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Supporting Information for:

Metal–organic Frameworks as Adsorbents for Hydrogen Purification and Pre-Combustion Carbon Dioxide Capture

Zoey R. Herm, Joseph A. Swisher, Berend Smit, Rajamani Krishna, Jeffrey R. Long*

†Department of Chemistry, University of California, Berkeley, CA 94720-1460, ‡Department of Chemical and Biomolecular Engineering, University of California, Berkeley, CA 94720-1460, §Van’t Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098

XH Amsterdam, The Netherlands

*email: jrlong@berkeley.edu

J. Am. Chem. Soc.

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Experimental Details

Dichloromethane was received from Aldrich and dried over activated 4 Å sieves prior to use.

Ethanol was heated to reflux for 24 h over Mg turnings and I2.1 All other reagents were obtained

from commercial vendors and used without further purification. Powder X-ray diffraction

patterns were obtained on a Bruker D8 Advance diffractometer with a Cu anode (λ = 1.5406 Å).

Infrared spectra were obtained on a Perkin-Elmer Spectrum 100 Optica FTIR spectrometer

furnished with an attenuated total reflectance accessory (ATR). Caution! Beryllium compounds

can pose a serious health risk through skin contact and inhalation. All manipulations of solid

beryllium-containing materials should be performed in a fumehood or glove bag, taking care not

to generate airborne dust in the open air under any circumstances.

Synthesis of 1,3,5-triphenylbenzene. 1,3,5-triphenylbenzene was prepared according to

literature procedure.2

Synthesis of 4,4',4''-benzene-1,3,5-triyl-tribenzoic acid (H3BTB). H3BTB was synthesized

from 1,3,5-triphenylbenzene and nitric acid according to literature procedure.3

Synthesis of MOF-177. MOF-177 was prepared according to literature procedure.4

Synthesis of Be12(OH)12(1,3,5-benzenetribenzoate)4 (BeBTB). The same sample

characterized in Sumida et al. was used for this study.5

Synthesis of 1,4-benzenedi(4’-pyrazolyl) (H2BDP). H2BDP was synthesized according to

literature procedure.6

Synthesis of CoBDP. CoBDP was synthesized according to literature procedure.6

Synthesis of 1,3,5-tris(triazol-5-yl)benzene (H3BTTri). H3BTTri was synthesized

according to literature procedure.7

Synthesis of CuBTTri. CuBTTri was synthesized according to literature procedure.7

Synthesis of Mg2(dobdc). Mg2(dobdc) was synthesized according to literature procedure.8

Activation of MOF-177.9 Activation of the sample was performed by transferring the

collected product into a nitrogen-filled glove bag, where the solid was soaked in N,N-

dimethylformamide (50 mL) for 24 h. The supernatant was decanted and replenished a further

two times over two days. The solid was then soaked in dichloromethane (50 mL) for 24 h. The

supernatant was decanted and replenished a further three times over three days, and after the

final wash a gentle stream of nitrogen was passed over the sample so as to remove excess solvent.

The product is hygroscopic and was therefore stored in a glove box under a dinitrogen

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atmosphere. The final degassing was performed on a vacuum manifold at 1 mTorr and 100 °C

for 10 h. Surface area was determined by 77 K N2 adsorption and confirmed with literature

data.10 Powder pattern was compared to the simulated pattern from the crystal structure.11

Activation of BeBTB. BeBTB was activated according to literature procedure.5

Activation of CoBDP. CoBDP was evacuated at ambient temperature at 1000 mTorr for 24

h and then transferred quickly to a Schlenk flask in a glovebag. The sample was then evacuated

at 1 mTorr for two days and brought to 170 °C at a ramp rate of 5 °C per hour.

