science.sciencemag.org/content/368/6488/297/suppl/DC1

Supplementary Materials for

Balancing volumetric and gravimetric uptake in highly porous materials for

clean energy

Zhijie Chen,* Penghao Li,* Ryther Anderson,* Xingjie Wang, Xuan Zhang, Lee Robison,

Louis R. Redfern, Shinya Moribe, Timur Islamoglu, Diego A. Gómez-Gualdrón, Taner Yildirim,

J. Fraser Stoddart, Omar K. Farha†

*These authors contributed equally to this work.

†Corresponding author. Email: o-farha@northwestern.edu

Published 17 April 2020, Science 368, 297 (2020)

DOI: 10.1126/science.aaz8881

This PDF file includes:

Materials and Methods

Supplementary Text

Figs. S1 to S54

Tables S1 to S10

References

Captions for Data S1 to S3

Other Supplementary Materials for this manuscript include the following:

(available at science.sciencemag.org/content/368/6488/297/suppl/DC1)

Data S1 to S3 (.cif)

2

Materials and Methods

Materials

All reagents were obtained from commercial sources and used without further purification,

unless otherwise noted. The ligand-peripherally extended triptycene (H6PET) was synthesized

according to the previous report.(37) NU-1500-Fe was synthesized according to the previous

work.(36) The synthesis of the extended ligand (H6PET-2) is the same as our recently reported

paper.(43) And the detailed synthetic procedures were provided in the following supporting

information.

Synthesis of NU-1500-Al (MOFkey(47): Al.PZUNVLJATCTESM.MOFkey-v1.acs)

AlCl3∙6H2O (90 mg, 0.373 mmol) and H6PET (30 mg, 0.031 mmol) were mixed in 5 mL of

N,N-dimethylformamide (DMF), 5 mL of acetonitrile and 3 mL acetic acid in a 34 mL Pyrex vial

and then the mixture was sonicated for 30 min. The resultant mixture was sealed and heated to

150°C for 18 h. The white crystalline powder was obtained via centrifugation (7000 rpm for 20

min) and washed with DMF 3x before soaking in DMF overnight. Next, the crystals were washed

in acetone 6x and soaked in acetone for two days. The acetone-exchanged samples were activated

under vacuum at 120 °C for 12 hours giving activated MOFs (yield: ~38 mg).

Synthesis of NU-1501-Fe (single crystals; MOFkey: Fe.GKGWJFNTVGTMJR.MOFkey-

v1.acs)

FeCl3∙6H2O (60 mg, 0.222 mmol) and H6(PET-2) (30 mg, 0.021 mmol) were dissolved in 6

mL of DMF and 0.6 mL trifluoroacetic acid (TFA) in a 34 mL Pyrex vial. Then, the mixture was

sonicated for 10 min. The resultant mixture was sealed and heated to 150 °C for 12 h. Yellow-

orange hexagonal block crystals were obtained. Crystals were harvested and washed with DMF 6x

over three days. Then the crystals were washed with ethanol (EtOH) 6x over three days. After

soaking in DMF and ethanol, the crystals were activated by supercritical CO2 followed by

evacuating under vacuum at 40 °C for 12 hours yielded activated MOFs (yield: ~41 mg).

Synthesis of NU-1501-Al (MOFkey: Al.GKGWJFNTVGTMJR.MOFkey-v1.acs)

AlCl3∙6H2O (60 mg, 0.249 mmol) and H6(PET-2) (30 mg, 0.021 mmol) were mixed in 4 mL

of DMF, 4 mL of acetonitrile and 2 mL acetic acid in a 34 mL Pyrex vial. The mixture was

sonicated for 60 min and the resultant mixture was sealed and heated to 150 °C for 18 h. The white

crystalline powder was obtained via centrifugation (7800 rpm for 20 min). The as-synthesized

material was found to be insoluble in H2O and common organic solvents. The white crystalline

powder was washed with DMF 3x and then soaked in DMF overnight. The crystals were washed

with EtOH 6x over three days. After soaking in DMF and ethanol, the crystals were activated by

supercritical CO2 followed by evacuating under vacuum at 40 °C for 12 hours yielded activated

MOFs (yield: ~35 mg).

Synthesis of NU-1501-Al (single crystals)

AlCl3∙6H2O (1 mg in 0.1 mL DMF from stock solutions, 0.004 mmol) and H6(PET-2) (1 mg

in 0.5 mL DMF from stock solutions, 0.010 mmol) were mixed in a 9 mL Pyrex vial. Then, 0.2 ml

CH3CN and 0.5 mL acetic acid were added to the mixture, followed by sonication for 5 min. The

resultant mixture was sealed and heated to 150 °C for 2 days. Colorless hexagonal block crystals

were obtained and used for single crystal X-ray diffraction measurements.

3

NU-1500-Al

MOFid:

[O-]C(=O)c1ccc(cc1)c1cc2c(cc1c1ccc(cc1)C(=O)[O-

])C1c3c(C2c2c1cc(c(c2)c1ccc(cc1)C(=O)[O-])c1ccc(cc1)C(=O)[O-

])cc(c(c3)c1ccc(cc1)C(=O)[O-])c1ccc(cc1)C(=O)[O-].[OH][Al][O]([Al][OH2])[Al][OH2]

MOFid-v1.acs.cat0;NU-1500-Al

MOFkey:

Al.PZUNVLJATCTESM.MOFkey-v1.acs

NU-1501-Al

MOFid:

[O-]C(=O)c1ccc(cc1)c1ccc(cc1)c1cc2c(cc1c1ccc(cc1)c1ccc(cc1)C(=O)[O-

])C1c3c(C2c2c1cc(c(c2)c1ccc(cc1)c1ccc(cc1)C(=O)[O-])c1ccc(cc1)c1ccc(cc1)C(=O)[O-

])cc(c(c3)c1ccc(cc1)c1ccc(cc1)C(=O)[O-])c1ccc(cc1)c1ccc(cc1)C(=O)[O-

].[OH][Al][O]([Al][OH2])[Al][OH2] MOFid-v1.acs.cat0;NU-1501-Al

MOFkey:

Al.GKGWJFNTVGTMJR.MOFkey-v1.acs

NU-1501-Fe

MOFid:

[O-]C(=O)c1ccc(cc1)c1ccc(cc1)c1cc2c(cc1c1ccc(cc1)c1ccc(cc1)C(=O)[O-

])C1c3c(C2c2c1cc(c(c2)c1ccc(cc1)c1ccc(cc1)C(=O)[O-])c1ccc(cc1)c1ccc(cc1)C(=O)[O-

])cc(c(c3)c1ccc(cc1)c1ccc(cc1)C(=O)[O-])c1ccc(cc1)c1ccc(cc1)C(=O)[O-

].[OH][Fe][O]([Fe][OH2])[Fe][OH2] MOFid-v1.acs.cat0;NU-1501-Fe

MOFkey:

Fe.GKGWJFNTVGTMJR.MOFkey-v1.acs

General Information for Synthesis of Ligands

All reagents were purchased from commercial suppliers and used without further purification.

Hexabromotriptycene(48), methyl 4-[4-(tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]benzoate(49)

and Pd SPhos Gen III catalyst(50) were synthesized according to known literature procedures.

Thin layer chromatography (TLC) was performed on silica gel F254 (E. Merck). Column

chromatography was carried out on silica gel 60F (Merck 9385, 0.040−0.063 mm). Developing

plates were visualized using UV light at wavelengths of 254 and 365 nm. High resolution mass

spectra were obtained on an Agilent 6210 Time of Flight (TOF) LC-MS, using an ESI source,

coupled with Agilent 1100 HPLC stack, using direct infusion (0.6 mL/min). Nuclear magnetic

resonance (NMR) were recorded on a Bruker Avance III 500 MHz system with DCH CryoProbe.

Chemical shifts are reported in parts per million (ppm) and are referenced to the residual protio-

solvent (CDCl3: δH = 7.26 ppm, δC = 77.16 ppm; DMSO-d6: δH = 2.50 ppm, δC = 39.52 ppm).

Spectra were analyzed with MestraNova software (Version 12.0). Data are represented as follows:

chemical shift, multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, bs = broad singlet, m

= multiplet), coupling constants in Hertz (Hz), and integration.

