Supporting Information

Screening of metal-organic frameworks for

highly effective hydrogen isotope separation
by quantum sieving

Guopeng Han,† Yu Gong,‡ Hongliang Huang,§ Dawei Cao,‡ Xiaojun Chen,*, ‡ Dahuan

Liu,*,† Chongli Zhong*,†,§

†
State Key Laboratory of Organic-Inorganic Composites, Beijing University of
Chemical Technology, Beijing, 100029, China
‡
Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics,
Mianyang, Sichuan, 621900, China

§
State Key Laboratory of Separation Membranes and Membrane Processes, Tianjin
Polytechnic University, Tianjin, 300387, China
*Corresponding authors
E-mail: liudh@mail.buct.edu.cn, xiaojunchen@caep.cn and
zhongcl@mail.buct.edu.cn

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 Contents
S1. Screening of MOFs ………………..….…...…..…………………….......…S-3
S2. Calculation of the PLD for materials….…...…..…………………….......…S-3
S3. Calculation of zero-point energy of D2 and H2.………………………….....S-3
S4. Calculation method of selectivity…..………..…...….…..………..….…….S-4
S5. Preparation and characterization of porous materials….…..………..….…..S-5
S6. Illustration of volumetric adsorption apparatus……………………….……S-10
S7. Desorption spectra of D2/H2 mixture..…..…………………..……….……..S-10
S8. Selectivities of MOFs obtained in this work.……..…….……….…….........S-12
References.……...………………………………..……………………….….....S-14

S-2
S1. Screening of MOFs
The screening methodology mainly includes the following steps. First, MOFs with
too small aperture sizes (less than the hard core sizes of H2 and D2, 2.96 Å) are not
suitable for the adsorption, among which those with too large aperture sizes (larger
than the effective diameter of H2 at 20 K considering the de Broglie wavelength,1-3
5.66 Å) are also excluded that may play a negative role on separation. Thus,
corresponding MOFs were selected from Cambridge Crystallographic Data Centre
(CCDC) database according to their pore limiting diameters (PLD). PLD values of
MOFs were obtained using the open source software Zeo++ for performing
high-throughput structural analysis of nanoporous materials.4 Then, on the basis of the
reported adsorption enthalpy for hydrogen isotopes in nanoporous materials (about
2.0-10.0 kJ/mol),5-8 MOFs with ZPE less than 2.0 kJ/mol were filtered out and the top
350 MOFs with large ∆ZPE values were further selected, as shown in Figure S1. The
MOFs with disordered structure were excluded from top 350 MOFs. Thirdly, 30
MOFs with 1D channel pore were considered, since 1D channel pore structure may
improve the sieving effect due to the narrow porosity in one dimension and can avoid
the diffusion by-pass in the framework. Bearing the convenience of synthesis and the
stability of framework in mind, SIFSIX-3-Zn was ultimately prepared as a candidate
in this work. In addition, this MOF contains abundant fluorine-containing groups
which may enhance the interactions with guest molecules.

S2. Calculation of the PLD for materials.

The open source software Zeo++ is a powerful tool for performing

high-throughput structural analysis of nanoporous materials.4 All the accessible
apertures of MOFs were calculated using the open source software Zeo++ as
mentioned in the main text. The values of several typical MOFs were compared to the
results in literature, which are in good agreement.
S3. Calculation of zero-point energy of D2 and H2.
Zero-point energy can be calculated using the following equation, and the
reliability of calculation can be verified by repeating the reported data 9:

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  ћ
  (1)

  

with i = 0, 1, 2…

γ0 = 2.4, ћ= h / 2π,  = 2.0 or 4.0 / (6.02×1026), kg/mol.

Figure S1. The difference in ZPE for D2 and H2 as a function of aperture.

