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Gas Adsorption of Two Dimensional Super Flexible and Three Dimensional Biporous Coordination Polymers with Identical Framework Composition A, Kondo, a, f H, Noguchi, b H, Kajiro, c L. Carlucci, d D. M. Proserpio, d G. Ciani, d Y. Hattori, e F. Okino, e T. Ohba, b K. Kaneko, b H. Kanoh b a: Collaborative Innovation Center for Nanotech FIBER (nanoFIC), Shinshu University, Ueda, Japan, b: Graduate School of Science, Chiba University, Yayoi, Inage, Chiba, Japan, c: Nippon Steel Corporation, Shintomi, Futtsu, Chiba, Japan, d: Dipartimento di Chimica Strutturale e Stereochimica Inorganica, Universita` di Milano, Via G. Venezian 21, Italy, e: Department of Chemistry, Faculty of Textile Science and Technology, Shinshu University, Ueda, Japan Present address f : Tokyo University of Agricculture and Technology, Graduate School of Engineering, Department of Applied Chemistry, Tokyo, Japan. E-mail: [email protected] 0.19 (6.2 mmol g −1 ) (61%) 0.095 (3.8 mmol g −1 ) (31%) 0.27 (8.0 mmol g −1 ) (87%) 3D PCP (mL g −1 ) 0.35 (12 mmol g −1 ) (250%) 0.23 (8.3 mmol g −1 ) (164%) 0.27 (7.9 mmol g −1 ) (193%) 2D PCP (mL g −1 ) Ar CO 2 N 2 ABSTRACT ABSTRACT Selective synthetic routes of [Cu(bpy) 2 (OTf) 2 ] n (bpy = 4,4΄-bipyridine, OTf = trifluoromethanesulfonate) with two and three dimensionalities by choosing each inherent different solvent- solution system were established. They have a quite similar local coordination structure around a Cu(II) ion, leading the 2D and 3D building-up structures with different connectivity. Although the two kinds of porous coordination polymers (PCPs) have framework flexibility, the 2D PCP (ELM-12) [1,2] is more flexible than the 3D PCP [3] , giving rise to different framework flexibility- associated gas adsorption behaviors. All adsorption isotherms for N 2 , CO 2 , and Ar on the 3D PCP are of type I, whereas the 2D PCP has stepwise gas adsorption isotherms for CH 4 and water in addition to these gases. The 3D PCP having hydrophilic and hydrophobic pores shows the size selective and quadrupole-surface electrical field interaction dependent adsorption [4] . The 2D PCP can accommodate remarkably greater amount of gas molecules than that corresponding to the inherent void volume through the framework structural change. In alcohol adsorption isotherms, however, the 2D PCP changes its framework structure through the guest accommodation, leading to no stepwise adsorption isotherms The structural diversity of the 2D PCP stems from the breathing phenomenon [5,6] and expansion/shrinkage modulation [7-9] . REFERENCES [1] Kondo, A.; Noguchi, H.; Carlucci, L.; Proserpio, D. M.; Ciani, G.; Kajiro, H.; Ohba, T.; Kanoh, H.; Kaneko, K. J. Am. Chem. Soc. 2007, 129, 12362−12363. [2] A. Kondo, A. Chinen, H. Kajiro, T. Nakagawa, K. Kato, M. Takata, Y. Hattori, F. Okino, T. Ohba, K. Kaneko, H. Kanoh, Chem. Eur. J., 2009, 31, 7549-7553. [3] Carlucci, L.; Cozzi, N.; Ciani, G.; Moret, M.; Proserpio, D. M.; Rizzato, S. Chem. Commun. 2002, 1354-1355. CONCLUSION CONCLUSION · The synthesis of 2D and 3D structures of [Cu(bpy) 2 (OTf) 2 ] can be controlled by using different kinds of alcohol as interlayer solvent. · The 2D PCP (ELM-12) shows stepwise adsorption isotherms due to not only the expansion / shrinkage structural transformation but also breathing phenomenon. The micropore filling is not indispensable for the structural change, which can occur without definite steps in adsorption isotherms. · The 3D PCP having hydrophilic and hydrophobic pores shows the size selective and quadrupole-surface electrical field interaction dependent adsorption and has potential to accommodate different kinds of molecules in the inherently different pores separately. [5] C. Serre, F. Millange, C. Thouvenot, M. Noguès, G. Marsolier, D. Louër, G. Férey, J. Am. Chem. Soc., 2002, 124, 13519-13526. [6] S. Bourrelly, P. L. Llewellyn, C. Serre, F. Millange, T. Loiseau, G. Férey, J. Am. Chem. Soc., 2005, 127, 13519-13521. [7] L. Di, K. Kaneko, Chem. Phys. Lett. 2001, 335, 50-56. [8] Noguchi, H.; Kondoh, A.; Kanoh, H.; Kajiro, H.; Kaneko, K. J. Phys. Chem. B 2005, 109, 13851−13853. [9] Kondo, A.; Noguchi, H.; Ohnishi, S.; Kajiro, H.; Tohdoh, A.; Hattori, Y.; Xu, W.