Supplementary Information
Supporting Information
Wide Control of Proton Conductivity in Porous Coordination Polymers Akihito Shigematsu,†,‡ Teppei Yamada,† and Hiroshi Kitagawa*,†,‡,§ †
Division of Chemistry, Graduate School of Science, Kyoto University, Kitashirakawa-Oiwakecho,
Sakyo-ku, Kyoto 606-8502, Japan,
‡
Department of Chemistry, Faculty of Science, Kyushu
University, Hakozaki 6-10-1, Higashi-ku, Fukuoka 812-8581, Japan, and §CREST, Japan Science and Technology Agency (JST), Sanban-cho 5, Chiyoda-ku, Tokyo 102-0075, Japan
Experimental Section Materials and reagents. All the reagents and solvents were commercially available and used without further purification.
Synthesis of Al(OH)(O2C–C6H4–CO2)(H2O) [MIL-53(Al)] (1). The synthesis of MIL-53(Al) was performed as described elsewhere.1 Al(NO3)3·9H2O 3.9 g (10.5 mmol), terephthalic acid 0.86 g (7.5 mmol), and water (30 mL) were added to a 70 mL Teflon-lined steel autoclave. The autoclave was heated in an oven at 473 K for three days. After filtering, washing with water and then drying in air, the compound was kept at 503 K in an electric furnace for three days to remove excess terephthalic acid in the pores. The calcined sample was refluxed in ethanol for a day and then dried at 473 K under vacuum. A white powder of 1 was obtained (0.50 g, 29.3%). Elemental analysis calcd. for C8H7O6Al: C, 42.49; H, 3.12%. Found: C, 42.89; H, 2.84%. Synthesis of Al(OH)(O2C–C6H3(NH2)–CO2)(H2O) [MIL-53(Al)–NH2] (2). The synthesis of MIL-53(Al)–NH2 was performed as described elsewhere.2 Al(NO3)3·9H2O 1.99 g (5.3 mmol), 2-aminoterephthalic acid 0.98 g (5.7 mmol), and water (13 mL) were added to a 70 mL Teflon-lined steel autoclave. The autoclave was heated in an oven at 423 K for five hours. After filtering, the compound was refluxed in N,N´-dimethylformamide at 423 K for 12 hours and then dried in an oven at 413 K for one day. A yellow powder of 2 was obtained (0.38 g, 30.3%). Elemental analysis calcd. for C8H8O6NAl: C, 39.85; H, 3.34; N, 5.81%. Found: C, 39.88; H, 3.17; N, 5.87%.
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Synthesis of Al(OH)(O2C–C6H3(OH)–CO2)(H2O)1.5 [MIL-53(Al)–OH] (3). The synthesis of MIL-53(Al)–OH was performed as described elsewhere.3 First, the synthesis of 2-hydroxyterephthalic acid was carried out from 2-aminoterephthalic acid in a one-step reaction using the same synthesis method. 2-hydroxyterephthalic acid 1.87 g (10.2 mmol) dissolved in N,N´-dimethylformamide (30 mL) was added dropwise to Al(NO3)3·9H2O 7.81 g (21 mmol) dissolved in water (30mL) at ambient temperature. The reaction mixture was heated to 363 K and held at the temperature for 40 hours. After filtering, the crude compound was refluxed in ethanol for 36 hours and then dried at 393 K under vacuum. A white powder of 3 was obtained (2.04 g, 80%). Elemental analysis calcd. for C8H8O7.5.Al: C, 38.26; H, 3.21%. Found: C, 37.84; H, 2.79%. Synthesis of Fe(OH)(O2C–C6H2(COOH)2–CO2)(H2O) [MIL-53(Fe)–(COOH)2] (4). The synthesis of MIL-53(Fe)–(COOH)2 was performed as described elsewhere.4 FeCl2·4H2O 1.13 g (5.68 mmol), 1,2,4,5-benzenetetracarboxylic acid 0.71 g (2.84 mmol), and HF (0.21 mL), and water (48 mL) were added to a 120 mL Teflon-lined steel autoclave. The autoclave was heated in an oven at 473 K for two days. After filtering and washing with water, orange crystals of 4 were obtained (0.15 g, 15.4%). Elemental analysis calcd. for C10H7O10Fe: C, 35.02; H, 2.06%. Found: C, 34.94; H, 2.04%.
