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SUPPLEMENTARY INFORMATIONDOI: 10.1038/NCHEM.1457

1

Supplementary Information

Selectivity and Direct Visualisation of Carbon Dioxide and Sulphur

Dioxide in a Decorated Porous Host

Sihai Yang,1* Junliang Sun,2 Anibal J. Ramirez-Cuesta,3 Samantha K. Callear,3 William I.F. David,3,4

Daniel Anderson,1 Ruth Newby,1 Alexander J. Blake,1 Julia E. Parker,5 Chiu C. Tang5 and Martin Schröder1*

[1] School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD (UK)

Fax: +44 115 951 3563 E-mail: [email protected]; [email protected]

[2] College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871 (China)

[3] ISIS Facility, Rutherford Appleton Laboratory, Chilton, Oxfordshire, OX11 0QX (UK)

[4] Inorganic Chemistry Laboratory, University of Oxford, South Parks Road, OX1 3QR (UK)

[5] Diamond Light Source, Harwell Science and Innovation

1

Supplementary Information

Selectivity and Direct Visualization of Carbon Dioxide and Sulfur

Dioxide in a Decorated Porous Host

Sihai Yang,1* Junliang Sun,2 Anibal J. Ramirez-Cuesta,3 Samantha K. Callear,3 William I.F. David,3,4

Daniel Anderson,1 Ruth Newby,1 Alexander J. Blake,1 Julia E. Parker,5 Chiu C. Tang5 and Martin Schröder1*

[1] School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD (UK)

Fax: +44 115 951 3563 E-mail: [email protected]; [email protected]

[2] College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871 (China)

[3] ISIS Facility, Rutherford Appleton Laboratory, Chilton, Oxfordshire, OX11 0QX (UK)

[4] Inorganic Chemistry Laboratory, University of Oxford, South Parks Road, OX1 3QR (UK)

[5] Diamond Light Source, Harwell Science and Innovation

© 2012 Macmillan Publishers Limited. All rights reserved.



2

Index

1. Experimental Section

1.1 Physical Characterisation

1.2 Gas Adsorption Isotherms

1.3 Inelastic Neutron Scattering

1.4 DFT Modelling and Simulations

2. In Situ Synchrotron X-Ray Powder Diffraction Patterns

3. Transmission Electron Microscopic (TEM) Study

4. Additional View of Crystal Structures

5. TGA plot for NOTT-300-solvate

6. Synchrotron Powder Diffraction Studies of Solvated NOTT-300

7. Variable Temperature Powder Diffraction

8. Additional Gas Sorption Isotherm Plots for NOTT-300

9. Exposure of NOTT-300 to water

10. Additional Inelastic Neutron Scattering Spectra

11. Analysis and Derivation of the Isosteric Heat of Adsorption for CO2

12. Calculation of Henry’s Law selectivity for gas adsorption

13. Summary of the hydrogen bond interaction

14. Film of the Dynamics of the Crystal Lattice upon CO2 Inclusion in NOTT-300

15. References




3

1. Experimental Section

1.1 Physical Characterisation.

All reagents were used as received from commercial suppliers without further purification. Analyses

for C, H and N were carried out on a CE-440 elemental analyzer (EAI Company). Thermal gravimetric

analyses (TGA) were performed under N2 flow (100 ml/min) with a heating rate of 2 °C/min using a TA

SDT-600 thermogravimetric analyzer (TA Company). IR spectra were recorded using a Nicolet Avatar 360

FT-IR spectrophotometer. High-resolution transmission electron microscopy (TEM) imaging was performed

using a Jeol 2100F transmission electron microscope using an accelerating voltage of 100 kV. TEM samples

were prepared by casting several drops of a suspension of the NOTT-300-solvate complex in water onto

copper-grid mounted lacy carbon film before drying under a stream of nitrogen. Variable temperature

powder X-ray diffraction data (PXRD) were collected over the 2θ range 4-50o on a Bruker Advance D8

diffractometer using Cu-Kα1 radiation (λ = 1.54056 Å, 40 kV/40mA), and the temperature was controlled by

an Oxford Cryosystems open-flow cryostat operating at 100–483 K.

1.2 Gas Adsorption Isotherms.

CO2, SO2, CH4, CO, N2, O2, H2 and Ar sorption isotherms were recorded at 77 K (liquid nitrogen),

87 K (liquid argon) or 273-303 K (temperature-programmed water bath from Hiden Company) on an IGA-

003 system at the University of Nottingham under ultra-high vacuum from a diaphragm and turbo pumping

system. All gases used were ultra-pure research grade (99.999%) purchased from BOC or AIRLIQUIDE.

