S-1
Supporting Information for:
Impact of Metal and Anion Substitutions on the Hydrogen Storage Properties of M-BTT Metal-Organic Frameworks
Kenji Sumida,† David Stück,† Lorenzo Mino,‡ Jeng-Da Chai,† Olena Zavorotynska,‡ Eric D.
Bloch,† Leslie J. Murray,† Mircea Dincă,† Sachin Chavan,‡ Silvia Bordiga,*,‡
Martin Head-Gordon*,†,¶ and Jeffrey R. Long*,†,§
†Department of Chemistry, University of California Berkeley, California 94720, United States
‡Department of Chemistry, NIS Centre of Excellence and INSTM, University of Torino, Via Quarello, 11 I-10135 Torino, Italy
¶Chemical Sciences Division and §Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
*email: silvia.bordiga@unito.it, mhg@cchem.berkeley.edu, jrlong@berkeley.edu
J. Am. Chem. Soc.
S-2 List of Figures
Figure S1. Infrared spectra for H2 desorption recorded at 14 K for Mn-BTT.
Figure S2. Infrared spectra for H2 desorption recorded at 14 K for Fe-BTT.
Figure S3. Infrared spectra for H2 desorption recorded at 14 K for Cu-BTT.
Figure S4. H2 adsorption isotherms for Mn-BTT collected at 77 K and 87 K.
Figure S5. H2 adsorption isotherms for Fe-BTT collected at 77 K and 87 K.
Figure S6. H2 adsorption isotherms for Cu-BTT collected at 77 K and 87 K.
Figure S7. The lowest-pressure region of the H2 adsorption isotherm for Fe-BTT collected at 77 K.
Table S1. Dual-site Langmuir fit parameters for the H2 isotherms for Mn-BTT in Figure S4.
Table S2. Dual-site Langmuir fit parameters for the H2 isotherms for Fe-BTT in Figure S5.
Table S3. Dual-site Langmuir fit parameters for the H2 isotherms for Cu-BTT in Figure S6.
Table S4. Dual-site Langmuir fit parameters for the lowest-pressure region of the Hadsorption data for Fe-BTT in Figure S7.
Complete citation for Reference 25:
Shao, Y.; Fusti Molnar, L.; Jung, Y.; Kussmann, J.; Ochsenfeld, C.; Brown, S. T.; Gilbert, A. T.
B.; Slipchenko, L. V.; Levchenko, S. V.; O’Neill, D. P.; DiStasio Jr, R. A.; Lochan, R. C.; Wang, T.; Beran, G. J. O.; Besley, N. A.; Herbert, J. M.; Lin, C. Y.; Van Voorhis, T.; Chien, S. H.; Sodt, A.; Steele, R. P.; Rassolov, V. A.; Maslen, P. E.; Korambath, P. P.; Adamson, R. D.; Austin, B.;
Baker, J.; Byrd, E. F. C.; Dachsel, H.; Doerksen, R. J.; Dreuw, A.; Dunietz, B. D.; Dutoi, A. D.;
Furlani, T. R.; Gwaltney, S. R.; Heyden, A.; Hirata, S.; Hsu, C.-P.; Kedziora, G.; Khalliulin, R.
Z.; Klunzinger, P.; Lee, A. M.; Lee, M. S.; Liang, W. Z.; Lotan, I.; Nair, N.; Peters, B.; Proynov, E. I.; Pieniazek, P. A.; Rhee, Y. M.; Ritchie, J.; Rosta, E.; Sherrill, C. D.; Simmonett, A. C.;
Subotnik, J. E.; Woodcock III, H. L.; Zhang, W.; Bell, A. T.; Chakraborty, A. K.; Chipman, D.
M.; Keil, F. J.; Warshel, A.; Hehre, W. J.; Schaefer III, H. F.; Kong, J.; Krylov, A. I.; Gill, P. M.
W.; Head-Gordon, M. Phys. Chem. Chem. Phys. 2006, 8, 3172.
S-3
Figure S1. Infrared spectra for H2 desorption recorded at 14 K for Mn-BTT, in which the pressure (and the total H2 remaining in the system) was gradually reduced.
S-4
Figure S2. Infrared spectra for H2 desorption recorded at 14 K for Fe-BTT, in which the pressure (and the total H2 remaining in the system) was gradually reduced.
S-5
Figure S3. Infrared spectra for H2 desorption recorded at 14 K for Cu-BTT, in which the pressure (and the total H2 remaining in the system) was gradually reduced.
S-6
Figure S4. H2 adsorption isotherms for Mn-BTT collected at 77 K (blue) and 87 K (green). The solid lines represent the dual-site Langmuir fit to the data, using the parameters tabulated in Table S1.
S-7
Figure S5. H2 adsorption isotherms for Fe-BTT collected at 77 K (blue) and 87 K (green). The solid lines represent the dual-site Langmuir fit to the data, using the parameters tabulated in Table S2.
S-8
Figure S6. H2 adsorption isotherms for Cu-BTT collected at 77 K (blue) and 87 K (green). The solid lines represent the dual-site Langmuir fit to the data, using the parameters tabulated in Table S3.
S-9
Figure S7. The lowest-pressure region of the H2 adsorption isotherm for Fe-BTT collected at 77 K. The solid line represents the dual-site Langmuir fit to the data, using the parameters tabulated in Table S4.
S-10
Table S1. Dual-site Langmuir fit parameters for the H2 isotherms for Mn-BTT in Figure S4.
Parameter
T
77 K 87 K
qsat1 1.21214 1.34085
b1 185.22316 32.77728
v1 0.92104 0.93787
qsat2 19.48467 16.67445
b2 0.9409 0.57771
v2 0.66854 0.77047
Table S2. Dual-site Langmuir fit parameters for the H2 isotherms for Fe-BTT in Figure S5.
Parameter
T
77 K 87 K
qsat1 7.9845 0.61692
b1 1.59297 455.7024
v1 0.97761 0.754
qsat2 50.0 50.0
b2 0.16279 0.18357
v2 0.27638 0.51252
S-11
Table S3. Dual-site Langmuir fit parameters for the H2 isotherms for Cu-BTT in Figure S6.
Parameter
T
77 K 87 K
qsat1 2.75088 2.76398
b1 456.97063 62.91413
v1 1.03415 1.00654
qsat2 18.30037 16.52023
b2 0.98154 0.57883
v2 0.66592 0.75204
Table S4. Dual-site Langmuir fit parameters for the lowest-pressure portion of the 77 K H2
isotherm for Fe-BTT in Figure S7.
Parameter
T
77 K
qsat1 1.27932
b1 417.16893
v1 0.63856
qsat2 0.00121
b2 5.22471E-06
v2 62.77542
