- Supplementary Information - Metal-Organic Frameworks in adsorption driven. fluid

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1 - Supplementary Information - Metal-Organic Frameworks in adsorption driven heat pumps: The potential of alcohols as working fluid Martijn F. de Lange a,b, Benjamin L. van Velzen a, Coen P. Ottevanger a, Karlijn J.F.M. Verouden a, Li-Chiang Lin b, Thijs J.H. Vlugt b, Jorge Gascon a, Freek Kapteijn a * a Catalysis Engineering, Chemical Engineering Department, Delft University of Technology, Julianalaan 136, 2628 BL Delft, The Netherlands. b Engineering Thermodynamics, Process & Energy laboratory, Delft University of Technology, Leeghwaterstraat 39, 2628 CB Delft, The Netherlands

2 SUPPLEMENTARY MATERIAL This supplementary information file contains the following information: S-1: List of symbols...3 S-2: Experimental details...5 S-3: Calculation details S-4: Characterization of MOFs under study S-5: MOF stability S-6: Equilibration time issue S-7: Comparison of methanol and ethanol adsorption S-8: Characteristic curves (methanol) S-9: Characteristic curves (ethanol) S-10: Enthalpy of adsorption (Isosteric) S-11: Working capacity of MOFs for heat pump conditions S-12: Working capacity of MOFs for refrigeration conditions S-13: Coefficients of performance for selected MOFs at refrigeration conditions S-14: Working capacity of MOFs for ice making conditions S-15: Extending T d for MIL-101 (refrigeration) for ethanol and methanol S-16: Comparison with activated carbon (G32-H) References

3 S-1: List of symbols Latin Symbol Meaning Units A Adsorption potential kj mol -1 COP Coefficient of performance - c p Heat capacity J g -1 K -1 / J mol -1 K -1 d Pore diameter Å D c Critical diameter nm m mass g M w Molar mass g mol -1 p Pressure bar p/p o Relative pressure - p o Saturation pressure bar q Amount adsorbed g g -1 Q Energy kj mol -1 [1] R Gas constant J K -1 mol -1 T Temperature K V p Pore volume ml(liq.) g -1 W Liquid volume adsorbed ml(liq.) g -1 [2] Greek Symbol Meaning Units α p/p o for which q = 0.5 q max - ads H Enthalpy of adsorption kj mol -1 vap H Enthalpy of evaporation kj mol -1 ρ Density g ml -1 σ Molecule size nm Subscripts subscript Meaning 1 Of point 1 (in Figure S 1) 2 Of point 2 (in Figure S 1) 3 Of point 3 (in Figure S 1) 4 Of point 4 (in Figure S 1) ads Adsorber/adsorption c Critical (point) c Crystal(line) C Cooling (COP) con Condenser 3

4 des ev H hex liq max min regen sat sorbent sorption W Desorption Evaporator Heating (COP) Heat exchanger Liquid Maximum Minimum Regeneration At saturation Adsorbent Adsorption For volume W adsorbed Superscripts Superscript Meaning effective Effective hex Heat exchanger sorbent adsorbent wf Working fluid H For which ads H is known Notes: [1] Except for Figure 5 where Q s are displayed per ml sorbent (ρ c used for conversion). [2] Except for Table 2, Figures 6-8, S 4, S 21-23, S and S where W is displayed in ml ml -1 sorbent (ρ c used for conversion). 4

5 S-2: Experimental details Materials: 2-Aminoterephthalic acid (Sigma-Aldrich, 99%), 2,5-hydroxyterephthalic acid (Sigma- Aldrich, 97%), 4,4 -benzophenonedicarboxylic acid (TCI Europe, 95%), 4,4'- Biphenyldicarboxylic acid (TCI Europe, 97%), terephthalic acid (Sigma-Aldrich, 98%), isophthalic acid (Sigma-Aldrich, 99%), fumaric acid (Simga-Aldrich, 99%), 2- methylimidazole (Sigma-Aldrich, 98%), AlCl 3 6H 2 O (Sigma-Aldrich, 99%), Al 2 (SO 4 ) 3 18H 2 O (Sigma-Aldrich, 98%), Al(NO 3 ) 3 9H 2 O (Sigma-Aldrich, 98%), titanium isopropoxide (Acros organics, 98+%), Cr(NO 3 ) 3.9H 2 O (Sigma-Aldrich, 97%), ZrCl 4 (Sigma- Aldrich, 99%), Zn(NO 3 ) 2.6H 2 O (Sigma-Aldrich, 98%), NaOH (Sigma-Aldrich, 98%), HF (Sigma-Aldrich, 40%), methanol (Sigma-Aldrich, 99.8%), ethanol (Sigma-Aldrich, 95%) and DMF (Sigma-Aldrich, 99.8%) were purchased from respective suppliers and were used without any further purification. CAU-1: The synthesis of CAU-1 was performed according to literature, 1 by suspending 379 mg of 2- aminoterephthalic acid and 1507 mg of AlCl 3 6H 2 O in 20 ml of methanol in a 30 ml Teflon insert inside a stainless steel autoclave. The mixture was heated for 5 h at 125 C. The residue after filtration was a yellow powder. The as-synthesized powder was washed overnight with 500 ml of deionized water three times. The final suspension was filtered and the product was dried in air. CAU-1-(OH) 2 : Again literature procedure was followed to synthesize CAU-1-(OH) 2. 2 A mixture of 1048 mg of AlCl 3 6H 2 O, 299 mg of 2,5-hydroxyterephthalic acid, 36 mg of NaOH and 10 ml 5

