Supporting Information

Transcription

1 Supporting Information Roles of Zeolite Confinement and Cu O Cu Angle on the Direct Conversion of Methane to Methanol by [Cu 2 (µ-o)] 2+ -exchanged AEI, CHA, AFX, and MFI Zeolites M. Haris Mahyuddin,, Aleksandar Staykov, Yoshihito Shiota, Mayuko Miyanishi, and Kazunari Yoshizawa*, Institute for Materials Chemistry and Engineering and IRCCS, Kyushu University, Fukuoka , Japan Department of Physics-Energy Engineering, Surya University, Tangerang 15810, Indonesia International Institute for Carbon-Neutral Energy Research, Kyushu University, Fukuoka , Japan * To whom all correspondence should be addressed ( kazunari@ms.ifoc.kyushu-u.ac.jp).

2 Table of Contents: Table S1. Relative energies and geometrical parameters for [Cu 2 (µ-o)] 2+ -AEI, -CHA, -AFX, and -MFI zeolites with different numbers of Si atom separating the Al pair. Figure S1. Relative energies and geometrical parameters for [Cu 2 (µ-o)] 2+ -AEI, CHA, -AFX, and -MFI zeolites with two Si atoms separating the Al pair located at different T sites. Table S2. Relative energies and geometrical parameters for the triplet state of all intermediates and transition states. Table S3. Relative energies and geometrical parameters for the singlet state all intermediates and transition states. Table S4. Atomic spin densities for the Cu and O oxo atoms of all intermediates and transition states in the triplet state. Table S5. Relative energies and geometrical parameters for N 2 O decomposition by [2Cu] 2+ -AEI zeolite. Figure S2. Optimized structures for N 2 O decomposition by [2Cu] 2+ -AEI zeolite. Figure S3. Relative energies and optimized structures for the four-t-site cluster models of [Cu 2 (µ-o)] 2+ -AEI, -CHA, -AFX, and -MFI zeolites. Figure S4. Partial DOS projected to C and H atoms of the confined and unconfined methane. Table S6. Geometrical parameters of the optimized two-t-site [Cu 2 (µ-o)] 2+ -zeolite cluster with different Cu O Cu angles. Details of calculations using Gaussian09 program code References

3 Table S1. Relative energies and geometrical parameters for Cu 2 (µ-o) in AEI, CHA, AFX, and MFI zeolites with different numbers of Si atom separating the Al pair, calculated in the triplet ground state. #Si separating ΔE d Al Al d Cu Cu Cu O Cu d Cu1 O d Cu2 O Al pair (kcal/mol) (deg) [Cu 2 (μ-o)] 2+ -AEI [Cu 2 (μ-o)] 2+ -CHA [Cu 2 (μ-o)] 2+ -AFX [Cu 2 (μ-o)] 2+ -MFI S1

4 Figure S1. Relative energies and geometrical parameters of (a) [Cu 2 (µ-o)] 2+ -AEI, (b) -AFX, and (c) -MFI zeolites with two Si atoms separating the Al pair located at different T sites. Cu Cu bond length is given in Å. S2

5 Table S2. Relative energies and geometrical parameters of intermediates and transition states in the triplet state for the reaction over [Cu 2 (μ-o)] 2+ -AEI, CHA, -AFX, and -MFI. ΔE d Cu Cu Cu O Cu d Cu1 O d Cu2 O d Cu1 C d Cu2 C d C H d O H d C O (kcal/mol) (deg) RC TS [Cu 2 (μ-o)] 2+ -AEI RI TS2 (d) MC TS2 (i) PC FC RC TS [Cu 2 (μ-o)] 2+ -CHA RI TS2 (d) MC TS2 (i) PC FC RC TS [Cu 2 (μ-o)] 2+ -AFX RI TS2 (d) MC TS2 (i) PC FC RC [Cu 2 (μ-o)] 2+ -MFI TS RI MC TS2 (i) PC FC RC: Reactant complex, TS: Transition state, RI: Radical intermediate, MC: Methyl complex, PC: Product complex, FC: Final complex, (d): direct and (i): indirect rebound mechanisms, O: Oxo atom, H: Abstracted H atom. S3

6 Table S3. Relative energies and geometrical parameters of intermediates and transition states in the open-shell and closed-shell SINGLET states for the reaction over [Cu 2 (μ-o)] 2+ -AEI, CHA, -AFX, -MFI with two Si atoms separating the Al pair located at T1/T1 site. ΔE d Cu Cu Cu O Cu d Cu1 O d Cu2 O d Cu1 C d Cu2 C d C H d O H d C O (kcal/mol) a (deg) RC [Cu 2 (μ-o)] 2+ -AEI TS RI MC TS2 (i) PC FC RC [Cu 2 (μ-o)] 2+ -CHA TS RI MC TS2 (i) PC FC RC [Cu 2 (μ-o)] 2+ -AFX TS RI MC TS2 (i) PC FC RC TS [Cu 2 (μ-o)] 2+ -MFI RI TS2(d) MC TS2(i) PC FC a Relative energies are measured from the corresponding RC in the triplet state. RC: Reactant complex, TS: Transition state, RI: Radical intermediate, MC: Methyl complex, PC: Product complex, FC: Final complex, (d): direct and (i): indirect rebound mechanisms, O: Oxo atom, H: Abstracted H atom. S4