4

Synthetic Protocols of Ligands

Scheme S1. Synthesis of H6PET-2

Synthesis of Me6PET-2

Hexabromotriptycene (3.77 g, 5.18 mmol), methyl 4-[4-(tetramethyl-1,3,2-dioxaborolan-2-

yl)phenyl]benzoate (12.3 g, 36.3 mmol), Pd SPhos Gen III catalyst (0.20 g, 0.26 mmol) and THF

(150 mL) were added to a 500 mL round-bottomed flask equipped with a magnetic stirrer bar. A

condenser was attached to the flask and the mixture was degassed by bubbling N2 for 30 min, at

which point degassed aqueous K3PO4 solution (2 M, 40 mL) was added. The reaction was heated

under reflux in an N2 atmosphere overnight. After cooling to room temperature, the aqueous layer

was removed by pipette. THF was removed under reduced pressure and the residue was dissolved

in CH2Cl2 (200 mL). The solution was washed with saturated brine solution (100 mL) and dried

(Mg2SO4). After removing the solvent, the crude solid was purified by chromatography (SiO2, 0%

to 10% EtOAc in CH2Cl2) to give the product as a colorless solid film (4.68 g, 60%). 1H NMR

(500 MHz, CDCl3), δ = 8.07 (d, J = 8.5 Hz, 12H, Ar-H), 7.65 (s, 6H, Ar-H), 7.65 (d, J = 8.5 Hz,

12H, Ar-H), 7.51 (d, J = 8.4 Hz, 12H, Ar-H), 7.25 (d, J = 8.4 Hz, 12H, Ar-H), 5.75 (s, 2H, Csp3-

H), 3.93 (s, 18H, Ome). 13C NMR (125 MHz, CDCl3), δ = 167.10, 145.08, 144.49, 141.40, 138.11,

137.43, 130.66, 130.23, 129.00, 127.01, 126.92, 126.41, 53.36, 52.27. ESI-HRMS calcd for

C104H74O12Na [M + Na]+, m/z = 1537.5078, found and 1537.5081.

5

Synthesis of H6PET-2

Me6PET-2 (2.66 g, 1.75 mmol) was dissolved in THF (50 mL) in a 250 mL round-bottomed flask

equipped with a magnetic stirrer bar. Aqueous NaOH solution (1 M, 50 mL) was added and the

resulting mixture was heated at 70 ˚C overnight. Upon cooling to room temperature, THF was

removed under reduced pressure and the remaining aqueous solution was acidified (pH = 1) with

aqueous HCl solution (2 M). The resulting white precipitate was collected by filtration, washed

with H2O (20 mL) and dried under high vacuum to give the product as a white solid (2.29 g, 91%). 1H NMR (500 MHz, DMSO-d6), δ = 12.94 (s, 6H, O-H), 7.96 (d, J = 8.1 Hz, 12H, Ar-H), 7.78 (d,

J = 8.1 Hz, 12H, Ar-H), 7.70 (s, 6H, Ar-H), 7.65 (d, J = 8.1 Hz, 12H, Ar-H), 7.26 (d, J = 8.1 Hz,

12H, Ar-H), 6.12 (s, 2H, Csp3-H). 13C NMR (125 MHz, DMSO-d6), δ = 167.07, 144.59, 143.39,

141.01, 136.84, 136.40, 130.20, 129.84, 129.49, 126.49, 126.45, 126.23, 51.56. ESI-HRMS calcd

for C98H62O12Na [M + Na]+, m/z = 1453.4139, found 1453.4156.

Methods

Powder X-Ray Diffraction Analyses. Powder X-ray diffraction (PXRD) of MOFs were measured

at room temperature on a STOE-STADIMP powder diffractometer equipped with an asymmetric

curved Germanium monochromator (CuKα1 radiation, λ = 1.54056 Å) and one-dimensional

silicon strip detector (MYTHEN2 1K from DECTRIS). The line focused Cu X-ray tube was

operated at 40 kV and 40 mA. The activated powder was sandwiched between two Kapton foils

and measured in transmission geometry in a rotating holder. Intensity data from 1 to 30 degrees

two theta were collected over a period of 6 minutes. The instrument was calibrated against a NIST

Silicon standard (640d) prior to the measurement. Variable temperature PXRD (VT-PXRD)

measurements were conducted on a STOE-STADI MP powder diffractometer operating at 40 kV

voltage and 40 mA current with Cu-Kα1 X-ray radiation (λ = 0.154056 nm) in sealed spinning

capillaries in the temperature range of 25 to 400 °C.

6

Single-crystal X-Ray Diffraction Analyses Single-crystal X-ray diffraction (SC-XRD) data of

NU-1501-Al was collected at 275 K using a Bruker KAPPA APEX II (Bruker, Billerica, MA)

equipped with an APEX2 CCD detector, Cryostream 80-400K (Oxford Cryosystems, Oxford,

United Kingdom), and CuKα (λ = 1.54178 Å) IμS microfocus source with MX Optics and a Kappa

geometry goniometer. The data of NU-1501-Fe was collected at 275 K on a 'Bruker APEX-II

CCD' diffractometer with a MoKα (λ = 0.71073 Å) microfocus X-ray source. The single crystals

were mounted on MicroMesh (MiTeGen) with paratone oil. The structures were determined by

intrinsic phasing (SHELXT 2014/5)(51) and refined by full-matrix least-squares refinement

(SHELXL-2017/1)(52) using the Olex2(53) software package. The disordered non-coordinated

solvents were removed using the PLATON SQUEEZE program.(54) Refinement results are

summarized in Tables S1-2. Crystallographic data in CIF format have been deposited in the

Cambridge Crystallographic Data Centre (CCDC) under deposition number CCDC 1909853,

1909854 and 1945113. The data can be obtained free of charge via

www.ccdc.cam.ac.uk/data_request/cif (or from the Cambridge Crystallographic Data Centre, 12

Union Road, Cambridge CB2 1EZ, U.K.)

N2 and Argon Sorption Measurements. Argon and N2 adsorption and desorption isotherms on

activated materials were measured at Northwestern University on an ASAP 2020 (Micromeritics)

instrument at 87 K and 77 K, respectively. Before high-pressure gas sorption studies, the N2

adsorption and desorption isotherms on activated materials (shipped from Northwestern

University) were measured at the National Institute of Standards and Technology (NIST) Center

for Neutron Research (NCNR) located at Gaithersburg, Maryland, United States.

Activation of NU-1500-Al and NU-1500-Fe was performed under a dynamic vacuum for 12

h on SVP at 120 ⁰C (2 ⁰C/min). Supercritical CO2 (ScCO2) was applied to activate NU-1501-Al

and NU-1501-Fe. After sc-CO2 drying, Activation of NU-1501-Al and NU-1501-Fe was

performed under a dynamic vacuum for 24 h on SVP at 40 ⁰C (2 ⁰C/min). The pore size

distributions of all MOFs in this work are calculated based on the density functional theory (DFT)

model with the geometry of slit (N2 DFT model) by using MicroActive Version 4.06.

Scanning electron micrographs (SEM) images were taken using a Hitachi SU8030 at the EPIC

facility (NUANCE Center-Northwestern University). Samples were activated and coated with

OsO4 to ~9 nm thickness in a Denton Desk III TSC Sputter Coater before imaging.

Optical photos of the single crystals were obtained from a Nikon SMZ1500 stereozoom

microscope coupled to a digital camera and PC (video monitor).

X-ray photoelectron spectroscopy (XPS) measurements were carried out at the KECK-

II/NUANCE facility at Northwestern University on a Thermo Scientific ESCALAB 250 Xi (Al

Kα radiation, hν = 1486.6 eV) equipped with an electron flood gun. XPS data were analyzed using

Thermo Scientific Advantage Data System software and all spectra were referenced to the C 1s

peak (284.8 eV).

Supercritical CO2 (sc-CO2) procedure: Supercritical CO2 activation experiments were

performed on Tousimis Samdri PVT-30 critical point dryer. Before doing the sc-CO2 drying, the

as synthesized materials were soaked in DMF for 3 days. The solvent was refreshed every 12 h,

for each time, 12 mL of fresh DMF was added into the vials (or tubes). After three days, the solvent

7

(DMF) was centrifuged and removed. The materials were then soaked in the ethanol for 3 days to

fully exchange with the DMF in the materials. During this time, the ethanol was refreshed every

12 h and 10 mL of fresh ethanol was added into the vials (or tubes) each time. After removing

solvents, the material was transferred to a small glass container for sc-CO2 drying (Note that do

not let the materials dry in ethanol, be sure the materials are always wet in ethanol before applying

sc-CO2 drying procedure).