The density of the desolvated NOTT-300 sample used in buoyancy corrections was 1.80 g cm-3 and was

estimated from the crystallographic density of the desolvated sample derived from the PLATON/SOLV1

results. In a typical gas adsorption experiment, ~100 mg of NOTT-300-solvate was loaded into the IGA, and

degassed at 120 oC and high vacuum (10-10 bar) for 1 day to give fully desolvated NOTT-300.

1.3 Inelastic Neutron Scattering.

INS spectra were recorded on the TOSCA spectrometer at the ISIS Facility at the Rutherford

Appleton Laboratory (UK) for energy transfers between ~-2 and 500 meV. In this region TOSCA has a

resolution of ~1% ΔE/E. The desolvated NOTT-300 sample was loaded into a cylindrical vanadium sample




4

container with an annealed copper vacuum seal and connected to a gas handling system. The sample was

degassed at 10-7 mbar and 140 °C for 1 day to remove any remaining trace guest water molecules. The

temperature during data collection was controlled using a helium cryostat (7 ± 0.2 K). The loading of CO2

was performed at room temperature in order to ensure that CO2 was present in the gas phase when not

adsorbed and also to ensure sufficient mobility of CO2 inside the crystalline structure of NOTT-300. The

loading of H2 was performed at 40-50 K in order ensure that H2 was adsorbed into NOTT-300. Subsequently,

the temperature was reduced to below 10 K in order to perform the scattering measurements with the

minimum achievable thermal motion for CO2 or H2. Background spectra (sample can plus NOTT-300) were

subtracted to obtain the difference spectra. INS was used to study the binding interaction and structure

dynamics in this case, because it has several unique advantages:

INS spectroscopy is ultra-sensitive to the vibrations of hydrogen atoms, and hydrogen is ten times

more visible than other elements due to its high neutron cross-section.

The technique is not subject to any optical selection rules. All vibrations are active and, in principle,

measurable.

INS observations are not restricted to the centre of the Brillouin zone (gamma point) as is the case

for optical techniques.

INS spectra can be readily and accurately modelled: the intensities are proportional to the

concentration of elements in the sample and their cross-sections, and the measured INS intensities

relate straightforwardly to the associated displacements of the scattering atom. Treatment of

background correction is also straightforward.

Neutrons penetrate deeply into materials and pass readily through the walls of metal containers

making neutrons ideal to measure bulk properties of this material.

INS spectrometers cover the whole range of the molecular vibrational spectrum, 0-500 meV (0-4000

cm-1)

INS data can be collected at below 10 K, where the thermal motion of the MOF material and

adsorbed CO2 molecules can be significantly reduced.




5

1.4 DFT Modelling and Simulations.

The vibrational properties of the NOTT-300 were calculated using a combination of density

functional theory (DFT) and plane-wave pseudopotential methods as implemented in the CASTEP code,2

using ultra-soft pseudopotentials with a plane-wave energy cutoff of 380 eV. Calculations were performed

under the PBE approximation3 for exchange and correlation. The unit cell used has a volume of 2589.2 Å3

and contains 144 and 156 atoms for the bare and CO2-loaded materials, respectively. The wave functions

were sampled according to the Monkhorst-Pack scheme with a k-points mesh of spacing ~0.05 Å-1. The

normal modes of the solid were determined from dynamical matrices calculated using finite displacements,

by numerical differentiation. The INS spectra was the calculated using the aClimax software.4

The calculation of the bare material is computationally stable, in the calculation of the vibrational

frequencies, all the frequencies are positive. In the calculation of the MOF material loaded with four CO2

molecules per unit cell (Fig. S1), corresponding to NOTT-300·1.0CO2, 8 imaginary frequency modes were

found. Following the methodology previously used in MOF modelling,5 we calculated the potential energy

surface (PES) along each of the negative frequency modes (corresponding to the rocking motion of the CO2

unit). The obtained PES (Fig. S1) confirms that the zero-point energy (ZPE) level (the ground state) lies at an

energy above the local minimum calculated by DFT. This means that these PES, although corresponding to

an unstable structure from a static classical point of view, are indeed stable structures from the quantum

mechanical view.

The location of SO2 molecules in NOTT-300 has been optimised by DFT modelling based on the

measured INS spectra. The DFT calculation was performed using the same settings as in the case of CO2.

