample P4 (200ºC, nfe/nc i = 0.05, 3 h,) before and after the post-treatment with nitrogen at high temperatures. S11

12 Figure S16. TG profile of the sample P4 (200ºC, nfe/nc i = 0.05, 3h) subjected to the post-treatment with N 2 at 600ºC, and then to air at 25ºC to study the oxidation of the sample after the posttreatment in air atmosphere. a) Initial part of the TG profile; b) Detail of the final part of the TG profile in which the sample weight during the stage of contact with air is presented. Table S3. Removal efficiencies after 165 h of experiment with the different materials tested. Reaction conditions: C i0 = 10 ppm, pho = 4.7, C Fe,0 = 1 g/l (except for AC-P600 in which the loading was 2.1 g/l). OMW-CE-nFe used was sample P4 (200ºC, nfe/nc i = 0.05, 3 h). Zn Cd Ni Cu Cr nzvi AC CE-nZVI CE-nZVI-P S12