Electronic Supplementary Material s29

Electronic Supplementary Material

Facile synthesis of -Fe2O3@porous carbon composite materials using Fe-based metal-organic framework: Structure and porosity study Euisoo Kim, Minyoung Yoon*

Department of Nanochemistry, College of Bionano, Gachon University, Sungnam, 461-701, Republic of Korea

*Corresponding author. Tel: +82-31-750-8721

E-mail addresses: [email protected] 1. MIL-100 synthesis and characterization

Synthesis of MIL-100 (Fe): MIL-100(Fe) was synthesized under hydrothermal conditions according to reported synthetic procedure. [S1] Typically, 1,3,5- benzenetricarboxylic acid (688 mg), iron powder (277.5 mg), hydrofluoric acid (200 L) and concentrated nitric acid (190 L) were mixed in a Teflon-lined steel bomb with 25 mL pure water. Followed by heating at 150 °C for 12 h in an oven. Resulting light orange solid was collected by filtration and washed with water and ethanol. The as-synthesized MIL-100 (Fe) was further purified by a using hot water and ethanol and the final product was analyzed by PXRD (Fig. S1).

Fig. S1. Simulated and experimental PXRD profiles of MIL-100 2. SEM image

Further SEM images of 1 – 3 are shown in Fig. S3.

Fig. S2. Additional SEM images of (A) for 1, (B) for 2, and (C) 3

3. TEM image

Further TEM images of resulting materials are shown in Fig. S3.

Fig. S3. Additional TEM images of (A) 1, (B) 2, and (C) 3

4. Carbon composite synthesis using other MOF, Co2(BDC)2(dabco)

The other candidate MOF, Co2(BDC)2(dabco) (CBD)was employed to present generality of this work. The framework was prepared following the reported procedure [2]. Structure of the prepared CBD was characterized by PXRD (Figure S4).

Fig. S4. PXRD profiles of resulting carbon materials S1 (black), S2 (red), and S3 (blue)

Using the prepared CBD, porous carbon composite was prepared using same synthetic procedure described in the main text. CBD-C1 (S1), CBD-C2 (S2), and CBD-C3 (S3) were successfully prepared from direct carbonization of CBD, CBD- FFA-wash, and CBD-FFA, respectively. Carbon contents of S1 (7.5%), S2 (26%) and S3 (30%) shows similar tendency as MIL-100, which was increased by treatment of FFA. Gas sorption experiment data and pore structure analysis data were presented in Fig. S5, Fig. S6, and Table S1. Although the porosity was exactly controlled, surface area of the resulting composite materials was increased as increasing carbon contents of the resulting materials. However, only S1 does not follow the result of main text. Fig. S5. (a) N2 sorption isotherms at 77 K and (b) cumulative pore volume for S1 – S3.

Table 1. Pore structure analysis summary of S1 – S3 Total pore Langmuir Micropore Mesopore Macropore

volume surface area volume volume volume S1 0.22 cm3/g 176 m2/g 0.02 cm3/g 0.17 cm3/g 0.03 m2/g S2 0.11 cm3/g 245 m2/g 0.07 cm3/g 0.02 cm3/g 0.02 m2/g S3 0.17 cm3/g 289 m2/g 0.08 cm3/g 0.05 cm3/g 0.04 m2/g

Fig. S6 Pore size distribution of S1 – S3. To demonstrate difference of S1 with other composite materials, PXRD of the composite material was measured (Fig. S7). PXRD data showed that S2 and S3 are

Co2O3 embedded porous carbon, whereas S1 is Co metal embedded composite. The difference may be derived from the nature of metal nanoparticle. Further work for the presented materials is in progress.

5. References

[1] G. Férey, C. Serre, C. Mellot-Draznieks, F. Millange, S. Surblé, J. Dutour, I. Margiolaki, Angew. Chem. Int. Ed. 43 (2004) 6296. [2] T. Takei, T. Ii, J. Kawashima, T. Ohmura, M. Ichikawa, M. Hosoe, Chem. Letter. 36 (2009) 1136.