Notably, a high symmetry configuration, which does not take into account the disorder of SO2 molecules in

the channel, was used.




6

Figure S1. The potential energy surface along the first vibrational eigenvector. At the centre it is clear thatthe potential would give an unstable configuration from a classical point of view. The calculated solution ofthe Schrödinger equation gives the energy levels at 14.2 and 81 cm-1. The ZPE is higher than the localmaximum so that from a quantum point of view, the system is in a stable equilibrium.




7

2. In Situ Synchrotron X-Ray Powder Diffraction Patterns

a

b

Figure S2. (a) PXRD patterns [observed (blue), calculated (red) and difference (grey)] for the Rietveldrefinement of the as-synthesized NOTT-300-solvate [λ = 0.826949(2) Å]; (b) higher angle data (2θ = 22.5-

55o) scaled up to show the quality of the fit between the observed and the calculated patterns.

5 10 15 20 25 30 35 40 45 50 55

ObservedCalculatedDifference

Inte

nsity

2degrees

25 30 35 40 45 50 55


Inte

nsity

2degrees




8

a

b

Figure S3. (a) PXRD patterns [observed (blue), calculated (red) and difference (grey)] for the Rietveldrefinement of the CO2-loaded NOTT-300·3.2CO2 [λ = 0.826126(2) Å]; (b) higher angle data (2θ = 22.5-60o)scaled up to show the quality of fit between the observed and the calculated patterns.

5 10 15 20 25 30 35 40 45 50 55 60


Inte

nsity

2degrees

25 30 35 40 45 50 55 60


Inte

nsity

2degrees




9

a

b

Figure S4. (a) PXRD patterns [observed (blue), calculated (red) and difference (grey)] for the Rietveldrefinement of the SO2-loaded NOTT-300·4SO2 [λ = 0.826126(2) Å]; (b) higher angle data (2θ = 22.5-55o)scaled up to show the quality of fit between the observed and the calculated patterns.

5 10 15 20 25 30 35 40 45 50 55


Inte

nsity

2degrees

25 30 35 40 45 50 55


Inte

nsity

2degrees




10

a

b

Figure S5. (a) Comparison of the powder diffraction patterns for original, evacuated, SO2-loaded, and finaldesolvated samples at 273 K; (b) higher angle data (2θ = 4.5-25o) has been scaled up to show the changesupon SO2 inclusion. NOTT-300 retains crystallinity after removal of SO2.

10 20 30 40

regenerated NOTT-300 after SO2removal

NOTT-300.SO2

1.0 bar SO2

NOTT-300.SO2

0.5 bar SO2

NOTT-300NOTT-300-solv

Inte

nsity

2degrees

6 8 10 12 14 16 18 20 22 24

regenerated NOTT-300 after SO2 removalNOTT-300 NOTT-300.SO2 0.5 bar SO2NOTT-300-solv NOTT-300.SO2 1.0 bar SO2

Inte

nsity

2degrees




11

a

b

Figure S6. (a) Powder X-ray diffraction patterns for original, evacuated, CO2-loaded, and final desolvatedsamples at 273 K; (b) higher angle data (2θ = 4.5-25o) has been scaled up confirming that NOTT-300 retainscrystallinity on removal of CO2.

10 20 30 40

regenerated NOTT-300 after CO2removal

NOTT-300.CO2

1.0 bar CO2

NOTT-300.CO2 0.5 bar CO2NOTT-300NOTT-300-solv

Inte

nsity

2degrees

6 8 10 12 14 16 18 20 22 24

regenerated NOTT-300 after CO2 removalNOTT-300 NOTT-300.CO2 0.5 bar CO2NOTT-300-solv NOTT-300.CO2 1.0 bar CO2

Inte

nsity

2degrees




12

Table S1. Atomic positions for non-hydrogen atoms in NOTT-300-solvate.

x y z Biso (Å2)

Al1 0.69426(5) 0.30574(5) 0.5 0.72(13)

O1 0.75744(13) 0.25 0.625 0.51(12)

O2 0.89782(9) 0.28675(9) 0.99869(15) 0.51(12)

O3 0.62165(10) 0.37371(10) 0.39436(12) 0.51(12)

C1 0.59280(15) 0.36039(14) 0.69453(19) 0.70(13)

C2 0.54498(10) 0.43181(7) 0.75722(10) 0.70(13)

C3 0.5 0.5 0.69649(14) 0.70(13)

C4 0.54071(10) 0.428618(71) 0.87716(8) 0.70(13)

C5 0.5 0.5 0.93474(11) 0.70(13)

O1w 0.91080(23) 0.80489(16) 0.94077(28) 21.6(2)

O2w 0.45734(19) 0.73953(30) 0.06123(32) 11.9(3)

O3w 0.13041(22) 0.29586(24) 0.53782(37) 35.7(3)




13

Table S2. Atomic positions for NOTT-300·3.2CO2.