6 methanol was fitted in a 30 ml Teflon insert, which was placed in a stainless steel autoclave. Hereafter, the autoclave was placed in an oven for 5 h at 125 C. A yellow product was obtained after filtration. The synthesized product was thoroughly washed five times with demineralized water. The residue was dried in air to obtain CAU-1-(OH) 2. CAU-3-(NH 2 ): CAU-3-(NH 2 ) 3 was synthesized in a 30 ml Teflon insert. In 32.0 ml methanol, 1080 mg of Al(NO 3 ) 3 9H 2 O, 80 mg of terephthalic acid (or aminoterephthalic acid) and mg of NaOH (Aldrich, 99.8%) were suspended. The insert was fitted in a stainless steel autoclave and then placed in an oven to heat up to 125 C in 12 h. This temperature was kept constant for 3 h and finally the insert was cooled down to room temperature. Afterwards, the mixture was filtered and washed with 30 ml of for 12 h at 115 C and 20 ml methanol at 65 C for 12 h. CAU-8: The synthesis of CAU-8 was performed according to 4. In a 30 ml Teflon insert, 2000 mg of 4,4 -benzophenonedicarboxylic acid, 2466 mg of Al 2 (SO 4 ) 3 18H 2 O, 8 ml of deionized H 2 O and 12 ml of DMF were mixed to a suspension. The insert was placed in a stainless steel autoclave and heated up in the oven to 140 C in 1 h. The autoclave was kept at this temperature for 12 h and then cooled down to room temperature. The reaction was followed by a filtration step. The obtained powder was thoroughly washed with 40 ml of DMF (Aldrich, 99.8%). After another filtration, the white solid was washed with water. Finally, the powder was dried in air. CAU-10-H: 6

7 CAU-10-H was synthesized according to 5 by adding 160 mg of isophthalic acid, 640 mg of Al 2 (SO 4 ) 3 18H 2 O, 0.8 ml of DMF and 3.2 ml of H 2 O to a Teflon insert, sealed within a stainless steel autoclave. The insert was placed in an oven, which was kept at 135 C for 12 h. The product, obtained from filtering, was dispersed in deionized water by sonication. The dispersion was filtered again and the white powder was dried in air under ambient conditions. Al-fumarate: Synthesis as reported by Jeremias et al. 6 To a round bottom Flask 26.9 g AlCl 3.6H 2 O, 15.4 g fumaric acid and 550 ml DMF were added. The turbid, yellowish mixture was stirred at 130 o C for 4 days. After cooling, the snow-white precipitate was filtered off and stirred twice in acetone (1 h and 24 h, 200 ml each), and twice in ethanol (1 h and 24 h, 200 ml each). MIL-53: 8.71 g of AlCl 3.6H 2 O, 2g of terephthalic acid and 30 ml H 2 O, were added in a Teflon insert, sealed within a stainless steel autoclave. The autoclave was then heated in an oven at 220 C for 72 h. After filtering, the powder was washed with methanol. The solid was then suspended in 20 ml DMF and kept overnight at 130 o C. The resulting suspension was filtered and washed with methanol. The solid was suspended once more in 10 ml methanol and kept at 70 o C for 5 h. The solid was collected by filtration and dried at 160 o C. MIL-53-NH 2 : Synthesis according to Stavitsky et al. 7 Water (28ml), DMF (2ml), AlCl 3.6H 2 O (1.97 g) and aminoterephthalic acid (1.5 g) are added in a Teflon insert, sealed within a stainless steel autoclave. The autoclave was heated in an oven at 150 C for 5 h. After reaction, the unreacted terephthalic acid remaining in the pores of the freshly filtered MOF was exchanged with DMF 7

8 at 130 ºC for 8 h. The DMF molecules are removed with methanol at 70 C for 4.5 h. Both processes are done in an autoclave. MIL-125(-NH 2 ): The synthesis of MIL-125(-NH 2 ) 8 was performed by dissolving either 2-aminoterephthalic acid (3.85 g) or terephthalic acid (3.53 g) in 56 ml of N,N -dimethylformamide (DMF) at room temperature under stirring. The mixture was placed in a round bottom flask (100 ml) and was warmed at 105 C under air for 2 h. After the water removal 14 ml of dry methanol was added to the mixture and a reflux condenser was applied. The mixture was kept at 105 C for another 1 h and then 4.2 ml of titanium isopropoxide (Acros organics, 98+ %) was added. The mixture was kept under stirring (magnetic stirring) and heated for 72 h at 100 C under air. The obtained solid was filtered and washed with DMF at room temperature. The activation consists of a 2-step treatment. The as-synthesized dried solid was dispersed at room temperature in DMF under stirring overnight (50 ml of DMF per 1 g of product) in order to remove residual free acid. Then, the same procedure was repeated twice using methanol instead of DMF to exchange the DMF within the pores. The solid was finally dried under air at 100 C. MIL-100: Synthesis of MIL-100(Cr) was performed in accordance with literature. 9,10 A mixture of 0.5 g chromium(vi) oxide, CrO3, 1.05 g of trimesic acid, C6H3-1,3,5-(CO2H)3 (97%), g hydrofluoric acid, HF, and 24 g of H2O was added to a Teflon container, inserted in a stainless steel autoclave. This was then heated in an oven at 493 K for 4 days under static conditions. The resulting solid was filtered off, washed with deionized water and subsequently acetone and finally dried overnight at 433 K and stored under air atmosphere. MIL-101: 8

