Supporting Information. High-throughput Computational Screening of the MOF Database for. CH 4 /H 2 Separations. Sariyer, 34450, Istanbul, Turkey

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1 Supporting Information High-throughput Computational Screening of the MOF Database for CH 4 /H 2 Separations Cigdem Altintas, a Ilknur Erucar b and Seda Keskin a* a Department of Chemical and Biological Engineering, Koc University, Rumelifeneri Yolu, Sariyer, 34450, Istanbul, Turkey b Department of Natural and Mathematical Sciences, Faculty of Engineering, Ozyegin University, Cekmekoy, 3474, Istanbul, Turkey *Corresponding author. skeskin@ku.edu.tr, Phone: +0 (212) Submitted to ACS Applied Materials & Interfaces S-1

2 35 σ H2 σ CH LCD (Å) PLD (Å) Figure S1. Pore limiting diameters (PLD) and the largest cavity diameters (LCD) of MOFs. Red lines show the kinetic diameters of the H 2 and CH 4 molecules. S-2

3 S acc (m 2 /g) LCD ( Å ) Figure S2. Porosities and accessible surface areas of MOFs, color-coded according to their largest cavity diameters. φ S-3

4 10 Gas uptake (mmol/g) closed symbols: simulations open symbols: experiments Pressure (bar) CH4 uptake at 28 K IRMOF-1 CuBTC UiO-66 ZIF-8 H2 uptake at 77 K IRMOF-1 CuBTC UiO-66 H 2 uptake at 28 K ZIF-8 Figure S3. Comparison of the adsorption isotherms of CH 4 and H 2 in some prototypical MOFs, IRMOF-1, CuBTC, UiO-66 and ZIF-8. Experimental data for adsorption isotherms of IRMOF-1, 1-2 CuBTC, 3-4 UiO and ZIF were taken from the literature. S-4

5 1.0 (a) 1 bar R S acc LCD φ 1/ AD Q 0 st 1.0 (b) 10 bar R S acc LCD φ Q 0 st 1/ AD Figure S4. R 2 values showing the relation between selectivity and several parameters calculated at (a) 1 bar (b) 10 bar. S-5

6 Table S1. Interaction potential parameters used for gas molecules Molecule σ (Å) ε/k B (K) H CH Table S2. Comparison of our simulated adsorption isotherms with the experimental data for CH 4 and H 2 in various MOFs. MOF Pressure and temperature Gas References IRMOF bar, 28 K CH 4 IRMOF bar, 28 K CH 4 PCN bar, 28 K CH 4 NU bar, 28 K CH 4 Bio-MOF bar, K H 2 Zn(bdc)(ted) bar, 28 K CH 4 COF-5, COF-6, COF bar, 77 K H 2 MMIF 0-1 bar, 15 K CH 4 ZIF bar, 28 K CH 4 ZIF-68, ZIF bar, 273 K CH 4, H 2 PCN bar, 77, 87, 15, 28 K CH 4, H 2 PCN-6, PCN-6', PCN-10, PCN-11, PCN-14, PCN-16, PCN-20, PCN-26, PCN-46, PCN-80 PCN-11, PCN-14, PCN-16, PCN-26, PCN- 46, PCN bar, 77, 87, 150, 28 K H bar, 26, 28, 300 K CH Table S3. Coefficients of the model used to predict selectivity of MOFs: S b ads = a (1/ AD) + c Coefficient Value a b c 0.17 d ( LCD) d S-6

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