Details of sc-CO2 drying procedure(28, 55):1. Make sure all the knobs and gas tank are closed.

Place the container into the dryer chamber slightly and screw the caps of the chamber tightly. 2.

Turn the power on and open the gas tank, then turn on the cool knob to set the temperature to be

in the range of 0-10 ºC and adjust the knob to make sure it is stable in this range. (Note: do not

open the knob too much in case the temperature decreases sharply and goes below 0 ºC) 3. Slightly

open the fill knob and the liquid CO2 will start to fill in the chamber, make sure the CO2 doesn’t

flow fast and turn off the fill knob as the liquid level gets to 70 % full of the container. 4. Wait for

the powder settle down and then open the fill knob again to fill the chamber (Note, make sure the

liquid CO2 slowly fills into the chamber and no particles come out from the container–always

control the temperature in the range of 0-10 ºC during the filling) 5.Turn the fill knob up to 15,

and open purge to 4 for 5 min. Turn off the purge knob and turn the fill knob down to 5. (Note:

During purging, the temperature will increase, so it is necessary to turn the cool knob up slightly

to make sure the temperature is still in the correct range. Turn it back when the purge is over.) 6.

Leave sample for 2 h and repeat these same steps 4 times. (Note: always check the temperature to

avoid going too high or too low during this time.) 7. After the last purge, turn off all the knobs and

gas tank and then switch the heat on to let the temperature rise to ~40 ºC. 8. Hook the pressure

gauge to the bleed port, then open the bleed to 0.5 cc/min. Wait for it to stabilize and then leave it

overnight. 9. Turn off the heat and open bleed to release the pressure. 10. Loosen the screws one

by one very slightly to release pressure, then open the chamber and take out the sample. 11.

Transfer the sample to a sorption tube in open air and complete SVP at 40 ºC for at least 12 h.

High-pressure Sorption Measurements. High-pressure gas sorption measurements were

performed on the activated samples at the NIST Center for Neutron Research (NCNR) using a

computer-controlled Sieverts apparatus. Specifics regarding the instrument and procedure were

previously reported.(56) All gases used for the adsorption measurements were high-purity grade

(99.999%).

Activated samples were packed in the argon atmosphere glovebox before shipping to NIST for

high pressure sorption measurement. Prior to the sorption study, NU-1500-Al was activated under

a dynamic vacuum for 12 h at 120 ⁰C, and NU-1501-Fe and NU-1501-Al were activated at 40 ⁰C

overnight.

High pressure adsorption measurements were performed using a custom developed fully

computer-controlled Sieverts apparatus as discussed in detail in Ref(56). Briefly, the fully

computer-controlled Sievert apparatus operates in a sample temperature range of 20 K to 500 K

and a pressure range of 0 to 100 bar. In the volumetric method, gas is admitted from a dosing cell

with known volume to the sample cell in a controlled manner; the gas pressure and temperature

are controlled and recorded.

Some unique features of the setup are as follows; The instrument has five gas inlets including He,

N2, CO2, CH4, and H2, which enables the first nitrogen pore volume and surface measurements

followed by He-cold volume determination and finally the gas adsorption measurements without

needing to move the sample from the cell. Two high precision digiquartz pressure gauges with

8

parts-per-billion resolution and typical accuracy of 0.01% (20 psia and 3000 psia, respectively)

were used to precisely measure the pressure. For isotherm measurements below room temperature,

the sample temperature was controlled using a closed cycle refrigerator (CCR). The difference

between the real sample temperature and the control set-point is within 1 K in the whole operating

temperature range. The connection between the sample cell and the dose cell is through 1/8’’

capillary high-pressure tubing, which provided a sharp temperature interface between the sample

temperature and the dose temperature (i.e., room temperature). The cold volumes for the empty

cell were determined using He as a function of pressure at every temperature before the real sample

measurement and were used to calculate the sample adsorption.

Since the adsorbed amount is deducted from the raw P-V-T data using a real gas equation of state,

a critically important issue is the accuracy of the chosen equation of state (EOS) in terms of

describing the real gas behavior within the desired temperature and pressure range. Using an empty

cell as a reference, we found that the MBWR EOS best describes the real gas behavior of He, H2

and CH4. Therefore, in all our isotherm data reduction, the NIST MBWR EOS is used. [NIST

Standard Reference Database 23:  NIST Reference Fluid Thermodynamic and Transport

Properties Database].

In the reported literature, the volumetric storage capacity of MOFs has been widely calculated with

the ideal crystallographic density. Nevertheless, it is impossible to fill a storage tank with a large

single crystal of adsorbent in practical use. That results in packing loss, which we didn’t include

in discussion in our work.

In this work, the capacity (in wt%) of H2 is calculated according to wt% = (mass of H2)/(mass of

H2 + mass of MOF) × 100%. It should be noted in some literature, the capacity (in wt%) of H2 is

calculated according to wt% = (mass of H2)/(mass of MOF) × 100%. For the sake of consistency

and comparison, we have converted uptakes reported in literature based on wt% = (mass of

H2)/(mass of MOF) × 100% to wt% = (mass of H2)/(mass of H2 + mass of MOF) × 100%.

Error Bars in High Pressure Isotherm Measurements

The errors in individual components like temperature, pressure and mass reading are very small,

all below 0.01 wt%. However, the real error in the measured adsorption arises from other factors

such as the quality of the high-pressure equation of state and the approximation that our sievert

system has two temperature zones; room temperature for dosing volume and the cold-temperature

(where the sample is located) with a very sharp temperature gradient. Hence, we found that the

best way to estimate the error bars on adsorption data is to repeat the measurements keeping

everything same but without any sample in the cell. In the scheme below, we show the apparent

adsorption from empty cell for methane and hydrogen gas at the same temperatures as the actual

data taken for 200mg of MOFs, which is a typical loading. As shown in the scheme, the errors are

largest at lowest temperature (probably due to two-temperature zone with a sharp gradient

approximation). The maximum error is about 0.03 mmol at 100 bar. Comparing this error with the

total adsorption for methane and hydrogen, we find that the maximum error at these pressures is

less than 0.4 wt%. Because of these small error bars, we did not show the error bars in the isotherm

plots as they won't be visible. We added a sentence in the scheme caption indicating that the error

bars are about the size of the filled symbols in the plots.

9

Scheme S2. Top: Total hydrogen (left) and methane (right) uptakes (in mmol) for 200 mg of NU-

1501-Al sample. The estimated error bars at 100 bar is also indicated. Bottom: The apparent

adsorption from empty cell as a function of pressure and temperature for hydrogen (left) and

methane (right). The error bars are about the size of the filled symbols in the isotherm plots.

Measured Isosteric Heat of Adsorption Qst

Our isotherm data at multiple temperatures enable us to extract the heat of adsorption Qst as a

function of the adsorbed amount. Qst is calculated using the “isosteric method” where a series of

isotherms are measured at multiple temperatures. These isotherms are then parameterized by

cubic-spline which does not require any fitting and allows us to interpolate the isotherm at a

constant loading. Then, the Qst is obtained from the ln(P) versus 1/T plots. As an alternative to

cubic-spline interpolation, we also obtain Qst by fitting the isotherm data using the following form

of a virial equation:

ln(𝑝) = ln(𝑣) +1

𝑇∑ 𝑎𝑖 𝑣

𝑖 + ∑ 𝑏𝑖 𝑣𝑖

𝑛

𝑖=0

𝑚

𝑖=0

where v, p, and T are the amount adsorbed, pressure, and temperature, respectively and ai and bi

are empirical parameters. The first four constants (i.e. a0, b0, a1, and b1) are obtained by linearizing

the isotherms (1/n versus ln p) and then we increase the number of parameters gradually (two at a

time) until the improvement in the fit is not significant. Usually 10 or 12 parameters are found to

be enough to obtain a good fit to the isotherms. After the isotherms are fitted, by applying Clausius-

Clapeyron equation, the heat of adsorption is obtained as

𝑄𝑠𝑡 = −𝑅 ∑ 𝑎𝑖𝑣𝑖

𝑚

𝑖=0

where R is the universal gas constant. The details can be found in ref(57, 58).