X y z Biso (Å2)

Al1 0.30694(4) -0.30694(4) 0.5 0.93(40)

O1 0.75117(13) 0.25 0.625 0.82(40)

H1 0.8123(17) 0.25 0.625 0.75(40)

O2 0.62152(22) 0.37975(22) 0.60276(28) 0.82(40)

O3 0.60511(22) 0.28380(22) 0.75032(28) 0.82(40)

C1 0.59215(19) 0.36044(15) 0.70222(15) 1.37(40)

C2 0.54078(8) 0.43003(6) 0.76456(13) 1.37(40)

C3 0.5 0.5 0.70584(14) 1.37(40)

H3 0.5 0.5 0.6125(7) 1.37(40)

C4 0.54078(8) 0.43003(6) 0.88199(13) 1.37(40)

H4 0.5675(4) 0.3842(6) 0.9205(6) 1.37(40)

C5 0.5 0.5 0.94071(14) 1.37(40)

C1_1 1.0335(25) 0.25 0.6676(12) 15.1(2)

O1_1 0.9673(23) 0.25 0.625 18.7(5)

O2_1 1.0998(22) 0.25 0.7102(24) 39.4(8)

C1_2 0.25 0.35535 0.375 18.3(2)

O1_2 0.32821 0.35535 0.375 38.4(8)




14

Table S3. Atomic positions for NOTT-300·4SO2.

X y z Biso (Å2)

Al1 0.30668(4) -0.30668(4) 0.5 0.83(11)

O1 0.75093(11) 0.25 0.625 0.50(11)

H1 0.8094(7) 0.2737(13) 0.6182(19) 0.75(17)

O2 0.87680(8) 0.12169(8) 0.10281(9) 0.50(11)

O3 0.89634(7) 0.21365(7) 0.25360(13) 0.50(11)

C1 0.85735(12) 0.09466(13) 0.79858(16) 0.90(12)

C2 0.53958(11) 0.43084(7) 0.75958(9) 0.90(12)

C3 0.5 0.5 0.69441(10) 0.90(12)

H3 0.5 0.5 0.6125(7) 1.09(14)

C4 0.54005(7) 0.42960(5) 0.87811(9) 0.90(12)

H4 0.57318 0.38162 0.90735 1.09(14)

C5 0.5 0.5 0.93693(9) 0.90(12)

S1 0.062518 0.257889 -0.415951 15.1(2)

O1s -0.036130 0.243180 -0.416293 5.8(2)

O2s 0.110299 0.250886 -0.525706 39.4(8)

S2 0.103150 0.184862 -0.037573 18.3(2)

O3s 0.117697 0.239213 -0.143103 38.4(8)

O4s 0.123069 0.242537 0.063692 24.4(4)




15

3. Transmission Electron Microscopic (TEM) Study.

A TEM image shows the crystals to have uniform morphology of ~1 μm plates (Fig. S7a,b), and a high

resolution (HRTEM) image confirms the presence of extended crystalline planes (Fig. S7c).

a

b

c

Figure S7. TEM images for NOTT-300-solvate.




16

4. Additional View of Crystal Structures.

Figure S8. View of the structure of NOTT-300-solvate along the a-axis.

a b

Figure S9. View of the structure of NOTT-300·1.0CO2 along the c-axis (a) and a-axis (b). The structure wasobtained by DFT simulation. The adsorbed CO2 molecules in the pore channel are highlighted by the use ofspacing filling style.




