utilizing super-atom orbital ideas to understand

1

Supporting Information

Utilizing Super-atom Orbital Ideas to

Understand Properties of Silver Clusters inside ZSM-5 Zeolite Takashi Yumura, †,* Mitsuhiro Kumondai,†

Yasushige Kuroda,‡ Takashi Wakasugi,† and Hisayoshi Kobayashi†

†Department of Chemistry and Materials Technology, Kyoto Institute of Technology, Matsugasaki,

Sakyo-ku, Kyoto, 606-8585, Japan ‡Department of Chemistry, Graduate School of Natural Science and Technology, Okayama

University, Tsushima, Kita-ku, Okayama 700-8530, Japan * To whom all correspondence should be addressed.

E-mail: [email protected] (Takashi Yumura)

S1. Optimized geometries for Ag3–ZSM-5(Al1) and Ag4–ZSM-5(Al2) zeolites obtained in the previous studies (Refs. 48 and 49) (Figure S1)

S2. QM/MM ONIOM calculations of a triangle Ag3 cluster inside ZSM-5(Al1) zeolite (Figure S2)

S3. Selected Ag5 and Ag6 clusters that are could be formed by the single-atom and dual-atom additions into Ag4 clusters (Figure S3)

S4. Optimized geometries for Ag5–ZSM-5(Alm) obtained in the current study and geometrical information in terms of separations between silver atoms and framework oxygen atoms (Figure S4 and Table S1)

S5. Optimized geometries for Ag6–ZSM-5(Alm) obtained in the current study and geometrical information in terms of separations between silver atoms and framework oxygen atoms (Figure S5 and Table S2)

S6. Estabilize values as a function of the number of atoms in silver clusters within ZSM-5 cavity by obtained from DFT calculations with different basis sets. (Figure S6 and Tables S3 and S4)

S7. Frontier orbitals of Ag5–ZSM-5(Al3) and its truncated model (Figure S7)

S8. Frontier orbitals of Ag6–ZSM-5(Al3) and its truncated model (Figure S8)

S9. Models for time-dependent DFT calculations (Figure S9)

S10. Time-dependent B3PW91 DFT calculations of Ag8 clusters inside LTA zeolites, whose geometries were taken from Ref. 82 (Table S5)

S11. Full lists in Refs. 66 and 67

Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2016

Al

AgO

Si

Fig. S1 B3PW91 optimized geometries for Ag3–ZSM-5(Al1) and Ag4–ZSM-5(Al2), obtained in Refs. 48 and 49: (a) triangle Ag3 cluster inside a ZSM-5(Al1) cavity (b) square Ag4 cluster inside a ZSM-5(Al2) cavity, and (c) tetragonal Ag4 cluster inside a ZSM-5(Al2) cavity. The cut-off length used to indicate formation of Ag–Ag bonds is 3 Å.

(a) (b) (c)

Fig. S2 Model of Ag3–ZSM-5(Al1), containing 1127 atoms (Ag3–Al1Si347O616H160), for QM/MM calculations using the two-layer ONIOM method. The model was generated by removing atoms from its periodic model, and then terminal Si atoms are saturated by H atoms. The QM region consists of Al1Si9O10 (the red part) plus a triangle Ag3 cluster, and the other atoms are involed in the MM region. Atoms in the QM region were fully relaxed. In the MM region, atoms connecting to QM atoms were also relaxed, however other atoms were frozen. B3PW91 functional was used as the QM method, and universal force field (UFF) was used as the MM method. The cep-121G basis set was used for silver atoms, and the 6-31G* basis set was used for silicon, aluminum, and oxygen atoms. The optimized silver separations in the inner cluster (2.670, 2.673, and 2.690 Å) are consistent with those obtained in our previous report (Ref. 48) (2.682, 2.703, and 2.709 Å). This consistence indicates accuracy of our cluster-model caluclaitons .

