Discovery of an Optimal Porous Crystalline Material for the Capture of. Chemical Warfare Agents

Transcription

1 Supporting Information for: Discovery of an Optimal Porous Crystalline Material for the Capture of Chemical Warfare Agents Ismael Matito-Martos, #,a,b Peyman Z. Moghadam, #, *,b Aurelia Li, b Valentina Colombo, c Jorge A. R. Navarro, d Sofia Calero, *,a and David Fairen-Jimenez*,b a Department of Physical, Chemical and Natural Systems, University Pablo de Olavide, Sevilla 41013, Spain b Adsorption & Advanced Materials Laboratory (AAML),Department of Chemical Engineering and Biotechnology, University of Cambridge, Philippa Fawcett Drive, Cambridge CB3 0AS, United Kingdom c Department of Chemistry, University of Milan, Milan 20133, Italy d Department of Inorganic Chemistry, University of Granada, Granada 18071, Spain # These authors contributed equally S1

2 Figure S1. Histograms of structural properties for the 2,932 MOF structures from the DDEC database: gravimetric surface area, pore volume, large cavity diameter, and helium void fraction. Gravimetric surface area was calculated using a probe radius of 1.86 Å (corresponding to N 2 ). Structures with PLD lower than 1.86 Å are depicted in red. Figure S2. Heat of adsorption (Q st ) as a function of gravimetric surface area of 1,647 MOFs for a. mustard gas, b. sarin, and c. soman. Color code represents the largest cavity diameter (LCD) of MOF structures. S2

3 Figure S3. Henry s constants (K H ) for water as a function of the largest cavity diameter (LCD) in 1,647 MOF structures at 298 K. Purple and blue dashed lines depict water K H in ZIF-8 and HKUST-1, respectively, as benchmarks for hydrophobicity and hydrophilicity in MOFs. Color code represents isosteric heat of adsorption (Q st ) for water. Figure S4. Selectivity of a., d. DES, b., e. DMMP, and c., f. DIFP over water based on the K H ration as a functional of surface area in 1,647 MOF structures at 298 K. The color code represents the isosteric heat of adsorption (Q st ) for water (a-c) and the largest cavity diameter (d-f) for each MOF structure. S3

4 Figure S5. Selectivity of a. mustard gas, b. sarin, c. soman, d. DES, e. DMMP, and f. DIFP over water based on the K H ration as a function of the surface area in 1,647 MOF structures. The color code shows the isosteric heat of adsorption (Q st ) for each CWA or simulant. Figure S6. GCMC simulations of water adsorption at 3,280 Pa (i.e. 80% RH) as a function of the largest cavity diameter (LCD) for 156 selected hydrophobic MOFs. The color code shows the isosteric heat of adsorption (Q st ) for water. Figure S7. GCMC calculated a. mustard, b. sarin, and c. soman loading at 13.8 Pa (mustard), 0.8 Pa (sarin and soman) as a function the largest cavity diameter (LCD) of 156 selected hydrophobic MOFs. The color code shows the isosteric heat of adsorption (Q st ) for each CWA. S4

5 Selection of top MOFs The synthesis of the first selected MOF structure (CSD code: BIBXUH), ([Ni 8 (OH) 4 (H 2 O) 2 (L) 6 ] n, where L = 1,4- (4-bispyrazolyl)benzene (H 2 BPB), was first reported by Padial et al. 1, along with an isoreticular series of MOFs based on bi-pyrazolate linkers and Ni II hydroxo clusters. The design of this MOF was oriented to the capture of VOCs under moisture conditions. Co26NDP* was also highlighted in our results, having built up by interconnecting 1D Co II polymer chains with naphthalene instead of benzene as spacer in the bipyrazolate linker. Finally, the MOF referenced as UTEWOG was reported by Colombo et al. 2 as one of four framework based on the ligand 1,3,5-tris(1H-pyrazol-4-yl)benzene (H 3 BTP). This MOF, also named Ni 3 (BTP) 2, shows an expanded sodalite-like topology. Figure S8. Crystal structure of NiBPB (CCDC code: BIBXUH). The inset shows the Ni(II) hydroxo cluster. Carbon, gray; nitrogen, blue; nickel, green; oxygen, red. Hydrogen atoms have been omitted for simplification. Figure S9. Atomic representation of the structure of Co26NDP i. Carbon, nitrogen, and cobalt atoms are depicted in grey, blue, and purple respectively. Hydrogen atoms have been omitted for simplification. i This MOF corresponds to core-mof-ddec-365 from the work from Nazarian et al.; no CSD code was provided in the paper, and is not found in the CSD, which strongly suggests it is a hypothetical structure. S5