Activation of CuBTTri. CuBTTri was activated according to literature procedure.7

Activation of Mg2(dobdc). Mg2(dobdc) was activated using a strategy adapted from the

literature procedure.8 The yellow microcrystalline material was combined and washed repeatedly

with DMF and soaked in DMF for 24 h. The DMF was decanted, and freshly distilled methanol

was added. The solid was then transferred to a nitrogen-filled glovebox. The methanol was

decanted and the solid was soaked in DMF on a hotplate set at 100 °C for 18 h. The DMF was

decanted and replaced, and the solid was soaked at 100 °C for 4 h. The DMF was decanted and

replaced by methanol, which was decanted and replenished 6 times with a minimum of 6 hours

between washes.

Low-Pressure Gas Sorption Measurements and Surface Area Calculations. Low-

pressure gas adsorption was used in two contexts in this study: to measure the surface area of the

prepared metal–organic framework samples and to measure adsorption of CO2 onto Mg2(dobdc)

below 1 bar. Mg2(dobdc) required this measurement due to the open Mg2+ sites which interact

strongly with CO2 (see Figure S20). During these measurements, glass sample tubes of a known

weight were loaded with approximately 200 mg of sample, and sealed using a TranSeal. Samples

were degassed on a Micromeritics ASAP 2020 analyzer until the outgas rate was no more than 1

mTorr/min as described above. The degassed sample and sample tube were weighed precisely

and then transferred back to the analyzer (with the TranSeal preventing exposure of the sample

to the air after degassing). The outgas rate was again confirmed to be less than 1 mTorr/min.

Adsorption isotherms were measured at 77 K in a liquid nitrogen bath for and N2 and 313 K in

an isothermal water bath for CO2. Langmuir and BET surface areas were calculated using the

Micromeritics software and the method of Snurr and coworkers, 12 respectively. Although

Langmuir surface areas are inherently inapplicable in microporous metal–organic frameworks,

due to the ambiguity in BET surface area calculations for flexible materials, we report both.13

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High-Pressure Gas Sorption Measurements. In a typical measurement, at least 200 mg of

sample was loaded in a sample holder in a glove box under an argon atmosphere. Hydrogen and

carbon dioxide excess adsorption measurements were performed on an automated Sieverts’

apparatus (PCTPro-2000 from Hy-Energy Scientific Instruments LLC) over a pressure range of

0-50 bar. UHP-grade hydrogen, carbon dioxide and helium (99.999% purity) were used for all

measurements. Total adsorption was calculated using NIST Thermochemical Properties of Fluid

Systems: CO2 and H2 densities between 0 and 50 bar were fit using a sixth-order polynomial,

then multiplied by the pore volume of each material.14

Interpolation of 313 K Adsorption Data for Zeolite 13X. Belmabkhout et al.15 reported

excess adsorption of CO2 and H2 on zeolite 13X at 303 K and 323 K. These were converted to

total adsorption using a pore volume of 0.34 cm3/g. Carbon dioxide uptake values and hydrogen

uptake values were fit to dual- and single-site Langmuir Freundlich fits, respectively. The

averages of these curves were taken at intervals of 0.1 bar from 0 to 14 bar, and then these

averaged values were again fit to dual- and single-site Langmuir Freundlich fits for the

interpolated CO2 and H2 data sets, respectively. See Figure S13 for the raw and interpolated data.

Ideal Adsorbed Solution Theory Calculations. The ideal adsorbed solution theory (IAST)

of Prausnitz and Myers was used to estimate the composition of the adsorbed phase from pure

component isotherm data.16,17 Experimental absolute isotherm data were fit to the dual-site

Langmuir-Freundlich isotherm for CO2 adsorption and the single-site Langmuir-Freundlich

model for H2. H2 saturation capacities were allowed to refine between two and three times the

saturation capacity for CO2, which was confirmed visually. The integrals were computed

numerically and the adsorbed phase composition that minimized the difference between the

integrals of the two spreading pressures was found using Mathematica®.18 A sample calculation

for determining the mole fraction of CO2 adsorbed in an 80:20 H2:CO2 mixture in Mg2(dobdc) is

included below. Selectivities were then calculated according to equation 1, where xi is the mole

fraction of component i in the adsorbed phase and yi is the mole fraction of component i in the

bulk. Working capacities were calculated according to equation 2 where nt is the total number of

adsorbed moles of gas per unit mass of adsorbent and ni

o is the number of moles of component i

in the adsorbed phase per unit mass of adsorbent.

