Supplementary Information. Comparison of the relative stability of zinc and lithium-boron zeolitic imidazolate frameworks

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Transcription:

Supplementary Information Comparison of the relative stability of zinc and lithium-boron zeolitic imidazolate frameworks Raimondas Galvelis, a Ben Slater, a Anthony K. Cheetham, b Caroline Mellot-Draznieks a, * a Department of Chemistry, University College London, 20 Gordon St., London, WC1H 0AJ, UK. E-mail: c.mellot-draznieks@ucl.ac.uk b Department of Materials Science and Metallurgy, University of Cambridge, Pembroke Street, Cambridge, CB2 3QZ, UK. S1

Table S1. Parameters of CP2K/Quickstep simulations. Parameter Method Functional Pseudo-potential Gaussian-type basis sets Plane-wave cut-off k-point sampling SCF optimizer Electron density convergence criteria Dispersive interaction correction Optimizer Constrains Convergence criteria Optimizer Constrains Convergence criteria Value Energy and atomic forces evaluation Mixed Gaussian and plane-wave (GPW) PBE Goedecker-Teter-Hutter (GTH) Molecular optimized double zetha-valence basis sets with a polarization function (DZVP-MOLOPT) 400 Ry Gamma-point only Orbital transformation with the direct inverse in the iterative subspace optimizer (OT/DIIS) 1.0 x 10-7 DFT-D2: s 6 = 0.75; d = 20; R cut-off = 12.0 Å. DFT-D3: s 6 = 1.000; s r6 = 1.127; s 8 = 0.722; R cut-off = 12.0 Å. Atomic positions optimization Broyden-Fletcher-Goldfarb-Shanno (BFGS) no symmetry constrains on atomic positions maximum force 4.5 x 10-5 Hartree/Bohr RMS force 3.0 x 10-5 Hartree/Bohr maximum coordinate change 3.0 x 10-4 Bohr RMS coordinate change 1.5 x 10-4 Bohr Unit-cell parameters optimization Conjugate gradient (CG; each cell optimization step is followed by geometry optimization at current cell parameters) external hydrostatic pressure 1 bar maximum force 4.5 x 10-4 Hartree/Bohr RMS force 3.0 x 10-4 Hartree/Bohr maximum parameter change 3.0 x 10-3 Bohr RMS parameter change 1.5 x 10-3 Bohr maximum pressure deviation 100 bar S2