10

Supplementary Text

Molecular Simulation

All simulated isotherms were computed using Monte Carlo simulations in the grand canonical

ensemble (GCMC simulations) in which chemical potential, volume, and temperature are held

constant. All GCMC simulations were performed using the RASPA code(59). In the grand

canonical ensemble, adsorbate molecules are allowed to translate, rotate, be inserted into the

framework, and be removed from the framework (the framework is modeled as rigid). Each

simulation is performed for N cycles, where each cycle consists of M moves (chosen from

translation, rotation, insertion, and deletion), and M is the maximum between the number of

adsorbates in the framework and 20. Each point in the simulated isotherms corresponds to a single

GCMC simulation at fixed adsorbate pressure. Each point in the nitrogen isotherms corresponds

to the average loading taken across 20000 production cycles, which were preceded by 20000

initialization (or equilibration) cycles, in which no data was recorded. Each point in the hydrogen,

and methane isotherm simulations corresponds to the average loading taken across 10000

production cycles, preceded by 10000 initialization cycles. Each point the hydrogen and methane

deliverable capacities simulated on the MOF database corresponds to 3000 initialization and 3000

production cycles. Adsorbate-adsorbate interactions were modeled using Lennard-Jones (LJ)

potentials together with electrostatic interactions described by Coulomb’s law. Adsorbate-

framework interactions were modeled only with Lennard-Jones potentials (no adsorbate-

framework electrostatic interactions were considered). All LJ interactions were truncated and

shifted to zero energy at 12.5 Å. LJ parameters and charges for nitrogen and methane were taken

from the Transferable Potentials for Phase Equilibria (TraPPE) force-field(60, 61). LJ parameters

and charges for hydrogen corresponded to the Darkim-Levesque model with Feynman-Hibbs

corrections,(62) which has been shown to produce accurate H2 adsorption results in numerous

studies(33, 63, 64), and produces close correlations with experiments in this study. LJ parameters

for framework atoms corresponded to the Dreiding force-field(65). LJ parameters for interactions

not explicitly parameterized were obtained using Lorentz-Berthelot mixing rules.

Geometric surface areas, helium void fractions, and geometric pore size distributions were all

computed using RASPA.(59) Enthalpies of adsorption (∆ℎads) where calculated during the GCMC

simulations implemented in RASPA using

(1) Δℎads = ⟨𝑈𝑁⟩ − ⟨𝑈⟩⟨𝑁⟩

⟨𝑁2⟩ − ⟨𝑁⟩2

where 𝑈 is potential energy, 𝑁 is the number of adsorbates in the system, and angled brackets

denote an ensemble average.(66) The reported values were taken from low pressure simulations

(i.e. conditions far from saturation loading), where good statistics can be obtained from equation

1.(67)

Database MOFs were constructed using ToBaCCo(42, 68), which builds MOFs using

crystallographic nets as blueprints, to which structural building units are added. The MOFs built

by ToBaCCo were then geometry optimized in LAMMPs(69) according to the universal force

field(70) with a conjugate gradient algorithm in an iterative approach. During each iteration the

atom coordinates were optimized keeping the unit cell parameters fixed, then the unit cell

parameters and atom coordinates were optimized together. Each individual optimization was

halted when the total energy did not change from the previous conjugate gradient step. This

iterative process was halted when the energy changed by less than 1 × 10−6 kcal/mol from the

previous iteration.

11

Database Simulations

To understand the trade-off of gravimetric and volumetric surface area (GSA and VSA,

respectively) we calculated the geometric surface areas in a 2800 MOF, topologically (58 topology)

diverse database. The VSA verses GSA relationship (and the related volumetric/gravimetric

deliverable capacity relationship) is well-known and has been studied on other MOF databases(33,

63), specifically, VSA exhibits a peak around 4,000 m2/g of GSA (see Fig. S50). Thus, to

maximize VSA, the GSA should be kept relatively low (i.e. a relatively dense MOF should be

used). However, we are focused on obtaining optimal VSA and GSA, for which we would expect

GSA to be much higher than 4,000 m2/g. We propose using the product of GSA and VSA to

identify MOFs that have both maximal GSA and VSA. To quantitatively identify those MOFs, we

define the “ideal trade-off region” of our database as MOFs in the 95th percentile of GSA × VSA.

This ideal trade-off region is located just to the right of the VSA peak in the VSA vs. GSA

relationship. Notably, NU-1501-Al is in this region ( Fig. S50b).

Fig. S51 shows several properties which influence the product of GSA and VSA. From Fig. S51

a, b we estimate that a void fraction (VF) and largest pore diameter (LPD) around 0.85 and 18.0

Å, respectively are associated with a maximum in GSA × VSA. In correspondence with our

estimation, MOFs in the ideal cutoff region have an average helium VF of 0.85 (NU-1501 = 0.87)

and an average largest pore diameter of 17.2 Å (NU-1501 = 18.8 Å). Fig. S51 c, d show more

quantitatively (than Fig. S49) that significant polydispersity is detrimental for MOF GSA × VSA.

Here, points are colored by pore size distribution standard deviation (pore size SD), which we

define as the weighted standard deviation of all the diameters considered in geometrically

calculated pore size distributions (0.1 to 60 Å in intervals of 0.1 Å), where each diameter is

weighted by its corresponding distribution height. Therefore, MOFs with multiple high peaks in

the PSD, will have a larger value of pore size SD, whereas MOFs with a single highest (perhaps

with some small peaks) will have a lower values of pore size SD. Notably, many MOFs with VFs

and LPDs in the correct ranges for high GSA × VSA, but with high pore size SD, are excluded

from the ideal trade-off region. Fig. S51 e, f show that MOFs with lower metal atom to organic

atom ratios tend to have higher GSA × VSA, this is because organic atom moieties (e.g. aromatic

rings) tend to provide large adsorption surfaces while being light compared to metals.

While the ideal VF and LPD of NU-1501-A1, together with its low pore polydispersity and metal

atom to organic atom ratio, contribute to its presence in the ideal trade-off region, the linker of

NU-1501 also helps to maximize GSA × VSA. To show this we built 50 MOFs using ToBaCCo

with the acs-b topology of NU-1501 with different organic linkers (see Fig. S52). The SMILES

strings for the dicarboxylic species corresponding to the linkers shown in Fig. S52 are given in

Table S10. We considered both MOFs with hexatopic organic linkers (as in NU-1501) and MOFs

with ditopic organic linkers, i.e. MOFs with aluminum metal nodes with six ditopic linkers in place

of the hexatopic organic linker. We then calculated the VSA and GSA for each of these 50 MOFs

in order to compare them to NU-1501-Al, these results are summarized in Fig. S53.

From Fig. S53 we can clearly see that a hexatopic organic linker is preferable to an additional

metal node and six ditopic organic linkers, as there are eight MOFs of the former composition and

only one of the latter composition in the ideal cut-off region. We also note that there are only seven

MOFs isoreticular to NU-1501-Al with higher GSA × VSA. Six of these are MOFs with L13, L14,

and L15 computational linkers and either of the six-connected nodular organic SBUs considered

12

(N1 or N2, see Fig. S52a). One is a MOF with ditopic organic linker L13, and one is a MOF (the

only MOF with a linker of similar length to NU-1501-Al) with linker L5 and the N1 nodular SBU.

MOFs with linkers L13, L14, and L15 can be synthetically challenging due to the potential

catenation. The N1 + L5 MOF, while promising, has significantly lower GCMC simulated

hydrogen and methane deliverable capacities that NU-1501-Al. Thus, we have shown that NU-

1501-Al possesses not only ideal textural properties, but also ideal composition for attaining

maximal VSA and GSA.

As a final exercise, we consider the tradeoff between gravimetric deliverable capacity (GDC) and

volumetric deliverable capacity (VDC) for hydrogen (100 bar/77 K → 5 bar/160) and methane

(100 bar/270 K → 5 bar/270 K and 100 bar/296 K → 5 bar/296 K) using an approach similar to

that employed for analyzing the VSA/GSA tradeoff. The results of this analysis are summarized

in Fig. S54.

