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Supplementary information for Adsorption Induced Transitions in Soft Porous Crystals: An Osmotic Potential Approach to Multistability and Intermediate

1 Supplementary information for Adsorption Induced Transitions in Soft Porous Crystals: An Osmotic Potential Approach to Multistability and Intermediate Structures D. Bousquet, F.-X. Coudert, A. G. J. Fossati, A. V. Neimark, A. H. Fuchs, A. Boutin α L Figure S1: Snapshot of a unit cell of our simplified MIL-53 model. i

2 h Figure S2: Snapshot of a unit cell of our slit pore model. fluid-fluid 3.5 Å 150 K host-fluid 3.4 Å 140 K Figure S3: Lennard Jones parameters for the fluid-fluid and host fluid interactions in the MIL53 model and in the slit pore model. ii

3 K H (bar -1 ) h (Å) Figure S4: Henry s constant (in logarithmic scale) of the slit pore as a function of slit pore height h. Black dots: numerical results from Grand Canonical Monte Carlo simulations; red curve: analytical fit using Eq N max (molecules/u.c.) Figure S5: α/α MCS Profile of saturation uptake (N max )asafunctionofporeopening for our simple MIL-53 model. Black dots: data obtained from Grand Canonical Monte Carlo simulations; red line: linear approximation N max = A + B, with B =0.216 and A = 4.85 iii

4 K (bar -1 ) H α/α MCS Figure S6: Henry s constant (in logarithmic scale) of adsorption in the simple MIL-53 model. Black dots: numerical results from Grand Canonical Monte Carlo simulations; red curve: analytical fit using Eq. 3, resulting in the parameters KH 0 = bar 1, 1 =23.57 and 2 = PHbarL ê 0 Figure S7: 2D surface of the osmotic potential as a function of pore opening and external gas pressure P in the case of a large adsorbate ( MCS =1.2 0 ). The color scale ranges from 50 (purle) to 30 kj/mol (red). iv

5 F host (kj.mol -1 ) F host (kj.mol -1 ) Figure S8: Profile of the host free energy, F host, of the simplified MIL-53 model in case A(top) and case B(bottom) as a function of pore opening v

6 α( ) σ(å) Figure S9: Evolution of the order parameter MCS as a function of the LJ parameter of the adsorbate Dependance of maximum loading and Henry s constant as a function of particle size Henry s constant and maximum loading profile as a function of the order parameter have been computed for a reference particle size (with LJ parameter ref and ref ). The single particle most comfortable state order parameter has been computed for a set of particle with increase size. The evolution of MCS appears to be roughly linear as a function of the Lennard Jones parameter (see Fig.S9). MCS ( )= Furthermore, the maximum loading for a particle with LJ parameters ref and extrapolated following : has been N max (, )=N max (, ref ref 3 ) vi

7 Figure S10: Profile of osmotic potential upon adsorption for a bistable material, as a function of the channel opening, for different values of external gas pressure, in case A Figure S11: Profile of osmotic potential upon adsorption for a bistable material, as a function of the channel opening, for different values of external gas pressure, in case A2 vii

8 0-50 Figure S12: Profile of osmotic potential upon adsorption for a bistable material, as a function of the channel opening, for different values of external gas pressure, in case A Figure S13: Profile of osmotic potential upon adsorption for a bistable material, as a function of the channel opening, for different values of external gas pressure, in case B1 viii

9 0-100 Figure S14: Profile of osmotic potential upon adsorption for a bistable material, as a function of the channel opening, for different values of external gas pressure, in case B Figure S15: Profile of osmotic potential upon adsorption for a bistable material, as a function of the channel opening, for different values of external gas pressure, in case B3 ix

10 N ads (molecules/u.c.) P(bar) Figure S16: Behavior of a bistable material upon gas adsorption, in case B2 (see Section III A). Top: evolution of host pore opening as a function of external gas pressure; bottom: adsorption isotherm. N max (molecules/u.c.) Figure S17: h(å) Profile of saturation uptake (N max )foraslitpore,asafunctionoftheslit pore height h. Black dots: data obtained from Grand Canonical Monte Carlo simulations; the red line is a guide for the eyes. x

11 N max (molecules/u.c.) Figure S18: α/α MCS Profile of saturation uptake (N max )asafunctionofporeopening for our simple MIL-53 model, in which we have introduced an artificial step at / 0 =1.3 to demonstrate the influence of packing effects on adsorption-induced transitions. xi

CARBON 2004 Providence, Rhode Island. Adsorption of Flexible n-butane and n-hexane on Graphitized Thermal Carbon Black and in Slit Pores

CARBON 2004 Providence, Rhode Island. Adsorption of Flexible n-butane and n-hexane on Graphitized Thermal Carbon Black and in Slit Pores CARBON Providence, Rhode Island Adsorption of Flexible n-butane and n-hexane on Graphitized Thermal Carbon Black and in Slit Pores D. D. Do* and H. D. Do, University of Queensland, St. Lucia, Qld 7, Australia