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1 Electronic Supplementary Material (ESI) for Journal of Materials Chemistry A. This journal is The Royal Society of Chemistry 2018 Electronic supplementary information Computational screening of hydrophobic metalorganic frameworks for the separation of H2S and C2 from natural gas Zhiwei Qiao, Qisong Xu and Jianwen Jiang * Department of Chemical and Biomolecular Engineering, National University of Singapore, , Singapore Table of Contents Lennard-Jones parameters of MFs Models of S, C 2,, C 2H 6 and C 3H 8 Lennard-Jones parameters and charges of adsorbates Bond bending potential of C 3 H 8 Adsorption capacities using two different GCMC cycles Adsorption isotherms of in ZIF-8 Total adsorption capacity and the adsorption capacity of in hydrophobic MFs Relationships between adsorption capacity and isosteric heat Q o st Relationships between total adsorption capacity N Total and VSA,, LCD Relationships between selectivity S S+C 2 /C1-C3 and VSA,, LCD Relationships between TSN and Q o st, S, VSA,, LCD Performance of ILUFUR Pearson correlation analysis S2 S3 S4 S4 S4 S5 S5 S6 S6 S6 S7 S7 S8 45 best MFs S9 Adsorption isotherms in 6 best MFs References S10 S11 S1

2 Table S1. Lennard-Jones parameters of MFs. 1 Atom ε/k B [K] σ [Å] Atom ε/k B [K] σ [Å] Atom ε/k B [K] σ [Å] Ac Ge Po Ag Gd Pr Al Pt Am Hf Pu Ar Hg Ra As Ho Rb At I Re Au In Rh B Ir Rn Ba K Ru Be Kr S Bi La Sb Bk Li Sc Br Lu Se C Lr Si Ca Md Sm Cd Mg Sn Ce Mn Sr Cf Mo Ta Cl N Tb Cm Na Tc Co Ne Te Cr Nb Th Cu Nd Ti Cs No TI Dy Ni Tm Eu Np U Er V Es s W F P Xe Fe Pa Y Fm Pb Yb Fr Pd Zn Ga Pm Zr S2

3 S C2 C 2H 6 C 3H 8 Fig. S1 Models of S, C 2,, C 2H 6, and C 3H 8. 2 S3

4 Table S2. Lennard-Jones parameters and charges of adsorbates. 3 Atom ε/kb [K] σ [Å] Charge (e) Atom ε/kb [K] σ [Å] Charge (e) C_C _tip4p_ew _C H_tip4p_ew CH M_tip4p_ew CH H_H2S CH S_H2S M_H2S Table S3. Bond bending potential of C3H8. 2 Type θ o k θ/k B (K/rad 2 ) CH 3CCH o There also exists bending potential in C 3H 8, u ( ) 0.5 k ( o ) 2 bending, where is the bending angle and k is the force constant. using cycles N C1-C3 N C2 N H2 S using cycles Fig. S2 Adsorption capacities of different gases in 9 MFs using two different GCMC cycles ( and ). S4

5 30 Loading (mmol/g) This study Exp P/P 0 Fig. S3 Adsorption isotherms of in ZIF-8 from this study and experiment Total Hydrophobic MF index Fig. S4 Total adsorption capacity and the adsorption capacity of in hydrophobic MFs. S5

6 2.0 (a) N H2 S (b) N C Q o st, S (kj/mol) Q o st, C (kj/mol) 2 Fig. S5 Relationships between adsorption capacity and isosteric heat (a) N H2 S ~ Q o st, S (b) N C2 ~ Q o st, C 2. (a) 15 (b) 15 (c) 15 N Total N Total N Total VSA (m 2 /cm 3 ) LCD (Å) Fig. S6 Relationships between total adsorption capacity N Total and (a) VSA (b) (c) LCD (a) (b) 10 5 (c) 10 6 S H2 S+C 2 /C1-C S H2 S+C 2 /C1-C S H2 S+C 2 /C1-C VSA (m 2 /cm 3 ) LCD (Å) Fig. S7 Relationships between selectivity S S+C 2 /C1-C3 and (a) VSA (b) (c) LCD. S6

7 (a) MFs in the shadow region of Fig. 3 (b) MFs in the shadow region of Fig. 3 TSN TSN (c) Q o st, S (kj/mol) MFs in the shadow region of Fig. 3 (d) VSA (m 2 /cm 3 ) MFs in the shadow region of Fig. 3 TSN 10-1 TSN LCD (Å) Fig. S8 Relationships between TSN and (a) Q o st, S (b) VSA (c) (d) LCD. The shadow region indicates TSN > 2, the green points represent the MFs in the shadow region of Fig. 3. Table S4. Performance of ILUFUR. N H2 S N C2 N CH4 N C2 H 6 N C3 H 8 N H2 N total Q o st, S (kj/mol) Q st o, C2 (kj/mol) S H2 S+C 2 /C 1 -C 3 TSN LCD (Å) VSA (m 2 /cm 3 ) S7