7 Table S4. Atomic spin density (SD) for the Cu and O oxo atoms of initial complex, reactant complex, TS1, radical intermediate, methyl complex, TS2, and product complex in the triplet state. Cu1 Cu2 O oxo IC [Cu 2 (μ-o)] 2+ -AEI RC TS RI MC TS PC IC [Cu 2 (μ-o)] 2+ -CHA RC TS RI MC TS PC IC [Cu 2 (μ-o)] 2+ -AFX RC TS RI MC TS PC IC [Cu 2 (μ-o)] 2+ -MFI RC TS RI MC TS PC IC: Initial complex of [Cu 2 (µ-o)] 2+ -zeolites with two Si atoms separating the Al pair, RC: Reactant complex, TS: Transition state, RI: Radical intermediate, MC: Methyl complex, PC: Product complex S5

8 Table S5. Relative energies and geometrical parameters of N 2 O adsorption and TS3 in the triplet and closed-shell singlet states for the N 2 O decomposition by [2Cu] 2+ -AEI zeolite Spin state Binding mode ΔE (kcal/mol) d N O d N N d Cu Cu Cu O Cu (deg) d Cu1 O or d Cu1 N d Cu2 O or d Cu2 N Triplet DL N 2 O ads μ-1,1-o η 1 -N TS3 μ-1,1-o CS-Singlet DL N 2 O ads μ-1,1-o η 1 -N TS3 μ-1,1-o DL: dissociation limit [2Cu] 2+ -AEI + N 2 O. Geometry optimizations for the µ-1,3-o,n binding mode cannot converge to the minimum required accuracy. Figure S2. Optimized structures of N 2 O adsorption and TS3 in the triplet and closed-shell singlet states for the N 2 O decomposition by [2Cu] 2+ -AEI zeolite. S6

9 Reactant complex TS1 (a) ΔE = 0.0 kcal/mol ΔE = 13.2 kcal/mol (b) ΔE = 0.0 kcal/mol ΔE = 15.3 kcal/mol (c) ΔE = 0.0 kcal/mol ΔE = 15.7 kcal/mol (d) ΔE = 0.0 kcal/mol ΔE = 20.5 kcal/mol Figure S3. Relative energies and optimized structures for reactant complexes and TS1s of (a) [Cu 2 (µ-o)] 2+ -AEI, (b) -CHA, (c) -AFX, and (d) -MFI zeolite clusters calculated in the triplet state. All energies include vdw-d2 dispersion corrections. The clusters are obtained from the optimized periodic-structures and then terminated by H atoms to construct neutral systems. During calculations, only the H-atom terminations are allowed to fully relax, while the others are fixed to their optimized positions. S7

10 Figure S4. Partial density of states (PDOS) projected to C and H atoms of methane (a) in the gas phase, confined in (b) AEI, (c) CHA, (d) AFX, and (e) MFI zeolites. E F and E VAC stand for Fermi energy and vacuum energy, respectively. For methane in the gas phase, the first high-intensity peak below E F (at 9.41 ev) corresponds to the threefold degenerate orbital of tetrahedral methane. After confinement in AEI, CHA, AFX, and MFI zeolites, this threefold degenerate orbital is split into two orbitals: one twofold degenerate orbital and one non-degenerate orbital, resulting in two lower-intensity peaks that are neighboring to each other. S8

11 Table S6. Relative energies and geometrical parameters of the optimized [Cu 2 (µ-o)] 2+ -zeolite cluster with different Cu O Cu angles Cu O Cu ΔE d Cu Cu d Cu1 O d Cu2 O (deg) (kcal/mol) Calculation Details: To optimize the above [Cu 2 (µ-o)] 2+ -zeolite clusters and obtain their MOs, we employed Gaussian09 program code with B3LYP method. This method consists of the Slater exchange, the Hartree-Fock exchange, the exchange functional of Becke, 1 the correlation functional of Lee, Yang, Parr (LYP), 2 and the correlation functional of Vosko, Wilk, and Nusair. 3 The G** basis set is used for Cu atom, while the D95** basis set is used for Al, O, C, and H atoms. During calculations, the Cu O Cu angle is fixed, while the other geometrical parameters are fully relaxed. References: (1) Becke, A. D. Phys. Rev. A: At., Mol., Opt. Phys. 1988, 38, (2) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B: Condens. Matter Mater. Phys. 1988, 37, (3) Vosko, S. H.; Wilk, L.; Nusair, M. Can. J. Phys. 1980, 58, S9