(a) view along the b-axis directed to straight channel (b) view perpendicular to the b-axis

2.690

2.67

3

2.670

QM/MM model (Ag3–Al1Si347O616H160)

Fig. S3 Schematic view of constructing larger silver clusters by the mono-atom addition into a 3- and 4-atom silver cluster .

(a) formation of 4-atom clusters from one-atom addition to a triangle cluster

(b) formation of 5-atom clusters from one-atom addition to a 4-atom cluster

(c) formation of 6-atom clusters from one-atom addition to a 5-atom cluster

(i-4) (ii-4) (iii-4)

(i-4) (i-5) (ii-5)

(i-4) (iii-5)

(iii-5)(iii-4)

(iii-4) (iii-5')

(ii-4) (iv-5)

(v-5)(ii-4)

(i-6) (ii-5)

(iv-5)(iii-5')

(iii-5')

(i-5) (ii-6)

(iii-6)

(iv-6)

(v-5)

(i-5')

Fig. S4 B3PW91 optimized geometries for Ag5–ZSM-5(Alm). (a) m = 1, (b) m = 2, (c) m = 3, (d) m = 4 and (e) m = 5. The cut-off length used to indicate formation of Ag–Ag bonds is 3 Å. Key parameters are given in Table 3. Relative energies for each Ag5–ZSM-5(Alm) are given in kcal/mol.

(a) Ag5–ZSM-5(Al1)

0 kcal/mol 1.6 kcal/mol 2.7 kcal/mol

(b) Ag5–ZSM-5(Al2)


(c) Ag5–ZSM-5(Al3)


(d) Ag5–ZSM-5(Al4)


(e) Ag5–ZSM-5(Al5)

(i) (ii) (iii)

(i) (ii) (iii)

(i) (ii) (iii)

(i) (ii)

(i)

Al

O

Si Ag

(iii)

2

Table S1. Ag−O separations in optimized Ag5–ZSM-(Alm) geometries a

m Structure label b Ag−O separations c

1 a (i) 2.33, 2.40, 2.42, 2.45

1 a (ii) 2.34, 2.37, 2.49, 2.55, 2.58

1 a (iii) 2.47, 2.49, 2.57, 2.58, 2.58, 2.59, 2.59

2 b (i) 2.27, 2.33, 2.34, 2.35, 2.50, 2.52

2 b (ii) 2.35, 2.38, 2.42, 2.44, 2.51

2 b (iii) 2.27, 2.37, 2.42, 2.42, 2.42

3 c (i) 2.26, 2.30, 2.32, 2.38, 2.39, 2.44, 2.45, 2.49, 2.58

3 c (ii) 2.34, 2.36, 2.41, 2.41, 2.42, 2.43, 2.48, 2.49, 2.52, 2.53, 2.59

3 c (iii) 2.30, 2.33, 2.33, 2.33, 2.40, 2.42, 2.53, 2.58

4 d (i) 2.28, 2.29, 2.30, 2.31, 2.34, 2.35, 2.38, 2.40, 2.46, 2.47, 2.49, 2.50

4 d (ii) 2.29, 2.30, 2.32, 2.33, 2.36, 2.36, 2.36, 2.37, 2.41, 2.43, 2.48, 2.57

4 d (iii) 2.29, 2.29, 2.30, 2.33, 2.34, 2.38, 2.47, 2.53, 2.58

5 e 2.25, 2.26, 2.32, 2.33, 2.38, 2.38, 2.41, 2.43, 2.43, 2.45, 2.47, 2.49, 2.50,

2.51, 2.53, 2.54, 2.56 a, b Optimized structures can be seen in Figure S4. c Separations between silver atoms and framework oxygen atoms less than 2.60 Å

are listed.