17

a b c

Figure S10. Detailed views of -OH and -CH groups binding CO2 in the “pocket” cavity of NOTT-300·1.0CO2. Views along (a) the a-axis, (b), the b-axis and (c) the c-axis. The moderate hydrogen bondbetween O(δ-) of CO2 and H(δ+) of -OH is highlighted in cyan, [O···H = 2.335 Å]. The weak cooperative

hydrogen bond between O(δ-) of CO2 and H(δ+) from -CH is highlighted in purple, [O···H = 3.029, 3.190Å

with each occurring twice]. Therefore, each O(δ-) centre interacts with five different H(δ+) centres.

a b

Figure S11. View of the structure of NOTT-300·4.0SO2 along the c-axis (a) and a-axis (b). The structure wasobtained by Rietveld refinement of high resolution powder diffraction data collected for NOTT-300·4.0SO2.The adsorbed SO2 molecules in the pore channel are highlighted by the use of spacing filling style.




18

a b c

Figure S12. Detailed views of -OH and -CH groups binding SO2 in the “pocket” cavity of NOTT-300·4.0SO2. Views along (a) the a-axis, (b), the b-axis and (c) the c-axis. The modest hydrogen bondbetween O(δ-) of SO2(I) and H(δ+) from -OH is highlighted in cyan, [O···H = 2.376(13) Å]. The weak

cooperative hydrogen bond between O(δ-) of SO2 and H(δ+) from -CH is highlighted in purple, [O···H =

2.806(14), 2.841(17), 3.111(16), 3.725(18) Å]. Therefore, each O(δ-) centre is interacting with five different

H(δ+) centres. The bond distance between S(δ+) of SO2(I) and O(δ-) of SO2(II) is 3.34(7) Å and highlightedin blue. The S-O bond distances are 1.481(4) and 1.500(8) Å for SO2(I) and SO2(II), respectively. The



19

5. TGA plot for NOTT-300-solvate.

A TGA plot shows that the as-synthesised sample NOTT-300-solvate loses solvent rapidly between 30 and

100 °C, with a plateau observed from 100-200 °C indicating no further weight loss to give NOTT-300. The

weight loss of 20.0 % from NOTT-300-solvate between 20 and 200 °C corresponds to a loss of three water

molecules per aluminium (calc. 20.6 wt%). Above 400°C NOTT-300 starts to decompose rapidly.

Figure S13. TGA plot for NOTT-300-solvate.

100 200 300 400 500 600 700 8000

20

40

60

80

100

Wei

ghtl

oss

(wt%

)

Temperature oC




20

6. Synchrotron Powder Diffraction Studies of Solvated NOTT-300.

To investigate the chemical stability of desolvated NOTT-300, an important feature for a capture material,

PXRD patterns were collected for a range of NOTT-300 samples under variable chemical environments.

After the collection of an original pattern for the as-synthesised sample, NOTT-300-solvate was degassed at

150 oC to generate desolvated NOTT-300. The desolvated material was then separated into ten portions, each

of which was exposed to air for one month, or immersed in water, methanol, ethanol, CHCl3, CH3CN, DMF,

THF, benzene or toluene for one week. Comparison of the resultant PXRD patterns confirms the excellent

stability of the desolvated NOTT-300 material under air, water and common organic solvents.

Figure S14. Comparison of powder diffraction patterns of NOTT-300 under different chemical environment[λ=0.826134(2) Å].

4 8 12 16 20 24 28 32 36 40

Inte

nsity

2degrees

ethanol toluenemethanol benzenewater THFexposed to air DMFNOTT-300 CH3CNNOTT-300-solv CHCl3




21

Figure S15. Comparison of unit cell parameters of NOTT-300 under different chemical environments.




22

7. Variable Temperature Powder Diffraction.

To investigate the possible framework phase change of NOTT-300-solvate as a function of temperature,

variable temperature PXRD patterns were collected at 100-483 K for NOTT-300-solvate (Fig. S16).

Comparison of the PXRD patterns confirms that there is no framework phase transition over this temperature

range and the framework of NOTT-300 remains intact after removal of the water molecules in the channels.

The lattice parameters were refined via Le Bail methods, and results are summarised in Table S3. The overall

change in the unit cell volume is less than 1.0 %, confirming the rigidity of the framework.

Figure S16. Variable temperature PXRD patterns for NOTT-300-solvate (λ = 1.54056 Å).

100 K 363 K140 K 383 K180 K 403 K220 K 423 K260 K 443 K273 K 463 K303 K 483 K333 K

10 20 30 40 50

Inte

nsity

2




23

Figure S17. Unit cell parameters for NOTT-300-solvate as a function of temperature.