-C.; Tanaka, H.; Kanoh, H.; Kaneko, K. Nano Lett. 2006, 6, 2581−2584 Expansion / shrinkage modulation Expansion / shrinkage modulation Expansion Expansion Shrinkage Shrinkage As synthesized 0.14 0.25 mL g -1 % 18 31 Void volume 5.65, 6.94 6.10 Offset (Å) 5.86, 6.73 7.16 Interlayer distance (Å) Guest free As synthesized Crystal state Structural parameters in the layered structures Structural parameters in the layered structures Guest free High pressure H High pressure H 2 , CH , CH 4 and CO and CO 2 adsorption isotherms adsorption isotherms on 2D PCP (ELM on 2D PCP (ELM- 12) 12) Cu(OTf) Cu(OTf) 2 (30.0 (30.0 mM mM, 10.0 , 10.0 mL mL) aqueous solution ) aqueous solution bpy bpy ethanolic ethanolic solution (60.0 solution (60.0 mM mM, 10.0 , 10.0 mL mL) Interlayer solvent ( 1.0 Interlayer solvent ( 1.0 mL mL) Dark blue crystals Dark blue crystals Dark blue crystals Dark blue crystals methanol, ethanol, methanol, ethanol, 1-propanol, 1 propanol, 1-butanol butanol 1-hexanol, 1 hexanol, 1-octanol octanol The 2D crystal The 2D crystal The 3D crystal The 3D crystal c b Interlayer solvent Interlayer solvent 2D crystal structure 2D crystal structure a b Hydrophobic Hydrophilic 37.7 0.31 Total pore volume 24.7 13.0 % 0.20 0.11 mL g -1 Pore volume Hydrophobic Hydrophilic c b 3D crystal structure 3D crystal structure Adsorption isotherms of N Adsorption isotherms of N 2 , CO , CO 2 , and , and Ar Ar on 2D and 3D PCPs on 2D and 3D PCPs 3D PCP 3D PCP 2D PCP (ELM 2D PCP (ELM-12) 12) Ar : 0.376 nm N 2 : 0.310 nm CO 2 : 0.340 nm Hydrophilic pore 0.33 ± 0.02 nm Hydrophobic pore > 0.45 nm Selective adsorption of 3D PCP Selective adsorption of 3D PCP Total pore volume (mL g −1 ) 0.31 Hydrophilic pore Volume (mL g −1 ) 0.11 Hydrophobic pore volume (mL g −1 ) 0.20 Adsorbed volume (mL g −1 ) N 2 0.27 Ar 0.19 CO 2 0.095 In situ IR spectra through CO In situ IR spectra through CO 2 adsorption adsorption Pore and adsorbed volume Pore and adsorbed volume Adsorbed amount of each gases on 2D and 3D PCP Used density for calculation of adsorbed amount in ml/g unit. N 2 : 0.808 g/mL, CO 2 , 1.565 g/mL, Ar: 1.395 g/mL. Each percentage shows the percentage of adsorbed amount against the void volumes of the guest free states. 0 5 10 15 20 25 30 0 1 2 3 4 5 6 Surface excess mass of CH 4 (mg/g) Fugacity (MPa) 0 20 40 60 80 100 120 140 160 0 0.5 1 1.5 2 2.5 Sueface excess mass of CO 2 (mg/g) Fugacity (MPa) Synchrotron XRD patterns of 2D PCP without guest, adsorbing alcohols and water at room temperature 1100 1200 1300 1400 1500 1600 1700 Intensity / a.u. Wavenumber / cm -1 Local structure Local structure around around Cu(II Cu(II) ion ) ion Synthesis of 2D and 3D crystals [Cu(bpy) Synthesis of 2D and 3D crystals [Cu(bpy) 2 (OTf) (OTf) 2 ] bpy bpy bending bending at 196 K at 196 K ν as of SO 3 in OTf 1120 1140 1160 1180 1200 Absorbance / a.u. Wavenumber / cm -1 1172 cm -1 1182 cm -1 N 2 : : Adsorption in both pore (hydrophilic and hydrophobic) Adsorption in both pore (hydrophilic and hydrophobic) Ar Ar: : Size selective adsorption into hydrophobic pore Size selective adsorption into hydrophobic pore CO CO 2 : : Quadrupole Quadrupole-surface electrical field interaction surface electrical field interaction (between CO (between CO 2 and and OTf OTf) dependent adsorption into ) dependent adsorption into hydrophilic pore hydrophilic pore 13.3 13.3 kPa kPa 0 0 kPa kPa CH 4 adsorption at 258 K CO 2 adsorption at 273 K Interaction between CO Interaction between CO 2 molecules and molecules and OTf OTf anions anions Carbon dioxide adsorption in hydrophilic pore Carbon dioxide adsorption in hydrophilic pore Isosbestic point Crystallographic pore volume Crystallographic pore volume 0 2 4 6 8 10 12 0 1 2 3 4 5 6 Surface excess mass of H 2 (mg/g) Fugacity (MPa) H 2 adsorption at 77 K 0 50 100 150 200 250 0 0.2 0.4 0.6 0.8 1 Adsorbed amounts (mg/g) P/P 0 ● MeOH ● EtOH ● 1-PrOH ● Water + guest - guest Expansion + guest - guest Dotted line: Length of diagonal length Arrow: Interlayer distance Distortion of 2D grid Expansion/shrinkage Alcohol adsorption isotherms No definite folding point Structural change can occur without definite folding points in isotherms. at room temp. Folding point Folding point Extend DR analysis of H 2 adsorption isotherm at 77 K Estimated saturated adsorption amount: 7 mg/g Experimental maximum adsorption amount ~10 mg/g Type I isotherms Almost no micropore filling Slight hysteresis Large hysteresis Hydrophobic nature a b
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