9 Synthesis of MIL-101(Cr) was performed as previously reported in literature g of Cr(NO 3 ) 3.9H 2 O, 0.7 g of terephthalic acid, 0 g of HF and 20 g of distilled water was added in a Teflon container, which was inserted in a stainless steel autoclave. The autoclave was heated for 8 h at 493 K in an oven under static conditions. After synthesis, the solid product was filtered from the synthesis solution. Afterwards a solvothermal treatment was performed using ethanol at 353 K for 24 h. The resulting solid was exchanged in a 1M solution of NH 4 F, at 343 K for 24 h and was immediately filtered off and washed with hot water. The solid was finally dried overnight at 433 K and stored under air atmosphere. MIL-140A: MIL-140A 13 was synthesized by dissolving 0.94 g of ZrCl 4 and 1.34 g of terephthalic acid in 23.7 g DMF at room temperature in an Teflon insert placed inside an autoclave. Loading of the insert occurred in a glove box. The autoclave was then heated in an oven at 220 C for 16 h. After cooling in air to room temperature the resulting solid was filtered, repeatedly washed with DMF and dried at room temperature. MIL-140C: MIL-140C 13 was synthesized by dissolving 1.17 g of ZrCl4 and 2.42 g of 4,4 -biphenyl dicarboxylic acid in 23.7 g DMF at room temperature in an Teflon insert placed inside an autoclave. Loading of the insert occurred in a glove box. The autoclave was then heated in an oven at 220 C for 12 h. After cooling in air to room temperature the resulting solid was filtered, repeatedly washed with DMF and dried at room temperature. UiO-66: Synthesis of UiO-66 was performed as previously reported g of ZrCl 4 and 02 g of terephthalic acid were dissolved in 24.9 g DMF at room temperature and added to a Teflon 9

10 insert placed in an autoclave. The autoclave was heated in an oven at 120 C for 24 h. After cooling in air to room temperature the resulting solid was filtered, repeatedly washed with DMF and dried at room temperature. UiO-67: Synthesis of UiO-67 was based on the protocol put forward by Guillerm et al gram ZrCl 4 was dissolved in 300 ml DMF in a round bottom flask (oven dried, 500mL) at room temperature and stirred to dissolve all the ZrCl 4. Afterwards 2.4 gram 4,4'- biphenyldicarboxylic acid was added. After strirring for 10 minutes 5 ml H 2 O and 50 ml DMF were added to wash down any solids on the sides of the flask. The mixture was then heated up to 95 o C in an oil bath without stirring for 100 h. Afterwards, the material was filtered and subsequently washed with DMF and methanol overnight. ZIF-8: The synthesis of ZIF-8 was based on previous literature. 15 Firstly, 1.17 g Zn(NO3)2 6H2O (Sigma-Aldrich, 98%) was dissolved in 8 g deionized (DI) water. Secondly, g 2- methylimidazole (Sigma-Aldrich, 98%) was dissolved in another 80 g DI water. The zinc nitrate solution was then mixed with the 2-methylimidazole solution under stirring. All the operations were performed at room temperature. After stirring for ~5 min, the product was collected by centrifuging, and then washed with DI water for several times. The product was dried at 65 C overnight in a drying oven. S-3: Calculation details Detailed heat pump cycle An adsorption driven heat pump cycle consists of four steps, two for adsorption and two for desorption. These steps are briefly explained with the aid of the cycle diagram (Figure S 1). 10

11 Figure S 1: Isosteric cycle diagram of an adsorption heat pump cycle, including the vapor pressure of the chosen working fluid (black line), minimum and maximum isosteres, lines of equal loading, W min and W max (grey dashed lines), temperature and pressure of the evaporator (T ev, p ev, blue dashed lines) and condenser (T con, p con, orange dashed lines), desorption temperature (T des, red dashed line) and intermediate cycle temperatures (T 1, T 2 and T 3, black dashed line). Reproduced from 16. In this diagram, the x-axis indeed is shown as -1/T, which is typically done in literature to ensure both that the isosteric lines are straight (ln p versus 1/T) and that the lowest temperature is at the left end of the figure. Starting from a fully saturated adsorbent (point I), the four steps are consecutively: Isosteric heating (I-II): The adsorbent is fully saturated (W max ) and requires regeneration or desorption of working fluid. Before working fluid can be released to the condenser, pressure needs to be increased from p ev to p con. This is realized by heating the adsorbent from T 1 to T 2. During this stage, ideally, no working fluid is desorbed and the adsorbent vessel is disconnected from both the condenser and evaporator. 11

12 Isobaric desorption (II-III): Adsorbent heating is continued. Because the adsorbent vessel is connected to the condenser in this stage, working fluid is allowed to desorb and no further pressure increase occurs. This process is stopped when desorption temperature (T des ) is reached and the adsorbent loading is minimal (W min ). The desorbed working fluid (W max - W min ) is condensed, releasing heat to the environment in the condenser (Q con, Figure 2). Isosteric cooling (III-IV): The adsorbent is regenerated and can be used for adsorption. However first the pressure needs to be reduced to p ev by cooling the vessel from T des to T 3, again isosterically and disconnected from condenser and evaporator. Isobaric adsorption (IV-I): Cooling is continued. Because the adsorbent vessel is connected to the evaporator in this stage, working fluid is allowed to adsorb and no further pressure decrease occurs. This process is stopped when T 1 is reached and the adsorbent loading is maximal again (W max ). The adsorbed working fluid (W max W min ) has taken up energy from the environment at a low temperature in the evaporator by its evaporation (Q ev, Figure 2), while releasing heat in the adsorber at an intermediate temperature level upon adsorption. The energy required for trajectories I-II and II-III combined is the energy required for desorption (Q des, Figure 2), the energy released during trajectories III-IV and IV-I is equal to the adsorption energy (Q ads, Figure 2). For practical reasons, in most cases it is chosen to equate T 1, often called (minimum) temperature of adsorption (T ads ), to the condenser temperature, T con. 21,24 The remaining temperatures and pressures used in this cycle cannot be 12