6 Figure S10. Temperature programed desorption of [Ni 3 (BTP) 2 ], blue curve, after the measurement of the DES breakthrough curve. 20 ml min -1 flow of N 2 and a heating rate of 10 ºC min -1. The released DES was studied by means of a mass spectrometer. Red curve represents the evolution of temperature with time. Figure S11. TGA of hydrated [Ni3(BTP) 2 ] a. before and b. after the DES breakthrough curve measurement at RH (80 %). Air atmosphere and heating rate of 20 ºC min -1. [Ni 3 (BTP) 2 ] 7.5H 2 O (H 2 O calc. 15.7%; found: 15.7 %) [Ni 3 (BTP) 2 ] 4H 2 O 0.5(DES), H 2 O calc. 8.6%; found: 8.5% ) DES calc. 5.4%; found: 4.6% ). S6

7 Figure S12. Diffuse reflectance spectra of hydrated [Ni 3 (BTP) 2 ] a. before and b. after the DES breakthrough curve measurement at RH (80 %). Scheme S1. Schematic representation of the experimental setup used to evaluate diethylsulphide (DES) capture by [Ni 3 (BTP) 2 ] MOF under humid conditions (80% relative moisture) at room temperature. S7

8 Table S1. Structural properties for the top three MOF structures and calculated adsorption loadings for mustard, sarin, soman and water at 298 K and at 3,280, 13.8 Pa and 0.8 Pa for water, mustard, and sarin and soman respectively. Loading CCDC Density LCD GSA HVF Mustard Sarin Soman Water (-) g cm -3 Å m 2 g -1 (-) mol kg -1 mol kg -1 mol kg -1 mol kg -1 BIBXUH Co26NDP* UTEWOG Table S2. Results obtained from Widom simulations in the top three MOF structures for mustard, sarin, soman and Water at 298 K. Mustard Sarin Soman Water Mustard / Water Sarin / Water Soman / Water CCDC Code Q st K H Q st K H Q st K H Q st K H SelQ st SelK H SelQ st SelK H SelQ st SelK H kj mol -1 mol kg -1 pa -1 kj mol -1 mol kg -1 pa -1 kj mol -1 mol kg -1 pa -1 kj mol -1 mol kg -1 pa -1 (-) (-) (-) (-) (-) (-) BIBXUH E E E E E E E+06 Co26NDP* E E E E E E E+07 UTEWOG E E E E E E E+11 S8

9 Computational Details. Force fields. Table S3. Parameters for non-bonded interactions. ε /kb [K] σ [Å] charge [e] ε /k B [K] σ [Å] charge [e] Mustard 3 Soman 4 S CH c / d / f CH a / b CH Cl C DES 5 O-(CH) S O=(P) CH P CH F Sarin 4 DIFP 6 CH d / e O=(P) CH-(O) O-(CH) O-(CH) CH-(O) O=(P) CH P F F P DMMP 4 Water (TIP4P) 7 CH c / d O O-(CH 3 ) H O=(P) L P a Site adjacent to Cl. b Site adjacent to S. c Site adjacent to oxygen. d Site adjacent to phosphorus. e Site adjacent to CH group. f Site adjacent to C. S9

10 Table S4. Vibration and Bending Parameters for DMMP, Sarin, and Soman; 4 Mustard, 3 DES, 5 and water. 7 Vibration Bond length (Å) Bending Bond angle (deg) kθ/kb (K) P=O O=P-CH P-CH O=P-O P-O CH 3 -P=O O-CH CH 3 -O-P CH 3 -CH O-P-O CH-O CH 3 -CH-O CH-C CH 3 -CH-CH CH 3 -C CH 3 -C-CH F-P CH 3 -P-F S-CH CH 3 -CH 2 -S CH 2 -CH CH 2 -CH 2 -S CH 2 -CH CH 2 -S-CH 2 a CH 2 -Cl CH 2 -S-CH 2 b O-H Cl-CH 2 -CH O-L H-O-L H-O-H a Bending parameters for DES. B Bending parameters for mustard gas Table S5. Vibration and bending parameters for DIFP. 6 k bond /k b (K) Bond length (Å) Bending Bond angle (deg) k θ /k b (K) P=O O=P-F F-P O=P-O P-O F-P-O O-CH O-P-O CH-CH P-O-CH O-CH-CH CH 3 -CH-CH S10