Powder X-ray diffraction (PXRD) measurements. PXRD measurements were carried out with a Bruker D8 ADVANCE using CuKα radiation.
Figure S1. Powder X-ray diffraction patterns of (a) Al(OH)(C8H4O4)·H2O simulated from
single-crystal X-ray diffraction analysis,1 (b) 1, (c) 2, (d) 3, (e) Fe(OH)(C10H4O6)·H2O simulated from single-crystal X-ray diffraction analysis,4 and (f) 4 at 298 K.
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Table S1. Cell parameters of hydrated or dehydrated 1–4 calculated with powder pattern fitting.
Infrared spectroscopy (IR) experiments. IR experiments were performed with a Perkin Elmer Spectrum 100 FT-IR spectrometer.
Figure S2. IR spectra of (a) 1, (b) 2, (c) 3, and (d) 4.
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Water adsorption and desorption isotherm measurements. Water adsorption and desorption isotherm measurements were carried out volumetrically with an automatic adsorption apparatus, BELSORP-max (BEL Japan). Samples were prepared by degassing at 473K for 24 hours.
Figure S3. Water adsorption (filled) and desorption (open) isotherms of dehydrated
1 (blue ■), 2 (pink ▼), 3 (green ▲) and 4 (red ●) at 298 K.
Conductivity measurements. Proton conductivity measurements of the compounds were determined using the conventional quasi-four-probe method, using gold paste and gold wires (50 μm φ) with a Solartron SI 1260 Impedance/Gain-Phase Analyzer and 1296 Dielectric Interface in the frequency range 1 Hz to 1 MHz at 298 K under humid conditions (controlled by using an Espec Corp. SH-221 incubator), using sample pellets of ~ 0.7 mm thickness and 2.5 mm φ.
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References (1) Loiseau, T.; Serre, C.; Huguenard, C.; Fink, G.; Taulelle, F.; Henry, M.; Bataille, T.; Férey, G. Chem.—Eur. J. 2004, 10, 1373–1382. (2) Ahnfeldt, T.; Gunzelmann, D.; Loiseau, T.; Hirsemann, D.; Senker, J.; Férey, G.; Stock, N. Inorg. Chem. 2009, 48, 3057–3064. (3) Himsl, D.; Wallacher, D.; Hartmann, M. Angew. Chem., Int. Ed. 2009, 48, 4639–4642. (4) Sanselme, M.; Grenéche, J.-M.; Riou-Cavellec, M.; Férey, G. Solid State Sci. 2004, 6, 853–858.
Complete list of refs 8b and 9 (8) (b) Horcajada, P.; Chalati, T.; Serre, C.; Gillet, B.; Sebrie, C.; Baati, T.; Eubank, J. F.; Heurtaux, D.; Clayette, P.; Kreuz, C.; Chang, J.-S.; Hwang, Y. K.; Marsaud, V.; Bories, P.-N.; Cynober, L.; Gil, S.; Férey, G.; Couvreur, P.; Gref, R. Nat. Mater. 2010, 9, 172–178. (9) Devic, T.; Horcajada, P.; Serre, C.; Salles, F.; Maurin, G.; Moulin, B.; Heurtaux, D.; Clet, G.; Vimont, A.; Grenéche, J.-M.; Le Ouay, B.; Moreau, F.; Magnier, E.; Filinchuk, Y.; Marrot, J.; Lavalley, J.-C.; Daturi, M.; Férey, G. J. Am. Chem. Soc. 2010, 132, 1127–1136.