13 all independently chosen. The condenser and evaporator pressure are inherently linked to their respective temperatures by the vapor-liquid equilibrium of the selected working fluid. For a given working pair, T 2 is related to T con via the maximum loading isostere (W max ). This means that, for a given working pair, T 2 is fixed by choosing the condenser temperature (and pressure). T 3 and T des are related through the minimum loading isostere (W min ) and T 3 is fixed when the evaporator temperature is selected. In summary, for a given working pair, the operational conditions are fully fixed when evaporator, condenser and (maximum) desorption temperature are chosen. Model equations The energy taken up by the evaporator (Q ev ) and released by the condenser (Q con ) can be calculated with knowledge of the enthalpy of evaporation, vap H, 16,25 by respectively: Q ev ( ) wf vaph Tev ρliq msorbent W = (S1) M w Q con wf ( ) ρ H T m W vap con liq sorbent = (S2) M w Here m sorbent is the amount of adsorbent used in the adsorption cycle. From here onwards this quantity is omitted making that the quantities of energy, Q i, are defined per unit of mass of the adsorbent used. W is the working capacity, ρ wf liq is the liquid density of the working fluid and M w the molar mass of the working fluid. The calculation of the energy required during the regeneration is more tedious as it comprises both isosteric heating (I-II) and isobaric desorption (II-III). 24 The energy required for isosteric heating can be determined with: 24 13

14 T2 T2 effective wf wf I II = p + liq max p Tcon Tcon ( ) ρ ( ) (S3) Q c T dt W c T dt Here c wf p is the heat capacity of the chosen working fluid and c effective p is the effective heat capacity of the adsorbent (sorbent) and heat exchanger (hex). In fact, the heat exchanger area (~mass) can be increased to increase heat transfer, at the cost of thermodynamic efficiency, and can thus be an important tuning parameter. Since the heat and mass transport properties of MOFs are scarcely known to best of our knowledge, this tuning cannot be performed in reality. Hence, for a comparison based on intrinsic MOF properties the mass of heat exchanger is assumed zero in the efficiency calculations, yielding thus: 24 effective p sorbent ( ) ( ) c T = c T (S4) p Note that the effect of heat exchanger mass on performance is generally speaking rather small. 16 The energy required for isobaric desorption is determined with: 24 Tdes T2 Tdes effective II III = p ( ) + T2 Q c T dt ρ W + W c ( T ) Q 2 wf max min wf liq p sorption (S5) Q sorption is the energy released during adsorption of the working fluid and can be calculated with: Q max 1 W wf sorption = ρliq ads M w Wmin ( ) H W dw (S6) Here M w is the molar mass of the working fluid and ads H the enthalpy of adsorption, which often has a significant dependence on loading (W). The estimation of ads H will be discussed 14

15 in more detail further on this manuscript. Finally, combining the energy required isosteric heating and isobaric desorption yields the total energy required for regeneration: Qregen = QI-II + QII-III (S7) The energy gained during the adsorption stage is a combination of the energy gained during isosteric cooling (Q III-IV ) and isobaric adsorption (Q IV-I ): Qads = QIII-IV + QIV-I (S8) The relation for the energy rejected during isosteric cooling is similar to that of isosteric heating (Eq. S3): T3 T3 effective wf wf III-IV = p + liq max p Tdes Tdes ( ) ρ ( ) (S9) Q c T dt W c T dt For isobaric adsorption, in line with Eq. S5, one could obtain: Tcon T3 IV-I Tcon T3 effective p ( ) Q = c T dt + ρ W + W c ( T ) + Q 2 wf max min wf liq p sorption (S10) When the maximum adsorbed volume for which ads H(W) is known does not extend to the maximum loading, Eq. 4 is expanded to include the assumption of the enthalpy of adsorption and of evaporation becoming equal: Q sorption w H wf Wmax liq ρ = M w Wmin ads ( ) H W dw wf ρliq H + ( Wmax Wmax) vaph M (S11) 15

16 The same can in principle be applied when W min < W H min, though this situation occurred less frequently in this study. Lastly, the loading averaged enthalpy of adsorption, as reported in Table 2 is calculated using full range of the enthalpy of adsorption as function of adsorbed volume (from W H min to W H max ): H Wmax ( ) H W dw ads H Wmin adsh H H Wmax Wmin = (S12) The loading-dependent enthalpy of adsorption, as used in this work, is shown for all materials under investigation in section S-10. Critical diameter Capillary condensation may occur when the pore diameter is larger than the so-called critical diameter (D c ), 16,26,27 as proposed by Coasne et al.: 28,29 4σ Tc Dc = T c T (S13) Here σ is the approximate size of a molecule, T c is the critical temperature of the same molecule and T is the actual temperature. Calculated critical diameters, at room temperature, are reported in Table S 1 for water, methanol and ethanol. Table S 1: Molecule size, σ, critical temperature and critical diameter (at 298 K) of working fluids, calculated according to Eq. S13. Vapor σ / nm T c / K 25 D c / nm Water Methanol Ethanol

17 S-4: Characterization of MOFs under study Nitrogen adsorption isotherms, measured at 77 K, are shown for all MOF structures under study in Figure S 2, except for MIL-53-NH 2, due to strong diffusional limitations. X-ray diffraction patterns of all MOFs are shown in Figure S 3. The relation between the pore volume determined with methanol/ethanol and nitrogen is shown in Figure S 4. 17

18 400 (a) (b) q / ml STP g q / ml STP g p p o -1 / p p o -1 / - q / ml STP g (c) p p o -1 / - q / ml STP g (d) p p o -1 / - Figure S 2: Nitrogen adsorption isotherms measured at 77 K for (a) Aluminium-hydroxide chain based MOFs, CAU-8 ( ), CAU-10-H ( ), Al-fumarate ( ) and MIL-53 ( ). For MIL-53-NH 2, no nitrogen adsorption isotherm could be collected. (b) MOFs based on 8- metal-ion ring-shaped clusters, CAU-1 ( ), CAU-1-(OH) 2 ( ), MIL-125 ( ) and MIL-125- NH 2 ( ). (c) Zirconium based MOFs, MIL-140A ( ), MIL-140C ( ), UiO-66 ( ) and UiO- 67 ( ). (d) Remaining MOFs, CAU-3 ( ), CAU-3-NH 2 ( ), MIL-100 ( ), MIL-101 ( ) and ZIF-8 ( ). Here p o is the saturated vapor pressure of nitrogen at measurement temperature and STP refers to standard temperature and pressure (0 o C, 1 bar). Closed symbols depict adsorption, closed desorption. 18