S4. Calculation method of selectivity

The selectivity is defined as the ratio of molar fractions in the adsorbed phase ()
10
and gas phase (y) :
 / , /,
2 2 2 2

 /

, /,
(2)
2 2 2 2

The direct mixture selectivity can be determined from the ratio of desorbed amount
of D2 over H2 (SD2/H2) for a 1:1 D2/H2 mixture. Thus, SD2/H2 can be obtained as:
, 
 /  
  ,"# (3)
,! ,"#

where D2,area and H2,area are the areas under the desorption peak of each species,
respectively.

S5. Preparation and characterization of porous materials.

S-4
 S5.1 SIFSIX-3-Zn.11,12 A solution of pyrazine prepared by dissolving pyrazine (0.10

g) in methanol (2.0 ml) was slowly added to a solution of ZnSiF6 comprising ZnSiF6

(0.13 g) and methanol (2.0 ml) without agitation. The reagents reacted at room

temperature for 3 d. After the reaction, obtained crystals were washed with a lot of

methanol and dried at 330 K in a vacuum oven. Then, the colorless crystal was

available.

S5.2 HKUST-1.13 A solid mixture of Cu(NO3)2•3H2O (2.07 g) and benzene-1, 3,

5-tricarboxylic acid (1.00 g) was added to a 1:1:1 (v/v/v) mixture of DMF–ethanol–

water (45.0 ml) and mixed thoroughly until it was completely dissolved. Then, the

resultant solution mixture was transferred into a Teflon liner (100 ml). It was kept at

373 K for 10 h in oven to yield small crystals. The autoclave was cooled down to

room temperature and the blue crystals were isolated by filtration. The suspension

was washed with the mixture of DI water and ethanol several times and dried.

S5.3 FCTF-1-400.14 Terephthalonitrile (2.50 g) and ZnCl2 (2.70 g) were well mixed

by grinding and the mixture was transferred into a Pyrex ampoule. The ampoule was

evacuated, sealed and heated at 673 K for 40 h. Then the ampoule was allowed to cool

to room temperature. The product was washed thoroughly with diluted HCl and DI

water overnight to remove the residual salt.

S5.4 STAM-1.15 A solid mixture of Cu(NO3)2•3H2O (0.99 g), benzene-1, 3,

5-tricarboxylic acid (0.86 g), MeOH (10.0 ml), DI water (10.0 ml) was mixed

thoroughly until it was completely dissolved. It was kept at 383 K for 7 days in oven

S-5
to yield small crystals. Then the autoclave was cooled down to room temperature

naturally and the blue crystals were isolated by filtration. The suspension was washed

with methanol several times and dried.

S5.5 KAUST-7.16 Pyrazine (384 mg), Ni(NO3)2•6H2O (174 mg), Nb2O5 (80 mg)

and HFaq 48% (0.26 ml) were mixed in a 20 ml Teflon liner. The mixture was diluted

with DI water (3.0 ml) and then the autoclave was sealed and heated to 400 K for 24

h. After cooling down to room temperature, the resultant violet square-shaped crystals

were collected by filtration, washed with ethanol and dried in air.

S5.6 SIFSIX-3-Cu.17 A methanol solution (5.0 ml) of pyrazine (0.30 g) was layered

in a glass tube onto a methanol solution (5.0 ml) of CuSiF6•H2O (0.36 g). On layering,

an extremely fast formation of light violet powder was observed, which was left for

24 h in the mother solution. The powder was then collected and washed extensively

with methanol then dried under vacuum.

S5.7 SIFSIX-3-Ni.18 A solid mixture of Ni(NO3)2 (870 mg), (NH4)2SiF6 (534 mg)

and of pyrazine (480 mg,) was added into water (4.0 ml) and stirred for 2 days. The

resulting suspension was filtered under vacuum and dried in air. This precursor was

soaked in methanol for 1 day and then washed twice with two portions of methanol

(10.0 ml) on a Buchner filter. After drying in air, the solid was heated at 413 K for 1

day to obtain SIFSIX-3-Ni.

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 S5.8 Cu-PYC.19 An aqueous ammonia solution (NH3/H2O 1:15, 30.0 ml) containing

4-carboxypyrazole (226 mg) and Cu(NO3)2 (376 mg) led to a blue solution. Dark blue

crystals can be obtained in three days.