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S =xiyj

x j yi (1)

1

nt

=xi

ni

o+xj

nj

o (2)

Literature data for zeolites and activated carbons that were reported for comparison to

metal–organic frameworks were taken from references as mentioned in the text. Zeolite 13X,

zeolite 5A, and BPL activated carbon were converted to absolute adsorption because the authors

confirmed the data reported were excess or no mention was made of conversion to absolute

adsorption in the text.

Ideal Adsorbed Solution Theory Validation for CO2/H2 Mixtures in Metal–organic

Frameworks. The accuracy of the IAST for estimation of component loadings for adsorption of

a wide variety of binary mixtures in zeolites has been established with the aid of

Configurational-Bias Monte Carlo (CBMC) simulations.19 As illustration of the validity of the

use of the IAST for estimation of CO2/H2 adsorption equilibrium in MOFs we present CBMC

results for adsorption of CO2/H2 mixtures in MOF-177 at 313 K, the temperature used in the

experimental work. The CBMC simulation methodology is similar to that described in published

work.20 The symbols in Figure S11 represent the pure component adsorption isotherms for CO2

and H2 in MOF-177 obtained from CBMC. The continuous solid lines in Figure S11 are the

dual-site Langmuir–Freundlich fits of the isotherms.

The component loadings in an 80:20 H2:CO2 mixture at 313 K, determined using CBMC

simulations, are presented Figure S12 as filled symbols. The continuous solid lines are the IAST

estimations using the dual-site Langmuir–Freundlich fits of the pure component isotherms. It is

to be noted that there is excellent agreement between the IAST predictions and the CBMC

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simulated component loadings in the mixture. This agreement is typical for adsorption of CO2:H2

mixtures in MOFs.

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Table S1. Adsorption data for MOF-177 at 313 K (pore volume = 1.59 mL/g).11

CO2 H2

Pressure(bar)

ExcessUptake(mmol/g)

TotalUptake(mmol/g)

Pressure(bar)

ExcessUptake(mmol/g)

TotalUptake(mmol/g)

1.28099 0.80392 0.8826 12.50214 0.63925 0.94352.33583 1.574 1.7181 24.88264 1.29281 1.90273.2927 2.28988 2.4939 37.31539 1.85425 2.7753

4.20058 2.98023 3.2415 5.10519 3.72392 4.0428

6.02287 4.49381 4.8716 6.88177 5.22727 5.6606 7.65575 5.93119 6.4150 8.70406 6.94189 7.4946 9.70338 7.91669 8.5358 10.7223 8.99689 9.6843 11.78041 10.17388 10.9331

12.82545 11.4115 12.2424 13.81171 12.59646 13.4958 14.79797 13.86746 14.8360 15.78423 15.17196 16.2105 16.76396 16.47119 17.5802 17.76001 17.72935 18.9108 18.75607 19.05304 20.3080 19.76846 20.34654 21.6773 20.86902 21.64585 23.0603 21.95651 22.78465 24.2832 23.093 23.90185 25.4899 24.21969 24.90446 26.5830 25.39536 25.74381 27.5187 26.59716 26.51542 28.3911 27.95245 27.46723 29.4596 29.26855 27.99777 30.1067 30.57159 28.50616 30.7339 31.91708 29.00954 31.3640 33.31157 29.47946 31.9698 34.71911 29.90054 32.5332 36.14624 30.12673 32.9096 37.63216 30.54338 33.4894 39.0593 30.69208 33.8020

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Table S2. Adsorption data for BeBTB at 313 K (pore volume = 1.701 mL/g).