19 (a) (b) MIL-53-NH 2 MIL-125-NH 2 MIL-53 I / a.u. Al-fumarate I / a.u. MIL-125 CAU-10-H CAU-1-(OH) 2 CAU-8 CAU Θ / o 2Θ / o (c) (d) UiO-67 ZIF-8 I / a.u. UiO-66 I / a.u. MIL-101 MIL-100 MIL-140C CAU-3-NH 2 MIL-140A CAU Θ / o 2Θ / o Figure S 3: X-ray diffraction patterns, measured with Co-Kα radiation, for (a) Aluminiumhydroxide chain based MOFs, CAU-8, CAU-10-H, Al-fumarate, MIL-53 and MIL-53-NH 2. (b) MOFs based on 8-metal-ion ring-shaped clusters, CAU-1, CAU-1-(OH) 2, MIL-125 and MIL-125-NH 2. (c) Zirconium based MOFs, MIL-140A, MIL-140C, UiO-66 and UiO-67. (d) Remaining MOFs, CAU-3, CAU-3-NH 2, MIL-100, MIL-101 and ZIF-8. 19

20 V p, alcohol / ml ml ZIF-8 UiO V p, nitrogen / ml ml -1 Figure S 4: Pore volume determined with methanol ( ) and ethanol ( ) as function of the pore volume obtained with nitrogen adsorption. Values are taken from Table 2 for the materials under study. Dashed line represents parity. S-5: MOF stability Nitrogen adsorption isotherms before and after all performed methanol and, if applicable, ethanol adsorption measurements, including the derived pore volume (at p/p o = 0.8), are shown for CAU-1 (Figure S 5), CAU-1-(OH) 2 (Figure S 6), CAU-3 (Figure S 7), CAU-3-NH 2 (Figure S 8), CAU-8 (Figure S 9), Al-fumarate (Figure S 10), MIL-53 (Figure S 11), MIL-125 (Figure S 12), MIL-100 (Figure S 13), MIL-101 (Figure S 14), MIL-140A (Figure S 15), MIL-140C (Figure S 16), UiO-66 (Figure S 17), UiO-67 (Figure S 18) and ZIF-8 (Figure S 19). 20

21 600 q / ml STP g Before (V p = 0.54 ml ml -1 ) After (V p = 0.52 ml ml -1 ) Figure S 5: Nitrogen adsorption measurements at 77 K on CAU-1 before ( ) and after ( ) two methanol adsorption measurements. Pore volumes determined from these isotherms are indicated in brackets. p p o -1 / Before (V p = 0.52ml ml -1 ) q / ml STP g After (V p = 8 ml ml -1 ) Figure S 6: Nitrogen adsorption measurements at 77 K on CAU-1-(OH) 2 before ( ) and after ( ) two methanol adsorption measurements. Pore volumes determined from these isotherms are indicated in brackets. p p o -1 / - 21

22 q / ml STP g After (V p = 0.56 ml ml -1 ) Before (V p = 0.57 ml ml -1 ) p p o -1 / - Figure S 7: Nitrogen adsorption measurements at 77 K on CAU-3 before ( ) and after ( ) two methanol and two ethanol adsorption measurements. Pore volumes determined from these isotherms are indicated in brackets q / ml STP g Before (V p = 0.58 ml ml -1 ) After (V p = 0.51 ml ml -1 ) Figure S 8: Nitrogen adsorption measurements at 77 K on CAU-3-NH 2 before ( ) and after ( ) two methanol adsorption measurements. Pore volumes determined from these isotherms are indicated in brackets. p p o -1 / - 22

23 Before (V p = 7 ml ml -1 ) q / ml STP g After (V p = 9 ml ml -1 ) Figure S 9: Nitrogen adsorption measurements at 77 K on CAU-8 before ( ) and after ( ) one methanol adsorption measurement. Pore volumes determined from these isotherms are indicated in brackets. p p o -1 / q / ml STP g Before (V p = 0.66 ml ml -1 ) After (V p = 0.66 ml ml -1 ) Figure S 10: Nitrogen adsorption measurements at 77 K on Al-fumarate before ( ) and after ( ) two methanol adsorption measurements. Pore volumes determined from these isotherms are indicated in brackets. p p o -1 / - 23

24 500 q / ml STP g After (V p = 0.51 ml ml -1 ) Before (V p = 0.50 ml ml -1 ) Figure S 11: Nitrogen adsorption measurements at 77 K on MIL-53 before ( ) and after ( ) two methanol adsorption measurements. Pore volumes determined from these isotherms are indicated in brackets. p p o -1 / Before (V p = 0.57 ml ml -1 ) q / ml STP g After (V p = 0.54 ml ml -1 ) Figure S 12: Nitrogen adsorption measurements at 77 K on MIL-125 before ( ) and after ( ) two methanol adsorption measurements. Pore volumes determined from these isotherms are indicated in brackets. p p o -1 / - 24

25 q / ml STP g Before (V p = 0.60 ml ml -1 ) After (V p = 0.55 ml ml -1 ) p p o -1 / - Figure S 13: Nitrogen adsorption measurements at 77 K on MIL-100 before ( ) and after ( ) two methanol and four ethanol adsorption measurements. Pore volumes determined from these isotherms are indicated in brackets. q / ml STP g After (V p = 0.70 ml ml -1 ) Before (V p = 0.67 ml ml -1 ) p p o -1 / - Figure S 14: Nitrogen adsorption measurements at 77 K on MIL-101 before ( ) and after ( ) two methanol and four ethanol adsorption measurements. Pore volumes determined from these isotherms are indicated in brackets. 25