S5.9 CPO-27-Co.20 A solid mixture of H4DOBDC (2, 5-dihydroxyterephthalic acid,

0.05 g) and Co(NO3)2•6H2O (0.24 g) was added to a 1:1:1 (v/v/v) mixture of DMF–

ethanol–water (20.0 ml) in a Teflon liner (100 ml). The suspension was mixed and

ultrasonicated until homogeneous. The system was heated to 373 K at a rate of 1

K/min, and held at 373 K for 24 h. After cooling to room temperature at a rate of 1

K/min, the resulting red-orange trigonal crystals were isolated, and washed four times

with methanol to remove the excess of unreacted H4DOBDC respectively, then the

crystals were decanted and activated under vacuum at 523 K over 5 hours.

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Figure S2. Experimental and simulation PXRD patterns of samples in this work: (a) SIFSIX-3-Zn;

(b) HKUST-1; (c) STAM-1; (d) KAUST-7; (e) SIFSIX-3-Ni; (f) SIFSIX-3-Cu; (g) SIFSIX-1-Cu;

(h) Cu-PYC; (i) CPO-27-Co; (j) FCTF-1-400.

S-8
 100

Weight (%)
75

50

25
300 400 500 600
Temperture (K)
Figure S3. TGA curves of SIFSIX-3-Zn.

Figure S4. SEM images of SIFSIX-3-Zn with different magnifications: (a) 1000; (b) 10000.

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S6. Illustration of volumetric adsorption apparatus.

(a) (b)

Figure S5. (a) Schematic diagram of volumetric adsorption apparatus. (b) Illustration of adsorption

and desorption process. (1, vacuum system; 2, pressure transducer; 3, quadrupole MS with turbo

molecular pump; 4, cold trap; 5, sample holder; 6, auxiliary heater; 7, thermocouple; 8, sample; 9,

cold finger. Ball valves: V1, V2, V3, V4, V5, V6 and V7)

S7. Desorption spectra of D2/H2 mixture.

Figure S6. H2 (black, filled symbols) and D2 (red, open symbols) desorption spectra of 3 kPa (1:1

D2/ H2 mixture) in CPO-27-Co: (a) 20 K; (b) 60 K.

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 Table S1. Comparisons of the results of CPO-27-Co with those in literature at 3 kPa.10

Selectivity D2 uptake (cc/g)

Comparison
This work Ref. 10 This work Ref. 10

20 K 3.0 3.0 315.6 313.2

60 K 12.1 11.8 67.6 66.0

Figure S7. H2 (black) and D2 (red) desorption spectra loading on different porous materials at 20 K

(1:1 D2/ H2 mixture, 10 kPa).

S-11
S8. Selectivities of MOFs obtained in this work.

Figure S8. Selectivities of D2/H2 and D2 uptake as a function of pressure at 20 K and 25 K.