Notably, there is a less distinct peak in the VDC/GDC tradeoff than in the VSA/GSA tradeoff,

meaning that MOFs with maximally high GDC (and thus generally maximally high GSA) are

included in the ideal tradeoff region. From Fig. S54 we see that there are many MOFs within the

ideal tradeoff region for deliverable capacity that have too high a GSA to be in the ideal tradeoff

region for surface area. NU-1501 lies exactly at the boundary of MOFs in the ideal tradeoff region

for deliverable capacity and MOFs in the ideal tradeoff region for surface area (in all cases),

meaning that NU-1501-Al maintains maximally high VSA for MOFs with GDC × VDC in the

95th percentile (most others having higher GSA and lower VSA).

13

Fig. S1. 1H NMR Spectrum (500 MHz, CDCl3, 298 K) of Me6PET-2.

14

Fig. S2. 13C NMR Spectrum (125 MHz, CDCl3, 298 K) of Me6PET-2.

15

Fig. S3. 1H NMR Spectrum (500 MHz, DMSO-d6, 298 K) of H6PET-2.

16

Fig. S4. 13C NMR Spectrum (125 MHz, DMSO-d6, 298 K) of H6PET-2.

17

Fig. S5.

PXRD patterns of NU-1500-Al and NU-1500-Fe. The phase purity of the bulk NU-1500-Al was

confirmed between the simulated and the as-synthesized powder X-ray diffraction (PXRD)

patterns.

18

Fig. S6.

PXRD patterns of NU-1501-Al and NU-1501-Fe.

19

Fig. S7.

PXRD patterns of NU-1501-Al and NU-1501-Fe before and after water treatment. The water

treatment consisted of soaking the dry MOF samples after sc-CO2 for 24 hours in DI water and

then washing the sample with EtOH.

20

Fig. S8.

PXRD patterns of DUT-6 and UMCM-1 before and after water treatment. The water treatment

consisted of soaking the dry MOF samples after N2 sorption in DI water for 24 hours and then

washing the sample with DMF 3 times and DCM 6 times over three days before activating from

DCM again. The synthesis and activation of DUT-6 and UMCM-1 were e performed according to

the previously reported literatures.(71, 72)

21

Fig. S9.

VT-PXRD patterns of NU-1501-Al.

22

Fig. S10.

SEM image (left) and EDS spectra (right) of a microcrystal of NU-1500-Al. EDS line scans for Al

(Kα1) and Cl (Kα1) are in black and red, respectively. The atomic percentage from the line scan:

Cl ~2% and Al ~98%. The nearly complete absence of chloride signals from energy-dispersive X-

ray spectroscopy (EDS) supports the formula, [Al3(µ3-O)(H2O)2(OH)(PET)] with OH− as the

charge-balancing anion.

23

Fig. S11.

A SEM image of microcrystals of NU-1501-Al.

24

Fig. S12.

SEM image (left) and EDS spectra (right) of a microcrystal of NU-1501-Al. EDS line scans for Al

(Kα1) and Cl (Kα1) are in black and red, respectively. The atomic percentage from the line scan:

Cl ~1% and Al ~99%.

0 2 4 6 8 10 12

0

5

10

15

20

25

30

Co

un

ts

Length (m)

Al Ka1 (counts)

Cl Ka1 (counts)

25

Fig. S13.

SEM image (left) and EDS spectra (right) of a microcrystal of NU-1501-Fe. EDS line scans for Fe

(Kα1) and Cl (Kα1) are in black and red, respectively. The atomic percentage from the line scan:

Cl ~0% and Fe ~100%.

0 50 100 150 200

0

2

4

6

8

10

12

14

16

18

20

Co

un

ts

Length (m)

Fe Ka1 (counts)

Cl Ka1 (counts)

26

Fig. S14.

Optical images of the single crystals of NU-1501-Fe after water treatment. The water treatment

consisted of soaking the dry MOF samples after sc-CO2 for 24 hours in DI water and then washing

the sample with EtOH 6 times over three days.

27

Fig. S15.

Experimental and simulated N2 adsorption isotherms at 77 K of NU-1500-Al. The bottom figure

is in log scale. Experimental isotherms were measured at both Northwestern University and NIST.

28

Fig. S16.

Experimental BET area calculation of NU-1500-Al based on N2 adsorption isotherms at 77K,

fulfilling all four BET criteria. The selected linear region is shown by empty circles and highlighted

in blue. A) Shows the BET equation around the selected linear region, B) shows N(1−P/P0), and

C) shows the isotherm around selected linear region on a log scale, the black line is the monolayer

loading and the orange line is 1/√C + 1.

29

Fig. S17.

Simulated BET area calculation of NU-1500-Al based on simulated N2 adsorption isotherms at 77

K, fulfilling all four BET criteria. The selected linear region is shown by empty circles and

highlighted in blue. A) Shows the BET equation around the selected linear region, B) shows N(1

−P/P0), and C) shows the isotherm around selected linear region on a log scale, the black line is

the monolayer loading and the orange line is 1/√C + 1.

30

Fig. S18.

Experimental and simulated N2 adsorption isotherms at 77 K of NU-1501-Al. The bottom figure

is in the log scale. Experimental isotherms were measured at both Northwestern University and

NIST.

31

Fig. S19.

A) Experimental N2 (77 K) sorption isotherms of NU-1501-Al, NU-1501-Fe, NU-1500-Al, and

NU-1500-Fe. B) DFT pore size distributions from N2 (77 K) adsorption isotherms.

32

Fig. S20.

Experimental N2 (77 K) and Ar (87 K) sorption isotherms of NU-1501-Al and NU-1501-Fe.

33

Fig. S21.

Experimental BET area calculation of NU-1501-Al based on N2 adsorption isotherms at 77 K,

fulfilling all four BET criteria. The selected linear region is shown by empty circles and highlighted

in blue. A) Shows the BET equation around the selected linear region, B) shows N(1−P/P0), and

C) shows the isotherm around selected linear region on a log scale, the black line is the monolayer

loading and the orange line is 1/√C + 1.

34

Fig. S22.

Simulated BET area calculation of NU-1501-Al based on simulated N2 adsorption isotherms at 77

K, fulfilling first two BET criteria. The selected linear region is shown by empty circles and

highlighted in blue. A) Shows the BET equation around the selected linear region, B) shows

N(1−P/P0), and C) shows the isotherm around selected linear region on a log scale, the black line

is the monolayer loading and the orange line is 1/√C + 1.

35

Fig. S23.

Experimental BET area calculation of NU-1501-Fe based on N2 adsorption isotherms at 77 K,

fulfilling all four BET criteria. The selected linear region is shown by empty circles and highlighted

in blue. A) Shows the BET equation around the selected linear region, B) shows N(1−P/P0), and

C) shows the isotherm around selected linear region on a log scale, the black line is the monolayer

loading and the orange line is 1/√C + 1.

36

Fig. S24.

Simulated BET area calculation of NU-1501-Fe based on simulated N2 adsorption isotherms at 77

K, fulfilling first two BET criteria. The selected linear region is shown by empty circles and

highlighted in blue. A) Shows the BET equation around the selected linear region, B) shows

N(1−P/P0), and C) shows the isotherm around selected linear region on a log scale, the black line

is the monolayer loading and the orange line is 1/√C + 1.

37

Fig. S25.

Experimental N2 (77 K) sorption isotherms of NU-1501-Al before and after water

treatment. The water treatment consisted of soaking the dry MOF samples after sc-CO2 in

water for 24 hours and then washing the sample with EtOH 6 times over three days before

applying sc-CO2 activation again.

38

Fig. S26.

Experimental N2 (77 K) sorption isotherms of NU-1501-Fe before and after water

treatment. The water treatment consisted of soaking the dry MOF samples after sc-CO2 in

water for 24 hours and then washing the sample with EtOH 6 times over three days before

applying sc-CO2 activation again.

39

Fig. S27.

Experimental N2 (77 K) sorption isotherms of DUT-6 and UMCM-1 before and after water

treatment. The water treatment consisted of soaking the dry MOF samples after N2 sorption in

water for 24 hours and then washing the sample with DMF 3 times and DCM 6 times over three

days before applying activation from DCM again.

40

Fig. S28.

(A-F) Trade-off between gravimetric and volumetric methane uptake for selected benchmark

MOFs, COFs, and activated carbon at room temperature and near freezing temperature.

41

Fig. S29.