26 200 q / ml STP g Before (V p = 2 ml ml -1 ) After (V p = 9 ml ml -1 ) Figure S 15: Nitrogen adsorption measurements at 77 K on MIL-140A before ( ) and after ( ) two methanol adsorption measurements. Pore volumes determined from these isotherms are indicated in brackets. p p o -1 / q / ml STP g Before (V p = 7 ml ml -1 ) After (V p = 9 ml ml -1 ) p p o -1 / - Figure S 16: Nitrogen adsorption measurements at 77 K on MIL-140C before ( ) and after ( ) two methanol and two ethanol adsorption measurements. Pore volumes determined from these isotherms are indicated in brackets. 26

27 Before (V p = 0.59 ml ml -1 ) q / ml STP g After (V p = 8 ml ml -1 ) Figure S 17: Nitrogen adsorption measurements at 77 K on UiO-66 before ( ) and after ( ) two methanol adsorption measurements. Pore volumes determined from these isotherms are indicated in brackets. p p o -1 / Before (V p = 0.66 ml ml -1 ) q / ml STP g After (V p = 4 ml ml -1 ) p p o -1 / - Figure S 18: Nitrogen adsorption measurements at 77 K on UiO-67 before ( ) and after ( ) two methanol and two ethanol adsorption measurements. Pore volumes determined from these isotherms are indicated in brackets. 27

28 Before (V p = 0.56 ml ml -1 ) q / ml STP g After (V p = 0.55 ml ml -1 ) p p o -1 / - Figure S 19: Nitrogen adsorption measurements at 77 K on ZIF-8 before ( ) and after ( ) two methanol and two ethanol adsorption measurements. Pore volumes determined from these isotherms are indicated in brackets. S-6: Equilibration time issue For ethanol use with MIL-100 and MIL-101 the adsorption equilibration time should be set at 40 s and not 30 s (298 K). This removes the artificial hysteresis observed when adsorption equilibrium is not attained in each step (Figure S 20). 28

29 25 20 q / mmol g Figure S 20: Ethanol adsorption at 298 K when varying equilibration interval for MIL-100 (30 s ( ) and 40 s ( )) and MIL-101 (30 s ( ) and 40 s ( )). Closed symbols depict adsorption, open desorption. p p o -1 / - S-7: Comparison of methanol and ethanol adsorption Ethanol and methanol adsorption isotherms are shown, for convenient comparison, for CAU- 3, ZIF-8 (both Figure S 21), MIL-100, MIL-101 (Figure S 22), MIL-140A and MIL-140C (Figure S 23), all per volume adsorbent (the crystal density is used for conversion) and using a logarithmic relative pressure axis. 29

30 W / ml ml Figure S 21: Comparison of methanol (, ) and ethanol (, ) adsorption isotherms (both 298 K) on CAU-3 (, ) and ZIF-8 (, ). Closed symbols depict adsorption, open desorption. Loading is represented per volume of adsorbent, the crystal density is used for the conversion. 1 1 p p o -1 / W / ml ml p p o -1 / - Figure S 22: Comparison of methanol (, ) and ethanol (, ) adsorption isotherms (both 298 K) on MIL-100 (, ) and MIL-101 (, ). Closed symbols depict adsorption, open 30

31 desorption. Loading is represented per volume of adsorbent, the crystal density is used for the conversion W / ml ml Figure S 23: Comparison of methanol (, ) and ethanol (, ) adsorption isotherms (both 298 K) on MIL-140C (, ) and UiO-67 (, ). Closed symbols depict adsorption, open desorption. Loading is represented per volume of adsorbent, the crystal density is used for the conversion. 1 1 p p o -1 / - S-8: Characteristic curves (methanol) Characteristic curves with methanol as adsorptive, constructed using Eqs. 5-6, are shown for CAU-1, CAU-1-(OH) 2 (both Figure S 24), CAU-3, CAU-3-NH 2 (Figure S 25), CAU-10, Alfumarate (Figure S 26), MIL-53, MIL-53-NH 2 (Figure S 27), MIL-100, MIL-101 (Figure S 28), MIL-140A, MIL-140C (Figure S 29), UiO-66, UiO-67 (Figure S 30), ZIF-8 and CAU-8 (Figure S 31). 31

32 W / ml g A / kj mol -1 Figure S 24: Characteristic curve of CAU-1 (288 K ( ) and 298 K ( )) and CAU-1-(OH) 2 (288 K ( ) and 298 K ( )), with methanol as adsorptive. Closed symbols depict adsorption, open desorption W / ml g A / kj mol -1 Figure S 25: Characteristic curve of CAU-3 (288 K ( ) and 298 K ( )) and CAU-3-NH 2 (288 K ( ) and 298 K ( )), with methanol as adsorptive. Closed symbols depict adsorption, open desorption. 32

33 W / ml g A / kj mol -1 Figure S 26: Characteristic curve of CAU-10 (288 K ( ) and 298 K ( )) and Al-fumarate (288 K ( ) and 298 K ( )), with methanol as adsorptive. Closed symbols depict adsorption, open desorption W / ml g A / kj mol -1 Figure S 27: Characteristic curve of MIL-53 (288 K ( ) and 298 K ( )) and MIL-53-NH 2 (288 K ( ) and 298 K ( )), with methanol as adsorptive. Closed symbols depict adsorption, open desorption. 33

34 W / ml g A / kj mol -1 Figure S 28: Characteristic curve of MIL-100 (288 K ( ) and 298 K ( )) and MIL-101 (288 K ( ) and 298 K ( )), with methanol as adsorptive. Closed symbols depict adsorption, open desorption W / ml g A / kj mol -1 Figure S 29: Characteristic curve of MIL-140A (288 K ( ) and 298 K ( )) and MIL-140C (288 K ( ) and 298 K ( )), with methanol as adsorptive. Closed symbols depict adsorption, open desorption. 34