Table S4. Summary of Le Bail refinement results and unit cell parameters for NOTT-300-solvate.

a, b (Å) c (Å) V (Å3) Unit cell change (%)100 K 14.78200(30) 11.76100(35) 2569.87(13) 0.000140 K 14.78821(29) 11.76287(33) 2572.44(12) 0.100180 K 14.79348(30) 11.76458(34) 2574.64(13) 0.186220 K 14.80187(30) 11.76717(34) 2578.13(13) 0.321260 K 14.81512(30) 11.77028(35) 2583.43(13) 0.527273 K 14.82847(31) 11.77667(37) 2589.50(13) 0.764303 K 14.83686(30) 11.77726(36) 2592.56(13) 0.883333 K 14.83822(31) 11.77750(38) 2593.09(14) 0.904363 K 14.83625(48) 11.78236(61) 2593.46(21) 0.918383 K 14.83288(42) 11.78464(54) 2592.79(19) 0.892403 K 14.82777(38) 11.78762(47) 2591.66(17) 0.848423 K 14.81612(45) 11.81073(51) 2592.66(19) 0.887443 K 14.81299(54) 11.81873(59) 2593.32(23) 0.912463 K 14.81193(51) 11.82149(60) 2593.55(22) 0.921483 K 14.8186(13) 11.8244(15) 2596.54(56) 1.04




24

8. Additional Gas Sorption Isotherm Plots for NOTT-300.

Figure S18. H2, N2 and Ar sorption isotherms at 77 or 87 K for NOTT-300. No significant uptake wasobserved for these adsorption isotherms.

0.0 0.2 0.4 0.6 0.8 1.00

20

40

60

80

100

H2 77 K adsN2 77 K adsAr 87 K ads

Gas

upta

ke(c

c/g)

Pressure (bar)

0

1

2

3

4

Gas

uptake(m

mol/g)




25

a b

c d

Figure S19. CO2 adsorption and desorption isotherms for NOTT-300 at (a) 273 K, (b) 283 K, (c) 293 K and(d) 303 K.

Figure S20. High pressure CO2 adsorption and desorption isotherms at 273 K for NOTT-300.

0.0 0.2 0.4 0.6 0.8 1.00

20

40

60

80

100

120

140

160

AdsorptionDesorption

CO

2up

take

(cc/

g)

Pressure (bar)

0

1

2

3

4

5

6

7

CO

2 uptake(m

mol/g)

0.0 0.2 0.4 0.6 0.8 1.00

20

40

60

80

100

120

140

160


CO

2up

take

(cc/

g)

Pressure (bar)

0

1

2

3

4

5

6

7C

O2 uptake

(mm

ol/g)

0.0 0.2 0.4 0.6 0.8 1.00

20

40

60

80

100

120

140


CO

2up

take

(cc/

g)

Pressure (bar)

0

1

2

3

4

5

6

CO

2 uptake(m

mol/g)

0.0 0.2 0.4 0.6 0.8 1.00

20

40

60

80

100


CO

2up

take

(cc/

g)

Pressure (bar)

0

1

2

3

4

CO

2 uptake(m

mol/g)

0 1 2 3 4 5 6 70

40

80

120

160

200

AdsorptionDesorptionC

O2

upta

ke(c

c/g)

Pressure (bar)

0.0

1.5

3.0

4.5

6.0

7.5

9.0

CO

2 uptake(m

mol/g)




26

Figure S21. Pore size distribution (PSD) plot and cumulative pore volume for NOTT-300. Data werecalculated the CO2 adsorption isotherm at 273 K using DFT/Monte Carlo methods.

Figure S22. Comparison of the gas adsorption isotherms for NOTT-300 at 273 K and 0.15 bar. NOTT-300exhibits highly selective uptake for CO2 and SO2 compared with CH4, CO, N2, H2, O2 and Ar. The CO2selectivities, calculated from the ratio of isotherm uptakes at 0.15 bar are 88, 99, 148, 197, 85, and 160 forCH4, CO, N2, H2, O2, and Ar, respectively. The SO2 selectivities, calculated from the ratio of isothermuptakes at 0.15 bar are 250, 278, 418, 557, 239, and 451 for CH4, CO, N2, H2, O2 and Ar, respectively.

4 6 8 10 12 14 16

0.0

0.1

0.2

0.3

0.4

0.5

0.6

dV/d(D)Pore volume

Pore width (0.1nm)

Por

evo

lum

e,dV

/d(D

)(cm

30.