Table S2. Structure parameters and total energies for Zn(Im) 2 and LiB(Im) 4. ZIFs obtained from DFT-D simulations with CP2K. Structure a, Å b, Å c, Å α, β, γ, V, Å 3 d,* nm -3 Energy, kj/mol*** Zn(Im) 2 with PBE-D2 cag (ZIF-4**) 15.601 14.958 18.086 90.0 90.0 90.0 4220.3 3.79-362544.08 DFT (ZIF-3**) 19.137 19.137 16.867 90.0 90.0 90.0 6177.2 2.59-362530.02 dia 7.969 7.969 16.647 90.0 90.0 90.0 1057.3 3.78-362531.59 GIS (ZIF-6**) 18.483 18.483 20.678 90.0 90.0 90.0 7064.2 2.26-362529.73 MER (ZIF-10**) 27.250 27.250 19.330 90.0 90.0 90.0 14354.0 2.23-362529.47 SOD (ZIF-8**) 17.018 17.018 17.018 90.0 90.0 90.0 4928.2 2.43-362530.57 zni 23.508 23.488 12.468 90.0 90.0 90.0 6884.6 4.65-362560.07 Zn(Im) 2 with PBE-D3 cag (ZIF-4**) 15.475 14.958 18.196 90.1 90.0 89.8 4211.9 3.80-362529.57 DFT (ZIF-3**) 19.124 19.124 16.837 90.0 90.0 90.0 6158.0 2.60-362515.44 dia 7.803 7.801 16.964 90.0 90.0 90.0 1032.7 3.87-362518.67 GIS (ZIF-6**) 18.489 18.490 20.663 90.0 90.0 90.1 7063.8 2.27-362514.34 MER (ZIF-10**) 27.239 27.239 19.308 90.0 90.0 90.0 14326.5 2.23-362514.53 SOD (ZIF-8**) 17.017 17.017 17.017 90.0 90.0 90.0 4927.8 2.44-362516.53 zni 23.552 23.522 12.458 90.0 90.0 90.0 6901.5 4.64-362546.90 LiB(Im) 4 with PBE-D2 cag 14.228 14.178 16.892 90.0 90.0 90.0 3407.7 4.70-217258.77 DFT 18.257 18.257 15.782 90.0 90.0 90.0 5260.2 3.04-217245.66 dia 7.583 7.592 14.981 90.0 90.0 90.0 862.4 4.64-217257.42 GIS 25.460 18.710 24.677 90.0 90.0 90.0 11754.9 2.72-217245.22 MER 25.729 25.729 17.738 90.0 90.0 90.0 11742.4 2.73-217245.73 SOD 15.833 15.832 15.832 90.0 90.0 90.0 3968.3 3.02-217245.14 zni (BIF-1) 22.375 22.375 11.331 90.0 90.0 90.0 5672.8 5.64-217278.59 LiB(Im) 4 with PBE-D3 cag 14.245 14.205 16.884 90.0 90.0 90.0 3416.3 4.68-217232.80 DFT 18.238 18.238 15.750 90.0 90.0 90.0 5238.6 3.05-217221.24 dia 7.520 7.521 15.145 90.0 90.0 90.0 856.6 4.67-217232.59 GIS 25.451 18.709 24.687 90.0 90.0 90.0 11755.1 2.72-217219.98 MER 25.734 25.734 17.723 90.0 90.0 90.0 11736.8 2.73-217220.60 SOD 15.875 15.852 15.858 90.0 90.0 90.0 3990.5 3.01-217220.57 zni (BIF-1) 22.410 22.415 11.419 90.0 90.0 90.0 5736.1 5.58-217252.61 * Framework densities are expressed as the number of tetrahedral T sites per unit volume, nm -3. ** The experimental structure contains guest molecules. *** We are aware that our computations refer to internal energies (being comparable to enthalpies, assuming the volumes changes are small at the given pressure). Turning to thermodynamics, stability is determined by free energy, which requires the knowledge of entropy, which is not computed here. S3

Figure S1. Experimental (green), simulated with PBE-D2 (red) and PBE-D3 (blue) structures of Zn(Im) 2 zni (a) and LiB(Im) 4 zni (b). The unit cells are viewed down the [001] direction. Excellent agreement is observed for the other experimental structures. (a) (b) S4

Table S3. The comparison of ZIFs' unitcell parameters and relative energies as simulated with CP2K/Quickstep and CASTEP using PBE-D2. For comparison with CP2K calculations, plane-wave calculations were performed on both MER and zni structures, considered here as benchmarks. These calculations used the PBE functional, a cut-off of 350 ev (or 25.7 Ry) and sampling at the Γ point. Energy differences at the DFT-D2 level between MER and zni were found to be 27.45 kj/mol and 29.87 kj/mol for the Zn-based and LiB-based structures, respectively, confirming the veracity of the CP2K results. Zn-based LiB-based Topology zni MER zni MER Code CP2K* CASTEP CP2K* CASTEP CP2K* CASTEP CP2K* CASTEP a, Å 23.508 23.502 27.250 27.093 22.375 22.419 25.729 25.730 b, Å 23.488 23.494 27.250 27.0923 22.375 22.392 25.729 25.730 c, Å 12.468 12.382 19.330 19.473 11.331 11.386 17.738 17.720 Volume, Å -3 6884.6 6836.4 14354.0 14293.9 5672.8 5715.9 11742.4 11731.0 Energy,** kj/mol 0.000 0.000 30.596 27.444 0.000 0.000 32.861 29.870 * CP2K/Quickstep DFT module ** The relative energy is measured with respect to zni and normalized per tetrahedral site (Zn or Li/B). S5

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