35 W / ml g A / kj mol -1 Figure S 30: Characteristic curve of UiO-66 (288 K ( ) and 298 K ( )) and UiO-67 (288 K ( ) and 298 K ( )), with methanol as adsorptive. Closed symbols depict adsorption, open desorption W / ml g A / kj mol -1 Figure S 31: Characteristic curve of ZIF-8 (288 K ( ) and 298 K ( )) and CAU-8 (298 K ( ) only), with methanol as adsorptive. Closed symbols depict adsorption, open desorption. 35

36 S-9: Characteristic curves (ethanol) Characteristic curves with methanol as adsorptive, constructed using Eqs. 5-6, are shown for CAU-3, ZIF-8 (both Figure S 32), MIL-100, MIL-101 (Figure S 33), MIL-140C and UiO-67 (Figure S 34) W / ml g A / kj mol -1 Figure S 32: Characteristic curve of CAU-3 (288 K ( ) and 298 K ( )) and ZIF-8 (288 K ( ) and 298 K ( )), with ethanol as adsorptive. Closed symbols depict adsorption, open desorption. 36

37 W / ml g A / kj mol -1 Figure S 33: Characteristic curve of MIL-100 (288 K ( ) and 298 K ( )) and MIL-101 (288 K ( ) and 298 K ( )), with ethanol as adsorptive. Closed symbols depict adsorption, open desorption W / ml g A / kj mol -1 Figure S 34: Characteristic curve of MIL-140C (288 K ( ) and 298 K ( )) and UiO-67 (288 K ( ) and 298 K ( )), with ethanol as adsorptive. Closed symbols depict adsorption, open desorption. 37

38 S-10: Enthalpy of adsorption (Isosteric) The isosteric enthalpies of methanol adsorption, computed with Eq. 4, are shown for all components except for CAU-8 (only one isotherm measured), in Figure S 35. For ethanol, results are shown in Figure S

39 80 70 (a) (b) ads H / kj mol ads H / kj mol q / mmol g -1 q / mmol g (c) (d) ads H / kj mol ads H / kj mol q / mmol g q / mmol g -1 Figure S 35: Isosteric enthalpy of adsorption, determined from isotherms at 288 and 298 K, for methanol and MOFs investigated in this work. (a) Aluminium-hydroxide chain based MOFs, CAU-10-H ( ), Al-fumarate ( ), MIL-53 ( ) and MIL-53-NH 2 ( ). (b) MOFs based on 8-metal-ion ring-shaped clusters, CAU-1 ( ), CAU-1-(OH) 2 ( ), MIL-125 ( ) and MIL-125-NH 2 ( ). (c) Zirconium based MOFs, MIL-140A ( ), MIL-140C ( ), UiO-66 ( ) and UiO-67 ( ). (d) Remaining MOFs, CAU-3 ( ), CAU-3-NH 2 ( ), MIL-100 ( ), MIL- 101 ( ) and ZIF-8 ( ). Straight line is the enthalpy of evaporation of methanol (298 K). Closed symbols indicate proper data points, open desorption are removed in calculations as the magnitude is lower than the enthalpy of evaporation. 39

40 ads H / kj mol q / mmol g -1 Figure S 36: Isosteric enthalpy of adsorption, determined from isotherms at 288 and 298 K, for ethanol and MOFs investigated in this work: CAU-3 ( ), MIL-100 ( ), MIL-101 ( ), MIL-140 ( ), UiO-67 ( ) and ZIF-8 ( ). Straight line is the enthalpy of evaporation of ethanol (298 K). Closed symbols indicate proper data points, open desorption are removed in calculations as the magnitude is lower than the enthalpy of evaporation. S-11: Working capacity of MOFs for heat pump conditions For methanol and heat pump conditions, the working capacities of the MOFs under investigation are shown in Figure S 37. For ethanol, results are shown in Figure S

41 (a) (b) W / ml ml -1 W / ml ml T d / K T d / K (c) (d) W / ml ml -1 W / ml ml T d / K T d / K Figure S 37: Volumetric working capacity, W, as function of desorption temperature, T d, for heat pump conditions (T ev = 288 K and T ads = 318 K), for methanol and MOFs investigated in this work: (a) Aluminium-hydroxide chain based MOFs, CAU-10-H ( ), Al-fumarate ( ), MIL-53 ( ) and MIL-53-NH 2 ( ). (b) MOFs based on 8-metal-ion ring-shaped clusters, CAU-1 ( ), CAU-1-(OH) 2 ( ), MIL-125 ( ) and MIL-125-NH 2 ( ). (c) Zirconium based MOFs, MIL-140A ( ), MIL-140C ( ), UiO-66 ( ) and UiO-67 ( ). (d) Remaining MOFs, CAU-3 ( ), CAU-3-NH 2 ( ), MIL-100 ( ), MIL-101 ( ) and ZIF-8 ( ).Loading is represented per volume of adsorbent, the crystal density is used for the conversion. 41

42 W / ml ml T d / K Figure S 38: Volumetric working capacity, W, as function of desorption temperature, T d, for heat pump conditions (T ev = 288 K and T ads = 318 K), for ethanol and MOFs investigated in this work: CAU-3 ( ), MIL-100 ( ), MIL-101 ( ), MIL-140C ( ), UiO-67 ( ) and ZIF-8 ( ). Loading is represented per volume of adsorbent, the crystal density is used for the conversion. S-12: Working capacity of MOFs for refrigeration conditions For methanol and refrigeration conditions, the working capacities of the MOFs under investigation are shown in Figure S 39. For ethanol, results are shown in Figure S