1nm

-1g-

1 )

0.0

0.1

0.2

0.3

0.4

Cum

ulativepore

volume

(cm3g

-1)

0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.160

30

60

90

120

150

180

Gas

uptakes(m

mol/g)

CO2 ads SO2 adsO2 ads CH4 adsH2 ads CO adsAr ads N2 ads

Gas

upta

kes

(cc/

g)

Pressure (bar)

0

1

2

3

4

5

6

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8




27

a b

c d

Figure S23. SO2 adsorption and desorption isotherms for NOTT-300 at (a) 273 K, (b) 283 K, (c) 293 K and(d) 303 K.

0.0 0.2 0.4 0.6 0.8 1.0

0

50

100

150

200

SO

2 uptake(m

mol/g)


SO

2up

take

(cc/

g)

Pressure (bar)

0

2

4

6

8

0.0 0.2 0.4 0.6 0.8 1.0

0

50

100

150

200

SO

2 uptake(m

mol/g)


SO

2up

take

(cc/

g)

Pressure (bar)

0

2

4

6

8

0.0 0.2 0.4 0.6 0.8 1.0

0

50

100

150

200

SO

2 uptake(m

mol/g)


SO2

upta

ke(c

c/g)

Pressure (bar)

0

2

4

6

8

0.0 0.2 0.4 0.6 0.8 1.0

0

50

100

150

200

SO

2 uptake(m

mol/g)


SO2

upta

ke(c

c/g)

Pressure (bar)

0

2

4

6

8




28

a

b

cFigure S24. Comparison of the gas adsorption isotherms for NOTT-300 at 283 K (a), 293 K (b), 303 K (c)and 1.0 bar. NOTT-300 exhibits highly selective uptake for CO2 and SO2 compared with CH4, CO, N2, H2,O2, and Ar.

0.0 0.2 0.4 0.6 0.8 1.00

40

80

120

160

200

CO2 ads SO2 ads

CO2 des SO2 desO2 ads CH4 adsH2 ads CO adsAr ads N2 ads

Gas

uptakes(m

mol/g)G

asup

take

s(c

c/g)

Pressure (bar)

0

1

2

3

4

5

6

7

8

0.0 0.2 0.4 0.6 0.8 1.00

40

80

120

160

200

O2 ads CH4 adsH

2ads CO ads

Ar ads N2 ads

CO2 ads SO2 adsCO2 des SO2 des

Gas

uptakes(m

mol/g)G

asup

take

s(c

c/g)

Pressure (bar)

0

1

2

3

4

5

6

7

8

0.0 0.2 0.4 0.6 0.8 1.00

40

80

120

160

200

O2 ads CH4 adsH2 ads CO adsAr ads N2 ads

CO2 ads SO2 ads

CO2 des SO2 des

Gas

uptakes(m

mol/g)G

asup

take

s(c

c/g)

Pressure (bar)

0

1

2

3

4

5

6

7

8




29

9. Exposure of NOTT-300 to water.

The NOTT-300-solvate material was loaded into an IGA and degassed at 120 oC and 10-10 bar for 24 h to

give the fully desolvated NOTT-300 material. A CO2 adsorption isotherm was then measured at 273 K and

up to 1.0 bar (noted as first cycle). The desolvated sample was then exposed to high temperature (90-100 oC)

water vapour for 1 h as a humidity treatment. The hydrated sample was then loaded into IGA and degassed

again at 120 oC and 10-10 bar for 24 h to give desolvated NOTT-300 material. A second CO2 adsorption

isotherm was then measured at 273 K and up to 1.0 bar (noted as the second cycle). The same humidity

treatment (hydration), degassing (de-hydration), and CO2 adsorption were repeated twice more (noted as

third and fourth cycles). Comparisons of these four CO2 adsorption isotherms confirm that there is no

apparent loss of uptake capacity and that the pore surface can be fully regenerated, showing that the

framework has good stability upon exposure to the above humidity cycle.

Figure S25. CO2 adsorption isotherms at 273 K for NOTT-300 upon cyclic hydration and desolvationprocess.

0.0 0.2 0.4 0.6 0.8 1.00

30

60

90

120

150

180

CO

2 uptake(m

mol/g)

First cycleSecond cycleThrid cycleFourth cycle

CO

2up

take

(cc/

g)

Pressure (bar)

0

2

4

6

8




30

10. Additional Inelastic Neutron Scattering Spectra.

Figure S26. Comparison of INS spectra for bare NOTT-300, 0.25 H2/Al and 0.5 H2/Al loaded-NOTT-300.