(A-B) Trade-off between gravimetric and volumetric deliverable methane capacity of MOFs for

5−80 bar (blue points) and 5−100 bar (purple points) at room temperature and near freezing

temperature. (C-F) Deliverable methane capacity for 5−100 bar/room temperature, 5−100 bar/ near

freezing temperature, 5−80 bar/room temperature, 5−80 bar/near freezing temperature. Methane

adsorption isotherms of MOFs in this work are performed at 296 K and 270 K, and methane

adsorption isotherms of other materials for comparison are performed at 298 K and 273 K.

42

Fig. S30.

(A) Trade-off between gravimetric and volumetric BET area for selected ultrahigh porous

materials. (B) Trade-off between gravimetric and volumetric deliverable hydrogen capacity under

combined temperature and pressure swing condition: 77 K/100 bar →160 K/5 bar.

43

Fig. S31.

Experimental high-pressure CH4 adsorption and desorption isotherms for NU-1500-Al at 270 K

and 296 K, respectively.

44

Fig. S32.

Experimental high-pressure H2 adsorption and desorption isotherms for NU-1500-Al at 77 K, 160

K and 296 K, respectively.

45

Fig. S33.

Experimental high-pressure CH4 total (left) and excess (right) isotherms for NU-1500-Al at 270 K

and 296 K, respectively. Connecting traces are guides for the eye.

46

Fig. S34.

The CH4 adsorption isotherms (dots) for NU-1500-Al and the virial fit (red-lines) along with the

fit parameters as well as the Qst and the lnP-1/T plot. The black line in the Qst plot is obtained from

the raw data using the spline method without any fitting.

47

Fig. S35.

Experimental high-pressure H2 total (left) and excess (right) isotherms for NU-1500-Al at 77 K,

160 K and 296 K, respectively. Connecting traces are guides for the eye.

48

Fig. S36.

The H2 adsorption isotherms (dots) for NU-1500-Al and the virial fit (red-lines) along with the fit

parameters as well as the Qst and the lnP-1/T plot. The black line in the Qst plot is obtained from

the raw data using the spline method without any fitting.

49

Fig. S37.

Experimental high-pressure CH4 adsorption and desorption isotherms for NU-1501-Al at 270 K

and 296 K, respectively.

50

Fig. S38.

Experimental high-pressure CH4 adsorption isotherms for NU-1501-Al and NU-1500-Al at 270 K

and 296 K, respectively.

51

Fig. S39.

Experimental high-pressure H2 adsorption and desorption isotherms for NU-1501-Al at 77 K, 160

K and 296 K, respectively.

52

Fig. S40.

Experimental high-pressure H2 adsorption isotherms for NU-1501-Al and NU-1500-Al at 77 K,

160 K and 296 K, respectively.

53

Fig. S41.

Experimental high-pressure CH4 total (left) and excess (right) isotherms for NU-1501-Al at 270 K

and 296 K, respectively. Connecting traces are guides for eyes.

54

Fig. S42.

The CH4 adsorption isotherms (dots) for NU-1501-Al and the virial fit (red-lines) along with the

fit parameters as well as the Qst and the lnP-1/T plot. The black line in the Qst plot is obtained from

the raw data using the spline method without any fitting.

55

Fig. S43.

Experimental high-pressure H2 total (left) and excess (right) isotherms for NU-1501-Al at 77 K,

160 K and 296 K, respectively. Connecting traces are guides for the eye.

56

Fig. S44.

The H2 adsorption isotherms (dots) for NU-1501-Al and the virial fit (red-lines) along with the fit

parameters as well as the Qst and the lnP-1/T plot. The black line in the Qst plot is obtained from

the raw data using the spline method without any fitting.

57

Fig. S45.

Experimental high-pressure CH4 total (left) and excess (right) isotherms for NU-1501-Fe at 270 K

and 296 K, respectively. Connecting traces are guides for the eye.

58

Fig. S46.

The CH4 adsorption isotherms (dots) for NU-1501-Fe and the virial fit (red-lines) along with the

fit parameters as well as the Qst and the lnP-1/T plot. The black line in the Qst plot is obtained from

the raw data using the spline method without any fitting.

59

Fig. S47.

Experimental high-pressure H2 total (left) and excess (right) isotherms for NU-1501-Fe at 77 K,

160 K and 296 K, respectively. Connecting traces are guides for the eye.

60

Fig. S48.

The H2 adsorption isotherms (dots) for NU-1501-Fe and the virial fit (red-lines) along with the fit

parameters as well as the Qst and the lnP-1/T plot. The black line in the Qst plot is obtained from

the raw data using the spline method without any fitting.

61

Fig. S49.

Geometrical calculation of pore size distribution from the crystal structures of the selected highly

porous materials. We calculated the geometric pore size distribution using the methods of Gelb

and Gubbins(73), where for a large number of random points in the pore volume, the largest sphere

that can enclose each point without overlapping framework atoms is determined.

62

Fig. S50.

VSA vs. GSA for our 2800 MOF database; a) is colored by the product of GSA and VSA, with

the red ‘X’ denoting the position of NU-1501-Al, b) shows the ideal trade-off region (purple

points), again with NU-1501-Al denoted by the red ‘X’.

NU-1501-Al

a b

63

Fig. S51.

a and b show GSA × VSA vs VF and LPD, respectively. The cutoff to be in the 95th percentile of

GSA × VSA is denoted by the red horizontal line, the average values of VF and LPD for MOFs

in the 95th percentile of GSA × VSA is denoted by the vertical, dashed, yellow, line. The position

of NU-1501 is shown by the yellow ‘X’. c and d are analogous to a and b but colored by MOF

pore size SD. e and f are analogous to a and b but colored by MOF metal atom to organic atom

ratio.

NU-1501-Ala b

c d

e f

NU-1501-Al

NU-1501-Al

64

Fig. S52.

The organic SBUs used to build the 50 acs-b MOFs. a shows the nodular organic SBUs (the

hexatopic linker “body”) and b shows the edge organic SBUs (the hexatopic linker “arms”). MOFs

with ditopic linkers were also considered, by replacing the nodular organic SBUs with the

aluminum metal node of NU-1501. Computational connect points are highlighted in yellow. We

have provided the SMILES strings for the dicarboxylic molecules corresponding to the in the

Table S10.

L9L8L7L6L5L4L3L2L1

L17L16L15L14L13L12L11L10

a

b

N1 N2

65

Fig. S53.

a Shows the VSA vs. GSA plots with MOFs in the 95th percentile of GSA × VSA shown in purple

and MOFs isoreticular with ditopic organic linkers to NU-1501 as orange stars. b Is analogous to

a but showing both isoreticular MOFs with ditopic organic linkers (orange stars) and hexatopic

organic linkers (red stars). c Shows only NU-1501-Al and the 50 isoreticular MOFs, those MOFs

with higher GSA × VSA than NU-1501-Al are colored purple.

a b

c

66

Fig. S54.

a-c Show VDC vs. GDC at the three indicated conditions considered in our 2800 MOF database,

MOFs in the 95th percentile of GDC x VDC are shown as red points, MOFs in the 95th percentile

of GSA x VSA are shown as purple points, MOFs in both categories are shown as red points

outlined in purple. d-f shows again the VSA vs. GSA relationship, but with the same coloration as

in a-c (note that the coloration in plots e and f are similar as MOFs in the 95th percentile of methane

DC at 270 K tend to also be in the 95th percentile at 296 K).

67

Empirical formula C98H56Al3O16

Formula weight 1570.43

Temperature/K 275.15

Crystal system hexagonal

Space group P-6m2

a/Å 24.679(3)

b/Å 24.679(3)

c/Å 17.512(2)

α/° 90

β/° 90

γ/° 120

Volume/Å3 9237(2)

Z 1

ρcalcg/cm3 0.282

μ/mm-1 0.221

F(000) 811.0

Crystal size/mm3 0.2 × 0.065 × 0.065

Radiation CuKα (λ = 1.54178)

2Θ range for data collection/° 4.134 to 108.478

Index ranges -25 ≤ h ≤ 20, -21 ≤ k ≤ 24, -17 ≤ l ≤ 18

Reflections collected 25360

Independent reflections 4103 [Rint = 0.0426, Rsigma = 0.0308]

Data/restraints/parameters 4103/5/126

Goodness-of-fit on F2 1.046

Final R indexes [I>=2σ (I)] R1 = 0.0275, wR2 = 0.0603

Final R indexes [all data] R1 = 0.0371, wR2 = 0.0626

Largest diff. peak/hole / e Å-3 0.10/-0.11

Flack parameter 0.13(4)

Table S1.