CO2 H2

Pressure(bar)

ExcessUptake(mmol/g)

TotalUptake(mmol/g)

Pressure(bar)

ExcessUptake(mmol/g)

TotalUptake(mmol/g)

1.01955 0.83121 0.8982 2.60997 0.14725 0.31811.96008 1.65886 1.7880 5.64386 0.38094 0.75102.83857 2.41599 2.6038 8.73327 0.68433 1.25803.65175 3.13348 3.3759 11.9272 0.97947 1.76434.35062 3.76628 4.0560 15.1244 1.27647 2.27354.99724 4.35232 4.6861 18.2628 1.64476 2.85085.6112 4.915 5.2908 21.3848 1.95715 3.3719

6.20231 5.48584 5.9023 24.4873 2.43727 4.06016.81954 6.08666 6.5459 27.5832 2.77537 4.60667.43023 6.62903 7.1308 30.7249 3.1204 5.16398.18462 7.36536 7.9200 33.8437 3.47542 5.73039.06638 8.18876 8.8057 37.0703 3.6363 6.11079.57584 8.76651 9.419710.1082 9.34372 10.035011.0748 10.28348 11.044412.0709 11.29378 12.127213.0865 12.30326 13.211514.0924 13.2408 14.223915.0917 14.25893 15.317316.1172 15.23615 16.372717.1589 16.13188 17.348918.1909 17.04832 18.346219.2621 17.88105 19.264020.3822 18.67675 20.150121.4403 19.49221 21.052522.518 20.16629 21.8165

23.5957 20.92294 22.664824.6832 21.5284 23.364525.8001 22.08062 24.015526.8942 22.69243 24.726128.0535 23.30218 25.443129.1508 23.87773 26.122630.2873 24.39172 26.746931.427 24.90074 27.3697

32.7039 25.21509 27.815333.958 25.45857 28.1920

35.1565 25.87987 28.7449

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Table S2 (continued)

CO2

Pressure(bar)

ExcessUptake(mmol/g)

TotalUptake(mmol/g)

36.3877 26.08858 29.093637.5961 26.50388 29.651338.8338 26.87481 30.1736

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Table S3. Adsorption data for CoBDP at 313 K (pore volume = 0.93 mL/g).6

CO2 H2

Pressure(bar)

ExcessUptake(mmol/g)

TotalUptake(mmol/g)

Pressure(bar)

ExcessUptake(mmol/g)

TotalUptake(mmol/g)

1.3102 0.23773 0.2848 1.99274 0.01417 0.08552.48914 0.61161 0.7015 3.93914 0.06728 0.20843.36436 1.54247 1.6644 5.77776 0.11685 0.32404.08609 2.88677 3.0354 7.71435 0.18732 0.46424.99724 3.3162 3.4987 10.0559 0.27214 0.63355.68632 4.65976 4.8680 12.4562 0.34693 0.79526.07494 7.10889 7.3318 14.8337 0.47771 1.01237.0612 7.82387 8.0841 17.3059 0.58183 1.2063

7.92989 8.31224 8.6057 19.7193 0.75408 1.46679.17741 8.86177 9.2034 22.1719 0.87632 1.678710.5066 9.39867 9.7923 24.5591 0.97944 1.869411.8782 9.85038 10.2984 27.0705 1.09966 2.082013.2466 10.29446 10.7975 29.5068 1.30781 2.380014.6574 10.70262 11.2633 31.9528 1.43945 2.602216.0159 11.05925 11.6764 34.4152 1.68712 2.941217.3777 11.39795 12.0727 36.8515 1.92359 3.268318.8277 11.75591 12.4931 39.2845 2.02955 3.465020.2679 12.15362 12.954121.6036 12.95162 13.812122.972 13.62928 14.5525

24.4318 13.95934 14.951225.9275 14.18185 15.245927.4102 14.35197 15.489828.9973 14.41467 15.634030.5583 14.53003 15.832332.0083 14.75041 16.132633.5433 14.82996 16.3001