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Wide Control of Proton Conductivity in Porous Coordination Polymers Akihito Shigematsu,†,‡ Teppei Yamada,† and Hiroshi Kitagawa*,†,‡,§ †
Division of Chemistry, Graduate School of Science, Kyoto University, Kitashirakawa-Oiwakecho,
Sakyo-ku, Kyoto 606-8502, Japan,
‡
Department of Chemistry, Faculty of Science, Kyushu
University, Hakozaki 6-10-1, Higashi-ku, Fukuoka 812-8581, Japan, and §CREST, Japan Science and Technology Agency (JST), Sanban-cho 5, Chiyoda-ku, Tokyo 102-0075, Japan
Experimental Section Materials and reagents. All the reagents and solvents were commercially available and used without further purification.
Synthesis of Al(OH)(O2C–C6H4–CO2)(H2O) [MIL-53(Al)] (1). The synthesis of MIL-53(Al) was performed as described elsewhere.1 Al(NO3)3·9H2O 3.9 g (10.5 mmol), terephthalic acid 0.86 g (7.5 mmol), and water (30 mL) were added to a 70 mL Teflon-lined steel autoclave. The autoclave was heated in an oven at 473 K for three days. After filtering, washing with water and then drying in air, the compound was kept at 503 K in an electric furnace for three days to remove excess terephthalic acid in the pores. The calcined sample was refluxed in ethanol for a day and then dried at 473 K under vacuum. A white powder of 1 was obtained (0.50 g, 29.3%). Elemental analysis calcd. for C8H7O6Al: C, 42.49; H, 3.12%. Found: C, 42.89; H, 2.84%. Synthesis of Al(OH)(O2C–C6H3(NH2)–CO2)(H2O) [MIL-53(Al)–NH2] (2). The synthesis of MIL-53(Al)–NH2 was performed as described elsewhere.2 Al(NO3)3·9H2O 1.99 g (5.3 mmol), 2-aminoterephthalic acid 0.98 g (5.7 mmol), and water (13 mL) were added to a 70 mL Teflon-lined steel autoclave. The autoclave was heated in an oven at 423 K for five hours. After filtering, the compound was refluxed in N,N´-dimethylformamide at 423 K for 12 hours and then dried in an oven at 413 K for one day. A yellow powder of 2 was obtained (0.38 g, 30.3%). Elemental analysis calcd. for C8H8O6NAl: C, 39.85; H, 3.34; N, 5.81%. Found: C, 39.88; H, 3.17; N, 5.87%.
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Synthesis of Al(OH)(O2C–C6H3(OH)–CO2)(H2O)1.5 [MIL-53(Al)–OH] (3). The synthesis of MIL-53(Al)–OH was performed as described elsewhere.3 First, the synthesis of 2-hydroxyterephthalic acid was carried out from 2-aminoterephthalic acid in a one-step reaction using the same synthesis method. 2-hydroxyterephthalic acid 1.87 g (10.2 mmol) dissolved in N,N´-dimethylformamide (30 mL) was added dropwise to Al(NO3)3·9H2O 7.81 g (21 mmol) dissolved in water (30mL) at ambient temperature. The reaction mixture was heated to 363 K and held at the temperature for 40 hours. After filtering, the crude compound was refluxed in ethanol for 36 hours and then dried at 393 K under vacuum. A white powder of 3 was obtained (2.04 g, 80%). Elemental analysis calcd. for C8H8O7.5.Al: C, 38.26; H, 3.21%. Found: C, 37.84; H, 2.79%. Synthesis of Fe(OH)(O2C–C6H2(COOH)2–CO2)(H2O) [MIL-53(Fe)–(COOH)2] (4). The synthesis of MIL-53(Fe)–(COOH)2 was performed as described elsewhere.4 FeCl2·4H2O 1.13 g (5.68 mmol), 1,2,4,5-benzenetetracarboxylic acid 0.71 g (2.84 mmol), and HF (0.21 mL), and water (48 mL) were added to a 120 mL Teflon-lined steel autoclave. The autoclave was heated in an oven at 473 K for two days. After filtering and washing with water, orange crystals of 4 were obtained (0.15 g, 15.4%). Elemental analysis calcd. for C10H7O10Fe: C, 35.02; H, 2.06%. Found: C, 34.94; H, 2.04%.