Fig. S5 B3PW91 optimized geometries for Ag6–ZSM-5(Alm). (a) m = 1, (b) m = 2, (c) m = 3, (d) m = 4 and (e) m = 5. The cut-off length used to indicate formation of Ag–Ag bonds is 3 Å. Key parameters are given in Table 4. Relative energies for each Ag6–ZSM-5(Alm) are given in kcal/mol.

(a) Ag6–ZSM-5(Al1)(i) (ii)

0 kcal/mol 8.7 kcal/mol

(b) Ag6–ZSM-5(Al2)


(i) (ii)

(c) Ag6–ZSM-5(Al3)


(i) (ii)

(d) Ag6–ZSM-5(Al4)


(e) Ag6–ZSM-5(Al5)

(i) (ii)

Al

O

SiAg


(i) (ii)

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Table S2. Ag−O separations in optimized Ag6–ZSM-(Alm) geometries a

m Structure label b Ag−O separations c

1 a (i) 2.39, 2.41, 2.44, 2.54

1 a (ii) 2.35, 2.37, 2.45

2 b (i) 2.31, 2.40, 2.44, 2.49, 2.51, 2.52, 2.52, 2.54

2 b (ii) 2.37, 2.44, 2.48, 2.48, 2.52, 2.54

3 c (i) 2.29, 2.35, 2.39, 2.39, 2.45, 2.48, 2.53, 2.55, 2.58

3 c (ii) 2.27, 2.31, 2.33, 2.35, 2.37, 2.37, 2.38, 2.47

4 d (i) 2.21, 2.28, 2.30, 2.37, 2.39, 2.40, 2.41, 2.43, 2.43, 2.57, 2.59

4 d (ii) 2.27, 2.31, 2.31, 2.32, 2.32, 2.39, 2.43, 2.45, 2.50, 2.51, 2.53, 2.57

5 e (i) 2.22, 2.22, 2.28, 2.29, 2.29, 2.41, 2.41, 2.42, 2.44, 2.44, 2.47, 2.50,

2.53, 2.54, 2.55

5 e (ii) 2.30, 2.31, 2.33, 2.35, 2.37, 2.41, 2.43, 2.45, 2.45, 2.50, 2.51, 2.52

a, b Optimized structures can be seen in Figure S5. c Separations between silver atoms and framework oxygen atoms less than 2.60 Å

are listed.

0

–100

–80

–60

–40

–20

2 3 4 5 6

Estabilize

n

m = 1

m = 2m = 3

m = 4

Fig. S6 Estabilize values, defined in the main text, as a function of the number of atoms in silver clusters within ZSM-5(Alm): blue marks for m = 1 (blue), m = 2 (red), m = 3 (green), and m = 4 (purple). Lines are provided for visual assistance. (a) system A; the CEP-121G basis set was used for Ag atoms, the 6-31G* basis set forsubstituted Al atoms and for the two O atoms bound to a substituted Al atom, and the 3-21G basis set for all other atoms. this grap is identical to that in Fig. 5. (b) system B; the CEP-121G basis set was used for Ag atoms, the 6-31G basis set forsubstituted Al atoms and for the two O atoms bound to a substituted Al atom, and the 3-21G basis set for all other atoms. The number of primitive gaussians in both systems can be seen in Table S3. Differences in Estabilize values between sytems A and B can be seen in Table S4.

(kcal/mol)

2 3 4 5 6n

m = 1

m = 2m = 3

m = 4

(a) system A (b) system B

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Table S3. The number of primitive gaussians in calculations of Agn−ZSM-5(Alm)