35.15 14.78923 16.355336.7241 14.77917 16.443538.2884 14.79576 16.562539.8658 14.67946 16.5546

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Table S4. Adsorption data for CuBTTri at 313 K (pore volume = 0.713 mL/g).7

CO2 H2

Pressure(bar)

ExcessUptake(mmol/g)

TotalUptake(mmol/g)

Pressure(bar)

ExcessUptake(mmol/g)

TotalUptake(mmol/g)

0.54601 1.14529 1.1603 1.10446 0.02549 0.05581.12732 2.14698 2.1780 2.11684 0.05627 0.11431.72822 3.05803 3.1057 3.03452 0.09193 0.17522.32912 3.85657 3.9210 3.8379 0.12982 0.23522.93002 4.56212 4.6434 4.5629 0.17124 0.29663.48519 5.18089 5.2778 5.23238 0.19824 0.34204.02078 5.74119 5.8533 5.89206 0.22761 0.38964.5433 6.25198 6.3789 6.56807 0.25349 0.4341

5.05276 6.71878 6.8603 7.27674 0.29308 0.49335.55895 7.16633 7.3224 8.09645 0.32657 0.54946.07494 7.61577 7.7867 9.17415 0.39017 0.64286.63665 8.06184 8.2490 10.2649 0.43593 0.71887.19183 8.44149 8.6448 11.4079 0.48571 0.80037.68496 8.79687 9.0147 12.0872 0.52621 0.85968.21075 9.1364 9.3697 13.2433 0.58992 0.95558.7398 9.4716 9.7205 14.4092 0.66541 1.0634

9.59543 9.94102 10.2154 15.5522 0.74826 1.178110.5066 10.4093 10.7111 16.7246 0.81965 1.282211.2087 10.7479 11.0709 17.8676 0.88799 1.382512.2276 11.1646 11.5188 19.1151 0.95697 1.486413.2563 11.5723 11.9583 20.3431 1.01692 1.580714.3079 11.9324 12.3512 21.522 1.07777 1.674615.3922 12.279 12.7322 22.6879 1.13504 1.764716.4535 12.5651 13.0523 23.8668 1.22634 1.889117.5639 12.8256 13.3490 25.0359 1.31062 2.006318.6873 13.0855 13.6460 26.2018 1.39803 2.126619.8728 13.3145 13.9148 27.3481 1.44238 2.203321.0093 13.4851 14.1242 28.5336 1.54581 2.340322.1164 13.7094 14.3870 29.7092 1.62159 2.449423.2463 13.8536 14.5712 30.8915 1.72425 2.585524.3893 14.0151 14.7740 32.1259 1.76311 2.659425.5683 14.1644 14.9668 33.6706 1.79973 2.740026.7472 14.3507 15.1975 35.5582 1.8809 2.874927.8968 14.436 15.3272 37.3871 1.96162 3.007929.0724 14.5764 15.5142 39.2289 2.0232 3.122130.2644 14.7691 15.755431.5609 14.8396 15.8802

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Table S4 (continued)

CO2

Pressure(bar)

ExcessUptake(mmol/g)

TotalUptake(mmol/g)

32.8542 15.0207 16.117234.1213 15.2035 16.356735.3982 15.2565 16.468836.6294 15.4253 16.696737.8834 15.5538 16.887639.1734 15.5909 16.9915

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Table S5. Adsorption data for Mg2(dobdc) at 313 K (pore volume = 0.5727 mL/g).