S-12
 Table S2. Comparisions of selectivities of D2/H2 in porous materials

Temperature Pressure D2 uptake Aperture

Materials (K) (kPa) S(D2/H2) (a) (cc/g) (Å) Reference

SIFSIX-3-Zn 20 10-25 50.0-53.8 21.5 3.86 This work

HKUST-1 20 10-25 17.0-26.0 408.0 6.66, 13.31 This work

FCTF-1-400 20 10 12.8 442.0 5.40 This work

Py@COF-1 22 2.6 10.0 15.7 2.90 21

STAM-1 20 10 9.9 64.0 6.19 This work

KAUST-7 20 10 9.8 8.5 2.65 This work

SIFSIX-1-Cu 20 10 7.1 3.0 7.11 This work

COF-1 19.5 10 7.0(b) 440.0 9.00 6

SIFSIX-3-Cu 20 10 3.5 1.5 3.56 This work

CPO-27(Co) 20 3 3.0 313.0 10.00 This work

Cu-PYC 20 10 2.2 234.0 6.49 This work

SIFSIX-3-Ni 20 10 1.9 18.8 3.68 This work

Fluorinated-ACFs 20 10 1.3(b) 284.0 8.80 5

ox-SWCNT 20 25 1.2(b) 672.0 1

SWCNT 20 25 1.2(b) 1052.8 20.00 4

band-SWCNT 20 25 1.1(b) 380.0 1

zeolite 5 Å 20.4 1 1.0 220.0 5.00 7

ZIF-8 19.5 10 1.0(b) 537.0 3.40 6

ZIF-7 19.5 10 1.0(b) 4.0 3.00 6

COF-102 19.5 10 1.0(b) 1411.0 12.00 6

(a) Experimentally determined (ACTDS) 1:1 D2/H2 mixture selectivity.

(b) D2/H2 molar ratios obtained from the pure gas adsorption isotherms.

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References
(1) Kagita, H.; Ohba, T.; Fujimori, T.; Tanaka, H.; Hata, K.; Taira, S.-I.; Kanoh, H.; Minami, D.;

Hattori, Y.; Itoh, T.; Masu, H.; Endo, M.; Kaneko, K. Quantum Molecular Sieving Effects of H2

and D2 on Bundled and Nonbundled Single-Walled Carbon Nanotubes. J. Phys. Chem. C 2012,

116, 20918-20922.

(2) Wang, Y.; Zhao, D. Beyond Equilibrium: Metal–Organic Frameworks for Molecular Sieving

and Kinetic Gas Separation. Cryst. Growth Des. 2017, 17, 2291-2308.

(3) Savchenko, I.; Mavrandonakis, A.; Heine, T.; Oh, H.; Teufel, J.; Hirscher, M. Hydrogen

Isotope Separation in Metal-Organic Frameworks: Kinetic or Chemical Affinity Quantum-Sieving?

Microporous Mesoporous Mater. 2015, 216, 133-137.

(4) Thomas, F. W.; Chris, H. R.; Michaeel, K.; Juan, C. M.; Maciej, H. Algorithms and Tools for

High-Throughput Geometry-Based Analysis of Crystalline Porous Materials. Microporous

Mesoporous Mater. 2012, 149, 134–141.

(5) Hattori, Y.; Tanaka, H.; Okino, F.; Touhara, H.; Nakahigashi, Y.; Utsumi, S.; Kanoh, H.;

Kaneko, K. Quantum Sieving Effect of Modified Activated Carbon Fibers on H2 and D2

Adsorption at 20 K. J. Phys. Chem. B 2006, 110, 9764-9767.

(6) Oh, H.; Park, K. S.; Kalidindi, S. B.; Fischerc, R. A.; Hirscher, M. Quantum Cryo-Sieving for

Hydrogen Isotope Separation in Microporous Frameworks: An Experimental Study on the

Correlation between Effective Quantum Sieving and Pore Size. J. Mater. Chem. A 2013, 1,

3244-3248.

(7) Xiong, R.; Xicohténcatl, R. B.; Zhang, L.; Li, P.; Yao, Y.; Sang, G.; Chen, C.; Tang, T.; Luo, D.;

Hirscher, M. Thermodynamics, Kinetics and Selectivity of H2 and D2 on Zeolite 5A below 77K.

Microporous Mesoporous Mater. 2018, 264, 22-27.

(8) Zhou, W.; Wu, H.; Yildirim, T. Enhanced H2 Adsorption in Isostructural Metal−Organic

Frameworks with Open Metal Sites: Strong Dependence of the Binding Strength on Metal Ions. J.

Am. Chem. Soc. 2008, 130, 15268-15269.

(9) Beenakker, J. J. M.; Borman, V. D.; Krylov, S. Y. Molecular Transport in Subnanometer Pores:

Zero-Point Energy, Reduced Dimensionality and Quantum Sieving. Chem. Phys. Lett. 1995, 232,

379-382.
S-14
(10) Oh, H.; Savchenko, I.; Mavrandonakis, A.; Heine, T.; Hirscher. M. Highly Effective

Hydrogen Isotope Separation in Nanoporous Metal–Organic Frameworks with Open Metal Sites:

Direct Measurement and Theoretical Analysis. ACS Nano 2014, 8, 761-770.