System A a System B b

n m m 1 2 3 4 5 1 2 3 4 5

1 5060 − − − − 5042 − − − − 2 5122 5173 − − − 5104 5137 − − − 3 5184 5235 5286 − − 5166 5199 5232 − − 4 5246 5297 5348 5399 − 5228 5261 5294 5327 − 5 5308 5359 5410 5461 − 5290 5323 5356 5389 − 6 5370 5421 5472 5523 5574 5352 5385 5418 5451 5484

a in system A, the CEP-121G basis set was used for Ag atoms, the 6-31G* basis set for substituted Al atoms and for the two O atoms bound to a substituted Al atom, and the 3-21G basis set for all other atoms. The system A was used in the current study. In fact, Estabilize values in Fig. 5 were obtained in this system. b in system B, the CEP-121G basis set was used for Ag atoms, the 6-31G basis set for substituted Al atoms and for the two O atoms bound to a substituted Al atom, and the 3-21G basis set for all other atoms. Estabilize values in Fig. S6(b) were obtained in this system. Table S4. Differences in Estabilize values of Agn−ZSM-5(Alm) between systems A and B a

n m 1 2 3 4

2 0.4 − − − 3 −1.3 4.4 − − 4 −8.3 −2.3 7.0 − 5 2.2 −3.8 −8.6 −17.0 6 5.1 0.8 −6.4 7.8

a Estabilize(system A) − Estabilize(system B) in kcal/mol. Estabilize(system A) values are plotted in Fig. 5, and Estabilize(system B) values are plotted in Fig. S6. Definition of systems A and B can be seen in captions of Table S3.

(i) Ag5–ZSM-5(Al3) model

HOMO

LUMO, 4.02 eV

LUMO+1, 5.13 eV

Fig. S7 Frontier orbitals of the optimized Ag5–ZSM-5(Al3) structure that is energetically stable. (i) whole Ag5–ZSM-5(Al3) structure obtained from B3PW91 optimization, and (ii) a truncated Ag5–ZSM-5(Al3) given in Fig. S9. In both cases, the frontier orbitals consist of 5s orbitals on the contained silver atoms. The orbital energies relative to the HOMO are given in eV.

LUMO+2, 5.57 eV

HOMO

LUMO, 4.01 eV

LUMO+1, 5.13 eV

LUMO+2, 5.61 eV

(ii) truncated Ag5–ZSM-5(Al3) model

(i) Ag6–ZSM-5(Al4) model

HOMO

LUMO, 3.75 eV

LUMO+1, 4.62 eV

Fig. S8 Frontier orbitals of the optimized Ag6–ZSM-5(Al4) structure that is energetically stable. (i) whole Ag6–ZSM-5(Al4) structure obtained from B3PW91 optimization, and (ii) a truncated Ag6–ZSM-5(Al4) given in Fig. S9. In both cases, the frontier orbitals consist of 5s orbitals on the contained silver atoms. The orbital energies relative to the HOMO are given in eV.

LUMO+2, 5.22 eV

HOMO

LUMO, 3.86 eV

LUMO+1, 4.72 eV

LUMO+2, 5.37 eV

(ii) truncated Ag6–ZSM-5(Al4) model

Ag6–Al4Si30O42H52Ag5–Al3Si30O41H50

Fig. S9 Silver containing ZSM-5 zeolite models were used for time-dependent DFT (TD-DFT) calculations. (a) a truncated model construction from the optimized geometry for Ag5–ZSM-5(Al3) by removing several atoms. (b) a truncated model construction from the optimized geometry for Ag6–ZSM-5(Al4).

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Table S5. Time-dependent B3PW91 DFT calculations of Ag6 clusters inside LTA zeolites, whose geometries were taken from Ref. 82.

Models a Electronic transitions b

Ag6 cluster inside (H2O)4(Na4Al8Si16O36H24) 394.0 (0.10), 406.1 (0.06), 474.7 (0.05), 522.2 (0.09)



a Models are taken from Ref. 82. b Excitation energy (nm) in an electronic transition, and its oscillatory strength in

parentheses.

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S11. Full lists in Refs. 66 and 67 Ref. 66 Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, J. A., Jr.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, Ö.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J.Gaussian 09, Gaussian, Inc.: Wallingford, CT, 2009. Ref. 67 Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A., Jr.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian 03; Gaussian, Inc.: Pittsburgh, PA, 2003.

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