8 Pearson Correlation Analysis Pearson correlation analysis is widely used to assess how two variables are associated together. Particularly, the correlation coefficient r xy is utilized to evaluate the relationship between two variables X and Y. 5 In the current study, the respective coefficients between the descriptor variable X (Q o st, S,, VSA and LCD) and the performance variable Y (N H2 S+C 2, S H2 S+C 2 /C 1 -C 3 and TSN) are estimated. All the descriptor and performance variables are normalized by mean-centering and scaling to unit variance. For n MF samples with variables X (x 1, x 2,, x n) and Y (y 1, y 2,, y n), the coefficient r xy of these two variables can be calculated by r xy 1 n 1 n i1 x i x yi y sx sy where x and y are the respective sample means of variables X and Y, s x and s y are the respective sample standard deviations of variables X and Y. The coefficient can take a range of value from 1 to +1. When r xy is positive, variable X associates positively with variable Y, and vice versa. A zero coefficient indicates no linear correlation between two variables. The absolute value of coefficient indicates the strength of linear relationship between X and Y. The higher the absolute value, the stronger is the linear relationship. Therefore, the coefficient value of 1 or +1 represents the perfect negative or positive linear correlation, respectively. S8

9 No. CSD code Q o st, S (kj/mol) VSA (m 2 /cm 3 ) Table S5. 45 Best MFs. LCD (Å) N S+C 2 S S+C 2/C 1 -C 3 TSN Metal rganic linker 1 FUSAL Ag 1,3,5-triaza-7- phosphaadamantane-7- sulfide (PTA=S) 2 ECIWUJ Zn Pyridine 3 NABCIE Co Pyridine 4 ZNBAH Zr ther groups without N 5 FIKQIB Pb ther groups without N 6 PEJRN Co Imidazole 7 ILUFUR Co Pyridine 8 TAKYEL Co Pyridine 9 PXLEV Th ther groups without N 10 ILUFIF Co Pyridine 11 ILUFL Co Pyridine 12 TAKYV Co Pyridine 13 ZNCAI Zn ther groups without N 14 HIQPEE Co Pyrazole 15 KUXTUT Cu Imidazole 16 YERJEL Ni Pyridine 17 XIPB Co Pyridine 18 XEHTUB Cd Tetrazole 19 DITYAH Co Pyridine 20 HIQPII Zn Pyrazole 21 ILUGAY Co Pyridine 22 CAYBA Cu 1,2,3-Triazole 23 AVEME Ag 24 DHYIJ Cu Pyridine 1,3,5-Triaza-7- phosphaadamantane-7- oxide (PTA=) 25 ECSIY Co 1,4-diazabicyclo[2,2,2] octane (DABC) 26 XANMIJ Co Pyridine 27 JASNEX Zn Pyridine 28 FUSEP Ag PTA=S 29 BUSGM Cu Pyridine 30 BUSGIG Cu Pyridine 31 DHYIJ Cu Pyridine 32 XHJUA Cu Pyridine 33 MIZKW Cu Pyridine 34 WNXIH Cu Pyridine 35 QPCII Mn ther groups without N 36 XEWRU Cd Tetrazole 37 FUDUQ Co Imidazole 38 PENZUE Zn Pyridine 39 UYAQER Zn Pyridine 40 AMIKX Cd Pyridine 41 IMIDZB Zn Imidazole 42 IMIDZB Zn Imidazole 43 IXFAD V ther groups without N 44 CAYBAH Cu 1,2,3-Triazole 45 GITZAM Cd Imidazole VSA = 0 is based on a probe size of 3.64 Å (the kinetic diameter of N2). S9

10 (a) C 2 H 6 FUSAL (b) C 2 H C 3 H 8 C 2 ECIWUJ C 3 H 8 C 2 S S (c) (e) C 2 H 6 C 3 H 8 C 2 S NABCIE C 2 H 6 C 3 H 8 C 2 S FIKQIB (d) (f) C 2 H 6 C 3 H 8 C 2 S ZNBAH C 2 H 6 C 3 H 8 C 2 S ILUFUR Fig. S9 Adsorption isotherms in 6 best MFs (a) FUSAL, (b) ECIWUJ, (c) NABCIE, (d) ZNBAH, (e) FIKQIB, (f) ILUFUR. S10

11 References 1. Rappe, A. K.; Casewit, C. J.; Colwell, K. S.; Goddard, W. A.; Skiff, W. M. UFF: A Full Periodic Table Force Field for Molecular Mechanics and Molecular Dynamics Simulations. J. Am. Chem. Soc. 1992,114: Martin, M. G.; Siepmann, J. I. Transferable Potentials for Phase Equilibria. 1. United-Atom Description of n-alkanes. J. Phys. Chem. B. 1998,102: Shah, M. S.; Tsapatsis, M.; Siepmann, J. I. Development of the Transferable Potentials for Phase Equilibria Model for Hydrogen Sulfide. J. Phys. Chem. B. 2015,119: Küsgens, P.; Rose, M.; Senkovska, I.; Fröde, H.; Henschel, A.; Siegle, S.; Kaskel, S. Characterization of Metal-rganic Frameworks by Water Adsorption. Microporous Mesoporous Mater. 2009,120: Hayter, A. J., Probability and Statistics for Engineers and Scientists. 4 th Ed.; Cengage Learning: hio, S11

The Periodic Table. Periodic Properties. Can you explain this graph? Valence Electrons. Valence Electrons. Paramagnetism

The Periodic Table. Periodic Properties. Can you explain this graph? Valence Electrons. Valence Electrons. Paramagnetism Periodic Properties Atomic & Ionic Radius Energy Electron Affinity We want to understand the variations in these properties in terms of electron configurations. The Periodic Table Elements in a column