CO2 H2

Pressure(bar)

ExcessUptake(mmol/g)

TotalUptake(mmol/g)

Pressure(bar)

ExcessUptake(mmol/g)

TotalUptake(mmol/g)

4.89E‐04 0.08847 0.0885 9.501613 0.3760545 0.58630.00223 0.37139 0.3715 18.95925 0.6575109 1.07920.00457 0.70464 0.7048 28.40383 0.8841854 1.51940.00911 1.27589 1.2761 37.90393 0.9772589 1.82950.01127 1.51993 1.5202 47.38443 1.188942 2.26010.01335 1.73344 1.73380.01838 2.18276 2.1832

0.02857 2.89747 2.8981 0.03608 3.30492 3.3057 0.05509 4.05642 4.0576 0.06996 4.47072 4.4723 0.08926 4.87361 4.8756 0.11189 5.22471 5.2272 0.15067 5.65046 5.6538 0.18915 5.95081 5.9550 0.22833 6.18138 6.1864

0.26812 6.37079 6.3767 0.30694 6.52658 6.5334 0.34563 6.66045 6.6681 0.38012 6.76798 6.7764 0.41452 6.86558 6.8747 0.44905 6.95605 6.9660 0.47911 7.03013 7.0407 0.51596 7.11556 7.1269 0.55246 7.19493 7.2071 0.58942 7.271 7.2840 0.62564 7.34277 7.3566 0.66295 7.41411 7.4287 0.70041 7.48288 7.4983 0.73641 7.54607 7.5623 0.77368 7.61024 7.6273 0.81001 7.67057 7.6885 0.84677 7.73013 7.7488 0.88381 7.78898 7.8085 0.92018 7.8457 7.8660 0.95642 7.90289 7.9240 0.9946 7.95821 7.9802

1.03031 8.00988 8.0327

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Table S5 (continued)

CO2

Pressure(bar)

ExcessUptake(mmol/g)

TotalUptake(mmol/g)

1.06713 8.06284 8.08642.31367 9.2023 9.20234.52786 10.94899 10.94907.23191 12.29122 12.2912

10.06332 13.16636 13.166413.0319 13.7347 13.7347

16.06906 14.27018 14.270219.1454 14.63902 14.6390

22.25767 14.70171 14.701725.38627 14.88092 14.880928.71734 14.86947 14.869531.92432 15.1501 15.150135.31745 15.06154 15.0615

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Table S6. Fit parameters used in this study for CO2 (equation 3) and H2, where n is gas

uptake in mmol/g.

a b c d e f

BPLCarbon

CO2 13.64863 0.09936 1.11448 1.15061 1.43805 1.2677

H2 44 0.00118 .9443 ActivatedCarbonJX101

CO2 7.09833 0.07527 0.98214 4.52688 0.29105 1.3196

H2 23 0.00137 1.078

Zeolite5ACO2 1 0.17293 2.03809 6 1.26959 5.04918

H2 21 0.00126 0.9551

Zeolite13XCO2 2.60453 0.38406 0.91271 3.73427 21.59517 0.67943

H2 12.2 0.00631 1.23043

Mg2(dobdc)CO2 6.84562 23.769474 1.011976 10.065635 0.1615107 1

H2 30 0.003 1.170

MOF‐177CO2 34.47581 3.16502*10‐4 0.37141 4.73161 0.11846 0.56647

H2 120 7.89134*10‐4 1.074

Be‐BTBCO2 33.6845 0.00262 0.51675 4.84087 0.19147 0.81552

H2 65 0.00155 0.8533

Co(BDP)CO2 10.79363 0.00172 0.26894 5.89547 2.61295*10‐8 0.17522

H2 39.5 6.9614*10‐4 0.7460

Cu‐BTTriCO2 20.74633 0.09711 0.98401 1.09309 1.89857*10‐19 0.0864

H2 63 5.13767*10‐4 0.8573

n =a*b* p

1/c

1+ b* p1/c+d *e* p

1/ f

1+ e* p1/ f

(3)

S-17

Table S7. Tabulated surface area and approximate pore volume data for the five metal–organic frameworks investigated in this study.