Crystal data and structure refinement conditions for NU-1501-Al.

68

MOF NU-1501-Fe-as-synthesized NU-1501-Fe-water treated

Empirical formula C98H56Fe3O16 C98H56Fe3O16

Formula weight 1657.04 1656.97

Temperature/K 275(2) 275(2)

Crystal system hexagonal hexagonal

Space group P-6m2 P-6m2

a/Å 24.963(7) 25.223(5)

b/Å 24.963(7) 25.223(5)

c/Å 17.091(4) 17.120(4)

α/° 90 90

β/° 90 90

γ/° 120 120

Volume/Å3 9223(6) 9433(4)

Z 1 1

ρcalcg/cm3 0.298 0.292

μ/mm-1 0.132 0.129

F(000) 850.0 850.0

Crystal size/mm3 0.3 × 0.2 × 0.2 0.3 × 0.2 × 0.2

Radiation MoKα (λ = 0.71073) MoKα (λ = 0.71073)

2Θ range for data

collection/° 2.382 to 47.048 1.864 to 31.476

Index ranges -28 ≤ h ≤ 21, -20 ≤ k ≤ 28, -

16 ≤ l ≤ 19

-18 ≤ h ≤ 19, -19 ≤ k ≤

14, -13 ≤ l ≤ 13

Reflections collected 40023 11541

Independent reflections 5118 [Rint = 0.0657, Rsigma =

0.0428]

1732 [Rint = 0.1035, Rsigma

= 0.0771]

Data/restraints/parameters 5118/1/126 1732/129/124

Goodness-of-fit on F2 1.361 0.836

Final R indexes [I>=2σ (I)] R1 = 0.0375, wR2 = 0.0768 R1 = 0.0316, wR2 = 0.0495

Final R indexes [all data] R1 = 0.0488, wR2 = 0.0807 R1 = 0.0485, wR2 = 0.0533

Largest diff. peak/hole / e Å-

3 0.22/-0.25 0.09/-0.12

Flack parameter 0.43(2) 0.31(3)

Table S2.

Crystal data and structure refinement results for as-synthesized and water treated NU-1501-Fe.

69

P/P0

(min)

a

P/P0 (max)

a

BET area

(m2 g-1)

Number of

selected

data points

C b R2 c Four BET

consistency

criteria

fulfilledd

0.097 0.102 9150 6 10.138 0.995 1,2

0.096 0.101 8670 5 11.378 0.998 1,2

0.093 0.099 7730 6 15.028 0.999 1,2

0.120 0.132 7310 7 51.912 0.992 1,2,3,4

Table S3.

The linear regions selected for the BET calculation of NU-1501-Al based on the N2 adsorption

isotherm at 77 K.

a Different linear regions were selected for the BET calculation. b C is related to the energetics of

adsorptions according to BET theory. c R2 is the correlation coefficient. d The four BET consistency

criteria proposed by Rouquerol et al.(39): (1) Only a range where N(1−P/P0) increases

monotonically with P/P0 should be selected. (N is the adsorbate loading and P/P0 is relative

pressure.) (2) The value of C resulting from the linear regression should be positive. (3) The

monolayer loading Nm should correspond to a relative pressure P/P0 falling within the selected

linear region. (4) The relative pressure corresponding to the monolayer loading calculated from

BET theory (1/√C + 1) should be equal to the pressure determined in criterion 3. (For this criterion,

Rouquerol et al. suggested a tolerance of 20%.).(40, 74)

70

Materials

Gravimetric

BET area

(m2 g-1)

Four BET

consistency

criteria

fulfilled

Simulated

gravimetri

c BET area

(m2 g-1)

(BET

criteria)

Crystallographic

density (g cm-3)

Pore

diameter

(Å)

Pore volume

(exp.a/sim.b)

(cm3·g-1)

Volumetric

BET areac

(m2 cm-3)

NU-1500-Ald 3560 1,2,3,4 3590

(1,2,3,4) 0.498 ~14 1.46/1.46 1770

NU-1501-Fed 7140 1,2,3,4 6848 (1,2,4) 0.299 15-25 2.90/2.87 2130

NU-1501-Ald 7310 1,2,3,4 6938 (1,2,4) 0.283 15-25 2.91/2.96 2060

NU-1501-Fee 7920 1,2,3 7776 (1,2,3) 0.299 15-25 2.88/2.87 2360

NU-1501-Ale 8145 1,2,3 7761 (1,2,4) 0.283 15-25 2.93/2.96 2300

Table S4.

Measured and Simulated Properties for NU-1500 and NU-1501. a calculated by single point method at P/P0=0.95. b calculated based on crystal structures or

optimized structure. c calculated based on crystallographic density. d calculated based on N2

adsorption isotherm at 77K. e calculated based on Ar adsorption isotherm at 87 K.

71

Table S5.

Comparison of BET area and porosity for selected highly porous materials.a

a Gravimetric BET area and experimental pore volume are obtained from reported value or N2

adsorption isotherm in the reported literatures. b Crystallographic density is calculated based on

crystal structures or optimized structure. c Volumetric BET area is calculated based on

crystallographic density. d Gravimetric BET area is calculated after satisfying all four BET

consistency criteria. e Gravimetric BET area is calculated after satisfying first two BET consistency

criteria.

Materials

Crystallogra

phic density

(g cm-3)b

Gravimetric

BET area

(m2 g-1)

Volumetric

BET areac

(m2 cm-3)

Pore

volume

(cm3 g-1)

Ref.

HKUST-1 0.881 1980 1740 0.77 (5, 41)

MOF-5 0.59 3800 2240 1.55 (75, 76)

MIL-101c 0.44 4230 1860 2.15 (24, 77)

bio-MOF-100 0.302 4300 1300 4.3 (78)

MOF-205/DUT-6 0.38 4460 1695 2.16 (7, 71)

MOF-177 0.43 4500 1935 1.89 (79)

MOF-200 0.22 4530 1000 3.59 (7)

PCN-68 0.402 5110 2050 2.13 (80)

UMCM-2 0.40 5200 2080 2.32 (72)

Al-soc-MOF-1 0.34 5590 1900 2.3 (13)

NU-100 0.29 6140 1780 2.82 (8)

MOF‐210 0.25 6240 1560 3.60 (7)

DUT‐76 0.289 6340 1830 3.25 (81)

DUT‐32 0.27 6410 1730 3.16 (27)

NU-1103 0.298 6550 1950 2.91 (82)

NU‐109 0.237 7010 1660 3.75 (28)

NU‐110 0.222 7140 1585 4.40 (28)

NU-1501-Fed 0.299 7140 2130 2.90 This work

NU-1501-Ald 0.283 7310 2060 2.91 This work

DUT-60e 0.187 7840 1470 5.02 (30)

NU-1501-Fee 0.299 8410 2510 2.90 This work

NU-1501-Ale 0.283 9140 2580 2.91 This work

72

Materials

PV

(cm3

g-1)

Density

(g cm-3)b T

Total uptake

(65 bar)

Total uptake

(80 bar)

Total uptake

(100 bar) Ref.

g g-1 (cm3

cm-3)c g g-1

(cm3

cm-3)c g g-1

(cm3

cm-3)c

Ni-MOF-74 0.56 1.195 273K 0.17 279 0.17 287 0.18 293

(5) 298K 0.15 259 0.16 267 0.17 277

HKUST-1 0.77 0.881 273K 0.24 293 0.24 301 0.25 306

(5) 298K 0.21 263 0.22 272 0.23 281

MOF-519 0.94 0.953

(26) 298K 0.19 259 0.21 279

UTSA-76 1.09 0.699 270K 0.39 300

(83) 298K 0.33 257

MOF-905 1.34 0.549

(25) 298K 0.27 206 0.30 228

NU-1500-Al 1.46 0.498 270K 0.35 241 0.37 255 0.39 273 This

work 296K 0.29 200 0.31 216 0.34 237

COF-102 1.55 0.43 273K 0.39 233

(18) 298K 0.32 195

AX-21 (activated carbon)

1.64 0.487

(5) 298K 0.30 203 0.33 222 0.35 238

NU-111 2.09 0.409 270K 0.50 284

(32) 298K 0.36 205

Al-soc-MOF-

1 2.30 0.34

273K 0.51 242 0.56 267 (13)

298K 0.41 197 0.47 222

ST-2 2.44 0.366 273K 0.43 223 0.48 246

(44) 298K 0.35 181 0.40 206

NU-1501-Fe 2.90 0.299 270K 0.51 214 0.57 239 0.63 264 This

work 296K 0.40 168 0.46 193 0.52 218

NU-1501-Al 2.91 0.283 270K 0.54 214 0.60 238 0.66 262 This

work 296K 0.41 163 0.48 190 0.54 214

MOF-210 3.60 0.25

(7) 298K 0.41 143 0.48 168

Table S6A.