(11) Uemura, K.; Maeda, A.; Maji, T. K.; Kanoo, P.; Kita, H. Syntheses, Crystal Structures and

Adsorption Properties of Ultramicroporous Coordination Polymers Constructed from

Hexafluorosilicate Ions and Pyrazine. Eur. J. Inorg. Chem. 2009, 2009, 2329-2337.

(12) Nugent, P.; Belmabkhout, Y.; Burd, S. D.; Cairns, A. J.; Luebke, R.; Forrest, K.; Pham, T.; Ma,

S.; Space, B.; Wojtas, L.; Eddaoudi, M.; Zaworotko, M. J. Porous Materials with Optimal

Adsorption Thermodynamics and Kinetics for CO2 Separation. Nature 2013, 495, 80-84.

(13) Lin, K. S.; Adhikari, A. K.; Ku, C. N.; Chiang, C. L.; Kuo, H. Synthesis and Characterization

of Porous HKUST-1 Metal-Organic Frameworks for Hydrogen Storage. Int. J. Hydrogen Energy

2012, 13, 13865-13871.

(14) Zhao, Y.; Yao, K.; Teng, B.; Zhang, T.; Han, Y. A Perfluorinated Covalent Triazine-Based

Framework for Highly Selective and Water–Tolerant CO2 Capture. Energy Environ. Sci. 2013, 6,

3684-3692.

(15) Mohideen, M. infas H.; Xiao, B.; Wheatley, P. S.; McKinlay, A. C.; Li, Y.; Slawin, A. M. Z.;

Aldous, D. W.; Cessford, N. F.; ¨ren, T. D.; Zhao, X.; Gill, R.; Thomas, K. M.; Griffin, J. M.;

Ashbrook, S. E.; Morris, R. E. Protecting Group and Switchable Pore-Discriminating Adsorption

Properties of a Hydrophilic–Hydrophobic Metal–Organic Framework. Nat. Chem. 2013, 3,

304-310.

(16) Cadiau, A.; Adil, K.; Bhatt, P. M.; Belmabkhout, Y.; Eddaoudi, M. A Metal-Organic

Framework–Based Splitter for Separating Propylene from Propane. Science 2016, 353, 137-140.

(17) Shekhah, O.; Belmabkhout, Y.; Chen, Z. J.; Guillerm, V.; Cairns, A.; Adil, K.; Eddaoudi, M.

Made-to-Order Metal-Organic Frameworks for Trace Carbon Dioxide Removal and Air Capture.

Nat. Commun. 2014, 5, No. 4228.

(18) Kumar, A.; Madden, D. G.; Lusi, M.; Chen, K.; Daniels, E. A.; Curtin, T.; Perry IV J. J.;

Zaworotko, M. J. Direct Air Capture of CO2 by Physisorbent Materials. Angew. Chem. Int. Ed.

2015, 54, 14372-14377.

(19) Procopio, E. Q.; Linares, F.; Montoro, C.; Colombo, V.; Maspero, A.; Barea, E.; Navarro, J. A.

R. Cation‐Exchange Porosity Tuning in Anionic Metal–Organic Frameworks for the Selective

S-15
Separation of Gases and Vapors and for Catalysis. Angew. Chem. Int. Ed. 2010, 49, 7308-7311.

(20) Caskey, S. R.; Wong-Foy, A. G.; Matzger, A. J. Dramatic Tuning of Carbon Dioxide Uptake

via Metal Substitution in A Coordination Polymer with Cylindrical Pores. J. Am. Chem. Soc. 2008,

130, 10870-10871.

(21) Oh, H.; Kalidindi, S. B.; Um, Y.; Bureekaew, S.; Schmid, R.; Fischerand, R. A.; Hirscher, M.

A Cryogenically Flexible Covalent Organic Framework for Efficient Hydrogen Isotope Separation

by Quantum Sieving. Angew. Chem. Int. Ed. 2013, 52, 13219-13222.

S-16