PoreVolume(cm3/g)

LangmuirSurfaceArea(m2/g)

BETSurfaceArea(m2/g)

Mg2(dobdc)0.5727 2060 1800

MOF‐177 1.59 5400 4690

Be‐BTB 1.701 4400 4030

Co(BDP) 0.93 2780 2030

Cu‐BTTri 0.713 2050 1750

S-18

Figure S1. Adsorption isotherm for N2 in MOF-177 at 77 K. Black and red circles represent

experimental and previously reported literature data, respectively.10

S-19

Figure S2. Adsorption isotherm for N2 in Be-BTB at 77 K. Black circles represent previously

reported literature data on the same sample used in this study. 5

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Figure S3. Adsorption isotherm for N2 in Co-BDP at 77 K. Black and red circles represent

experimental and previously reported literature data, respectively.6

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Figure S4. Adsorption isotherm for N2 in Cu-BTTri at 77 K. Black and red circles represent

experimental and previously reported literature data, respectively.7

S-22

Figure S5. Adsorption isotherm for N2 in Mg2(dobdc) at 77 K. Black and red circles represent

experimental and previously reported literature data, respectively.8b

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Figure S6. Gas adsorption isotherms for CO2 on Mg2(dobdc). Green triangles represent the

isotherms measured for this study at 313 K and black diamonds are data recorded at 303 K by

Dietzel et al.21

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Figure S7. Gas adsorption isotherms for CO2 on Mg2(dobdc). Green triangles represent the

isotherms measured for this study at 313 K and black diamonds22 and blue circles11 are data

recorded at 298 K by Yaghi and coworkers.

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Figure S8. Total adsorption isotherms for CO2 (green triangles) and H2 (blue circles) at 313 K in

Be-BTB.

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Figure S9. Absolute adsorption isotherm for CO2 (green triangles) at 313 K in Mg2(dobdc)

expressed in mmol/g and molecules of CO2 per magnesium site.

S-27

Figure S10. Absolute adsorption isotherm for CO2 (green triangles) at 313 K in Cu-BTTri

expressed in mmol/g and molecules of CO2 per magnesium site.

S-28

Figure S11. Configurational-Bias Monte Carlo simulations of absolute pure-component

adsorption isotherms for CO2 (green triangles) and H2 (blue circles) at 313 K in MOF-177. The

continuous solid lines are the dual-site Langmuir–Freundlich fits of the pure component

isotherms.

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Figure S12. The component loadings in an 80:20 H2:CO2 mixture for CO2 (green triangles) and

H2 (blue circles) at 313 K in MOF-177 determined using CBMC simulations. The continuous

solid lines are the IAST estimations of the same mixture using the dual-site Langmuir–

Freundlich fits of the pure component isotherms.

S-30

Figure S13. Absolute adsorption of CO2 and H2 at 303 K (red circles and green diamonds

respectively) and 323 K (orange triangles and purple squares respectively) on zeolite 13X

reported by Belmabkhout et al.15 Solid lines are interpolated 313 K data from this study using

dual-site Langmuir—Freundlich fits of the averages of the 303 K and 323 K data for CO2 (blue)

and H2 (black).

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Figure S14. IAST-calculated selectivities for an 80:20 H2:CO2 mixture. References for literature

data are mentioned in the text.

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Figure S15. IAST-calculated selectivities for a 60:40 H2:CO2 mixture. References for literature

data are mentioned in the text.

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Figure S16. IAST-calculated gravimetric working capacities for an 80:20 H2:CO2 mixture.

References for literature data are mentioned in the text.

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Figure S17. IAST-calculated volumetric working capacities for an 80:20 H2:CO2 mixture.

References for literature data are mentioned in the text.

S-35

Figure S18. IAST-calculated gravimetric working capacities for a 60:40 H2:CO2 mixture.

References for literature data are mentioned in the text.

S-36

Figure S19. IAST-calculated volumetric working capacities for a 60:40 H2:CO2 mixture.

References for literature data are mentioned in the text.

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Figure S20. Literature values for the heat of adsorption of CO2 on Mg2(dobdc)8a (red line) and

Cu-BTTri7 (blue circles).

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