11 Water molecule is defined as rigid, with fixed bond lengths and angles. 7 The TraPPE force fields 4,5 as well as Mûller et al. 3 uses fixed bond lengths, while the Vishnyakov et al. 6 force field uses a harmonic potential to model bond stretching [1]: = ( ) [1] where k θ is the force constant and l o is the equilibrium bond length. In all force fields, a harmonic potential was used to describe bond angle bending [2]: = ( ) [2] where θ is the measured bond angle, θ 0 the equilibrium bond angle, and k θ the force constant. Table S7. Torsional Parameters for DMMP, Sarin, and Soman; 4 DES; 5 mustard gas; 3 and DIFP. 6 Torsion c 0 /k b (K) c 1 /k b (K) c 2 /k b (K) c 3 /k b (K) c 4 /k b (K) c 5 /k b (K) f a O=P-O-CH a CH 3 -CH-O-P a CH 3 -P-O-CH a O=P-O-CH a CH 3 -C-CH-O a CH 3 -C-CH-CH a CH 2 -S-CH 2 -CH a P-O-CH-CH b F-P-O-CH c 0 /k b (K rad -2 ) τ c CH 2 -S-CH 2 -CH c Cl-CH 2 -CH2-S Rotation about dihedral angles was controlled through a cosine series a, which included a phase angle term f to account for asymmetric rotational barriers [3]: = + + ( + ) + ( + ) + + ( + ) [3] where φ is the dihedral angle, and C i are Fourier constants. Additionally, a six-cosine dihedral b [4] is employed to describe the F-P-O-CH dihedral angle for DIFP. 6 = ( )= ( )+ ( ) ( )+ ( ) ( ) [4] Finally, the harmonic dihedral potential c was used by Müller et al. 3 to describe intramolecular rotations about bonds in mustard gas molecule [5]. = ( ) [5] S11

12 References and notes (1) Padial, N. M.; Quartapelle Procopio, E.; Montoro, C.; López, E.; Oltra, J. E.; Colombo, V.; Maspero, A.; Masciocchi, N.; Galli, S.; Senkovska, I.; et al. Highly Hydrophobic Isoreticular Porous Metal-Organic Frameworks for the Capture of Harmful Volatile Organic Compounds. Angew. Chemie - Int. Ed. 2013, 52, (2) Colombo, V.; Galli, S.; Choi, H. J.; Han, G. D.; Maspero, A.; Palmisano, G.; Masciocchi, N.; Long, J. R. High Thermal and Chemical Stability in Pyrazolate-Bridged Metal organic Frameworks with Exposed Metal Sites. Chem. Sci. 2011, 2, (3) Müller, T. J.; Müller-Plathe, F. A Comparison of Sulfur Mustard and Heptane Penetrating a Dipalmitoylphosphatidylcholine Bilayer Membrane. J. Hazard. Mater. 2009, 168, (4) Sokkalingam, N.; Kamath, G.; Coscione, M.; Potoff, J. J. Extension of the Transferable Potentials for Phase Equilibria Force Field to Dimethylmethyl Phosphonate, Sarin, and Soman. J. Phys. Chem. B 2009, 113, (5) Stubbs, J. M.; Potoff, J. J.; Siepmann, J. I. Transferable Potentials for Phase Equilibria. 6. United-Atom Description for Ethers, Glycols, Ketones, and Aldehydes. J. Phys. Chem. B 2004, 108, (6) Vishnyakov, A.; Gor, G. Y.; Lee, M. T.; Neimark, A. V. Molecular Modeling of Organophosphorous Agents and Their Aqueous Solutions. J. Phys. Chem. A 2011, 115, (7) Jorgensen, W. L.; Chandrasekhar, J.; Madura, J. D.; Impey, R. W.; Klein, M. L. Comparison of Simple Potential Functions for Simulating Liquid Water. J. Chem. Phys. 1983, 79, 926. S12