43 (a) (b) W / ml ml -1 W / ml ml T d / K T d / K (c) (d) W / ml ml -1 W / ml ml T d / K T d / K Figure S 39: Volumetric working capacity, W, as function of desorption temperature, T d, for refrigeration conditions (T ev = 278 K and T ads = 303 K), for methanol and MOFs investigated in this work: (a) Aluminium-hydroxide chain based MOFs, CAU-10-H ( ), Al-fumarate ( ), MIL-53 ( ) and MIL-53-NH 2 ( ). (b) MOFs based on 8-metal-ion ring-shaped clusters, CAU-1 ( ), CAU-1-(OH) 2 ( ), MIL-125 ( ) and MIL-125-NH 2 ( ). (c) Zirconium based MOFs, MIL-140A ( ), MIL-140C ( ), UiO-66 ( ) and UiO-67 ( ). (d) Remaining MOFs, CAU-3 ( ), CAU-3-NH 2 ( ), MIL-100 ( ), MIL-101 ( ) and ZIF-8 ( ). Loading is represented per volume of adsorbent, the crystal density is used for the conversion. 43

44 W / ml ml T d / K Figure S 40: Volumetric working capacity, W, as function of desorption temperature, T d, for refrigeration conditions (T ev = 278 K and T ads = 303 K), for ethanol and MOFs investigated in this work: CAU-3 ( ), MIL-100 ( ), MIL-101 ( ), MIL-140C ( ), UiO-67 ( ) and ZIF-8 ( ). Loading is represented per volume of adsorbent, the crystal density is used for the conversion. S-13: Coefficients of performance for selected MOFs at refrigeration conditions The working capacity and COP for the most promising MOF-methanol pairs for refrigeration selected from Figure S 39 are shown in Figure S 41. For MOF-ethanol pairs (Figure S 40), working capacity and COP are shown for the most promising MOFs in Figure S

45 COP C / W / ml ml T d / K Figure S 41: COP C (left vertical axis, closed symbols) and volumetric working capacity, W (right vertical axis, open symbols), as function of desorption temperature, T d, for refrigeration conditions (T ev = 278 K and T ads = 303 K) for the three best MOF-methanol working pairs: CAU-3 ( ), UiO-67 ( ) and ZIF-8 ( ).Loading is represented per volume of adsorbent, the crystal density is used for the conversion. 45

46 COP C / W / ml ml T d / K Figure S 42: COP C (left vertical axis, closed symbols) and volumetric working capacity, W (right vertical axis, open symbols), as function of desorption temperature, T d, for refrigeration conditions (T ev = 278 K and T ads = 303 K) for the three best MOF-ethanol working pairs: CAU-3 ( ), UiO-67 ( ) and ZIF-8 ( ). S-14: Working capacity of MOFs for ice making conditions For methanol and ice making conditions, the working capacities of the MOFs under investigation are shown in Figure S 43. For ethanol, results are shown in Figure S

47 (a) (b) W / ml ml -1 W / ml ml T d / K T d / K (c) (d) W / ml ml -1 W / ml ml T d / K T d / K Figure S 43: Volumetric working capacity, W, as function of desorption temperature, T d, for ice making conditions (T ev = 268 K and T ads = 298 K), for methanol and MOFs investigated in this work: (a) Aluminium-hydroxide chain based MOFs, CAU-10-H ( ), Al-fumarate ( ), MIL-53 ( ) and MIL-53-NH 2 ( ). (b) MOFs based on 8-metal-ion ring-shaped clusters, CAU-1 ( ), CAU-1-(OH) 2 ( ), MIL-125 ( ) and MIL-125-NH 2 ( ). (c) Zirconium based MOFs, MIL-140A ( ), MIL-140C ( ), UiO-66 ( ) and UiO-67 ( ). (d) Remaining MOFs, CAU-3 ( ), CAU-3-NH 2 ( ), MIL-100 ( ), MIL-101 ( ) and ZIF-8 ( ).Loading is represented per volume of adsorbent, the crystal density is used for the conversion. 47

48 W / ml ml T d / K Figure S 44: Volumetric working capacity, W, as function of desorption temperature, T d, for ice making conditions (T ev = 268 K and T ads = 298 K), for ethanol and MOFs investigated in this work: CAU-3 ( ), MIL-100 ( ), MIL-101 ( ), MIL-140C ( ), UiO-67 ( ) and ZIF-8 ( ). Loading is represented per volume of adsorbent, the crystal density is used for the conversion. S-15: Extending T d for MIL-101 (refrigeration) for ethanol and methanol The effect on working capacity and COP of extending desorption temperature for MIL-101, both for ethanol and methanol, under refrigeration conditions is shown in Figure S

49 COP C / W / ml ml T d / K Figure S 45: COP C (left vertical axis, closed symbols) and volumetric working capacity, W (right vertical axis, open symbols), as function of desorption temperature, T d, for refrigeration conditions (T ev = 278 K and T ads = 303 K) for MIL-101 with either methanol ( ) or ethanol ( ) as working fluid. Loading is represented per volume of adsorbent, the crystal density is used for the conversion. S-16: Comparison with activated carbon (G32-H) For comparison, the results previously obtained 16 for activated carbon G32-H 30 and methanol are shown in Figure S 46, alongside the results for the most promising MOF-methanol pairs identified in this work (see Fig. 6a), both for heat pump conditions. 49

50 COP H / W / ml ml T d / K Figure S 46: COP H (left vertical axis, closed symbols) and volumetric working capacity, W (right vertical axis, open symbols), as function of desorption temperature, T d, for heat pump conditions (T ev = 288 K and T ads = 318 K) for the best MOF-methanol working pairs: CAU-3 ( ), UiO-67 ( ) and ZIF-8 ( ), and for the activated carbon G32-H 30 -methanol working pair (, results from 16 ). Loading is represented per volume of adsorbent, the crystal density is used for the conversion. 50

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