Powder X-ray diffraction (PXRD) measurements. PXRD measurements were carried out with a Bruker D8 ADVANCE using CuKα radiation.
Figure S1. Powder X-ray diffraction patterns of (a) Al(OH)(C8H4O4)·H2O simulated from
single-crystal X-ray diffraction analysis,1 (b) 1, (c) 2, (d) 3, (e) Fe(OH)(C10H4O6)·H2O simulated from single-crystal X-ray diffraction analysis,4 and (f) 4 at 298 K.
S2
Table S1. Cell parameters of hydrated or dehydrated 1–4 calculated with powder pattern fitting.
Infrared spectroscopy (IR) experiments. IR experiments were performed with a Perkin Elmer Spectrum 100 FT-IR spectrometer.
Figure S2. IR spectra of (a) 1, (b) 2, (c) 3, and (d) 4.
S3
Water adsorption and desorption isotherm measurements. Water adsorption and desorption isotherm measurements were carried out volumetrically with an automatic adsorption apparatus, BELSORP-max (BEL Japan). Samples were prepared by degassing at 473K for 24 hours.
Figure S3. Water adsorption (filled) and desorption (open) isotherms of dehydrated
1 (blue ■), 2 (pink ▼), 3 (green ▲) and 4 (red ●) at 298 K.
Conductivity measurements. Proton conductivity measurements of the compounds were determined using the conventional quasi-four-probe method, using gold paste and gold wires (50 μm φ) with a Solartron SI 1260 Impedance/Gain-Phase Analyzer and 1296 Dielectric Interface in the frequency range 1 Hz to 1 MHz at 298 K under humid conditions (controlled by using an Espec Corp. SH-221 incubator), using sample pellets of ~ 0.7 mm thickness and 2.5 mm φ.
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References (1) Loiseau, T.; Serre, C.; Huguenard, C.; Fink, G.; Taulelle, F.; Henry, M.; Bataille, T.; Férey, G. Chem.—Eur. J. 2004, 10, 1373–1382. (2) Ahnfeldt, T.; Gunzelmann, D.; Loiseau, T.; Hirsemann, D.; Senker, J.; Férey, G.; Stock, N. Inorg. Chem. 2009, 48, 3057–3064. (3) Himsl, D.; Wallacher, D.; Hartmann, M. Angew. Chem., Int. Ed. 2009, 48, 4639–4642. (4) Sanselme, M.; Grenéche, J.-M.; Riou-Cavellec, M.; Férey, G. Solid State Sci. 2004, 6, 853–858.
Complete list of refs 8b and 9 (8) (b) Horcajada, P.; Chalati, T.; Serre, C.; Gillet, B.; Sebrie, C.; Baati, T.; Eubank, J. F.; Heurtaux, D.; Clayette, P.; Kreuz, C.; Chang, J.-S.; Hwang, Y. K.; Marsaud, V.; Bories, P.-N.; Cynober, L.; Gil, S.; Férey, G.; Couvreur, P.; Gref, R. Nat. Mater. 2010, 9, 172–178. (9) Devic, T.; Horcajada, P.; Serre, C.; Salles, F.; Maurin, G.; Moulin, B.; Heurtaux, D.; Clet, G.; Vimont, A.; Grenéche, J.-M.; Le Ouay, B.; Moreau, F.; Magnier, E.; Filinchuk, Y.; Marrot, J.; Lavalley, J.-C.; Daturi, M.; Férey, G. J. Am. Chem. Soc. 2010, 132, 1127–1136.
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