Methane total uptake for selected benchmark MOFs, COFs, and activated carbon. a

a Methane total uptake are obtained or estimated from the methane isotherms in the reported

literatures. b Crystallographic density of MOFs is calculated based on crystal structures or

optimized structure. c Volumetric total uptake is calculated based on crystallographic density.

73

Materials T

Total uptake

(80 bar)

Total uptake

(100 bar)

Deliverable

capacity (5-80

bar)

Deliverable

capacity (5-

100 bar) Ref.

g g-1 (cm3

cm-3)c g g-1

(cm3

cm-3)c g g-1

(cm3

cm-3)c g g-1

(cm3

cm-3)c

Ni-MOF-74 273K 0.17 287 0.18 293 0.08 129 0.08 135

(5) 298K 0.16 267 0.17 277 0.09 152 0.10 162

HKUST-1 273K 0.24 301 0.25 306 0.15 190 0.16 195

(5) 298K 0.22 272 0.23 281 0.16 198 0.17 207

MOF-519

(26) 298K 0.21 279 0.17 230

MOF-905

(25) 298K 0.30 228 0.26 203

NU-1500-Al 270K 0.37 255 0.39 273 0.30 206 0.32 224 This

work 296K 0.31 216 0.34 237 0.26 181 0.29 202

AX-21

(activated

carbon)

(5) 298K 0.33 222 0.35 238 0.26 174 0.28 190

Al-soc-MOF-

1

273K 0.56 267 0.50 238 (13)

298K 0.47 222 0.42 201

ST-2 273K 0.48 246 0.43 220

(44) 298K 0.40 206 0.36 185

NU-1501-Fe 270K 0.57 239 0.63 264 0.51 214 0.57 239 This

work 296K 0.46 193 0.52 218 0.42 176 0.48 201

NU-1501-Al 270K 0.60 238 0.66 262 0.54 214 0.60 238 This

work 296K 0.48 190 0.54 214 0.44 174 0.50 198

MOF-210

(7) 298K 0.48 168 0.45 157

Table S6B.

Methane total uptake and deliverable capacities for selected benchmark MOFs and activated

carbon.a a Methane total uptake are obtained or estimated from the methane isotherms in the

reported literatures. b Crystallographic density of MOFs is calculated based on crystal structures

or optimized structure. c Volumetric total uptake is calculated based on crystallographic density.

74

Table S7. Gravimetric BET area, pore volume, density, volumetric BET area, and H2 working

performance for the MOFs studied.a

a Gravimetric BET area, pore volume, density, gravimetric and volumetric deliverable capacities

are obtained in the reported literatures. The capacity (in wt%) of H2 is calculated according to wt%

= (mass of H2)/(mass of H2 + mass of MOF) × 100%. b Crystallographic density is calculated based

on crystal structures or optimized structure. c Volumetric BET area is calculated based on

crystallographic density.

Materials

BET

area

(m2 g-1)

PV

(cm3 g-1)

Density

(g cm-3)b

Vol.

BET

areac

(m2

cm-3)

H2@(77

K/100 bar

→160 K/5

bar)

Qst (kJ

mol-1) Ref.

wt% g L-1

MOF-5 3510 1.36 0.59 2070 7.8 51.9 - (34)

IRMOF-20 4070 1.65 0.51 2080 9.1 51 - (34)

HKUST-1 1980 0.75 0.881 1740 4.9 46 6.5 (41)

TT-112 3440 1.44 0.446 1530 8.3 41 5.1 (41)

NU-125 3230 1.33 0.578 1870 7.8 49 5.1 (41)

rht-MOF-7 1950 0.79 0.789 1540 4.5 37 5.9 (41)

Cu-MOF-74 1270 0.47 1.323 1680 2.9 39 5.6 (41)

PCN-250 1780 0.71 0.896 1595 4.9 47 6.6 (41)

NU-1000 2200 1.48 0.571 1260 7.7 48 5 (41)

UiO-67 2360 0.91 0.688 1620 5.7 41 5.8 (41)

UiO-68-Ant 3030 1.17 0.607 1840 7.2 47 6 (41)

CYCU-3-Al 2450 1.56 0.477 1170 8.0 41 4.5 (41)

Zn2(BDC)2(DABCO) 2020 0.76 0.873 1760 4.6 42 4.9 (41)

NU-1101 4340 1.72 0.459 1990 9.1 47 5.5 (33)

NU-1102 3720 1.65 0.403 1500 9.6 44 4.5 (33)

NU-1103 6245 2.72 0.298 1860 12.6 43 3.8 (33)

SNU-70 4940 2.14 0.411 2030 10.6 47.9 - (45)

UMCM-9 5040 2.31 0.37 1860 11.3 47.4 - (45)

NU-100 6050 3.17 0.29 1755 13.9 47.6 - (45)

NU-1500-Al 3560 1.46 0.498 1770 8.2 44.6 4.9 This

work

NU-1501-Fe 7140 2.90 0.299 2130 13.2 45.4 4 This

work

NU-1501-Al 7310 2.91 0.283 2060 14.0 46.2 4 This

work

75

Materials Nitrogen (m2 g-1)

NU-1501-Al 5714

NU-1501-Fe 5513

NU-1500-Al 3634

Table S8.

Geometric surface areas calculated with N2 probe.

76

MOF adsorbate H (kJ mol-1)

NU-1500-Al H2 -5.0 ± 0.5

NU-1501-Al H2 -4.0 ±0.3

NU-1501-Al CH4 -10.3 ±0.5

Table S9.

Enthalpies of adsorption (H)a calculated at 296 K, 5 kPa (from fluctuation formula). a Calculations of H from GCMC simulations have good statistics at loadings much lower than

saturation. Heat of adsorption = -H; isosteric heat of adsorption = -H + RT.

77

Linker SMILES

L1 O=C(O)c1ccc(C(=O)O)cc1

L2 O=C(O)c1ccc(C(=O)O)c2ccccc12

L3 O=C(O)c2ccc1cc(C(=O)O)ccc1c2

L4 O=C(O)C#CC#CC(=O)O

L5 O=C(O)C#Cc1ccc(C(=O)O)cc1

L6 O=C(O)c2ccc(c1ccc(C(=O)O)cc1)cc2

L7 O=C(O)c3ccc2c(ccc1cc(C(=O)O)ccc12)c3

L8 O=C(O)c3ccc2cc1cc(C(=O)O)ccc1cc2c3

L9 O=C(O)c1cc2ccc3cc(C(=O)O)cc4ccc(c1)c2c34

L10 O=C(O)c3ccc(c1ccc(C(=O)O)c2ccccc12)cc3

L11 O=C(O)c3ccc(c1ccc(C(=O)O)c2ccccc12)c4ccccc34

L12 O=C(O)c4ccc2c(ccc3c1ccc(C(=O)O)cc1ccc23)c4

L13 O=C(O)C#Cc1ccc(C#CC(=O)O)cc1

L14 O=C(O)c2ccc(C#Cc1ccc(C(=O)O)cc1)cc2

L15 O=C(O)C#Cc2ccc(c1ccc(C(=O)O)cc1)cc2

L16 O=C(O)c3ccc(c2ccc(c1ccc(C(=O)O)cc1)cc2)cc3

L17 O=C(O)c4ccc(c2ccc(c1ccc(C(=O)O)cc1)c3ccccc23)cc4

Table S10.

The SMILES strings for the dicarboxylic species corresponding linkers shown in Fig. S52.

78

Data S1. Crystallographic Information File for as-synthesized NU-1501-Al

Data S2: Crystallographic Information File for as-synthesized NU-1501-Fe

Data S3: Crystallographic Information File for NU-1501-Fe after soaking in liquid water

79

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