0 50 100 150 200 2500.0

0.1

0.2

0.3

0.4

0.5 0 400 800 1200 1600 2000

Bare NOTT-3000.25 H2/Al loading0.50 H2/Al loading

Neutron Energy Loss/cm-1

S(Q

,)/A

rb.U

nits

Neutron Energy Loss/meV




31

a b

Figure S27. Difference INS spectra plot for forward (red) and back (black) scattering between bare and0.25H2/Al-loaded NOTT-300. The broad hump shows recoil of hydrogen; a very small and poorly definedpeak at 10meV suggests a very weak interaction. A detailed view of the low energy transfers has been scaledup in Figure b.

a b

Figure S28. Difference INS spectra plot for forward (red) and back (black) scattering between bare and 0.5H2/Al-loaded NOTT-300. The broad hump shows recoil of hydrogen. The peak at 10meV is still broad andvery weak, but can be seen to have increased in intensity slightly. Furthermore, an additional peak at ~15meV can be observed. This peak is very close to the rotational line of hydrogen (14.7 meV), furtherindicating that the interactions between the hydrogen and the NOTT-300 framework are very weak. Adetailed view of the low energy transfers has been scaled up in Figure b.

0 50 100 150 200 2500.00

0.05

0.10

0 400 800 1200 1600 2000Neutron Energy Loss/cm-1

S(Q

,)/A

rb.U

nits

Neutron Energy Loss/meV0 10 20 30 40 50

0.00

0.05

0.10

0 80 160 240 320 400Neutron Energy Loss/cm-1

S(Q

,)/A

rb.U

nits


0 50 100 150 200 2500.00

0.05

0.10

0.15

0.20

0.250 400 800 1200 1600 2000


S(Q

,)/A

rb.U

nits

Neutron Energy Loss/meV0 10 20 30 40 50

0.00

0.05

0.10

0.15

0.20

0.250 80 160 240 320 400


S(Q

,)/A

rb.U

nits





32

11. Analysis and Derivation of the Isosteric Heat of Adsorption for CO2.

To estimate the isosteric enthalpies (ΔH) for CO2 adsorption, all isotherms at 273—303 K were fitted to the

van’t Hoff equation (1):

RH

Tdpd

)/1()ln( (1)

where p is pressure, T is the temperature, R is the real gas constant. Selected linear fitting plots at 0.5, 1.0,

1.5 and 2.0 mmol g-1 are shown in Figure S25. All linear fittings show R2 above 0.999, indicating

consistency of the isotherm data.

Figure S29. Linear fitting of Van’t Hoff plots for the CO2 adsorption isotherms at 0.5, 1.0, 1.5 and 2.0 mmolg-1 loadings.

0.0033 0.0034 0.0035 0.0036 0.00377.8

8.0

8.2

8.4

8.6

8.8

9.0

9.2

Experiment at 0.5 mmol/gLinear fitting

lnP

(lnpa

)

1/T (K-1)

Equation y = a + b*xAdj. R-Square 0.99931

Value Standard Error0.5 Intercept 20.12553 0.17550.5 Slope -3323.96663 50.42876

0.0033 0.0034 0.0035 0.0036 0.0037

8.6

8.8

9.0

9.2

9.4

9.6

9.8

10.0

1/T (K-1)

lnP

(lnpa

)



Value Standard Error1 Intercept 21.01538 0.080271 Slope -3376.16146 23.06491

0.0033 0.0034 0.0035 0.0036 0.0037

9.0

9.2

9.4

9.6

9.8

10.0

10.2

10.4

lnP

(lnpa

)

1/T (K-1)




0.0033 0.0034 0.0035 0.0036 0.00379.2

9.4

9.6

9.8

10.0

10.2

10.4

10.6

1/T (K-1)

lnP

(lnpa

)







33

12. Calculation of Henry’s Law selectivity for gas adsorption.

To estimate the selectivity of CO2 and SO2 over other gases at zero surface coverage, all low pressure

isotherm data at 273 K were fitted using a linear virial-type expression (2) employed previously to model gas

sorption in MOFs. For the isotherms with overall low uptakes, where a good linear fitting cannot be obtained

at low pressure, the non-linear virial type expression (3) was employed to achieve reasonable virial fitting

with inclusion of data at relatively high pressure.6

nAApn 10)/ln( ……. (2)

......)/ln( 2210 nAnAApn (3)

where p is the pressure expressed, n is the amount adsorbed, Ai are virial coefficients, and i represent the

number of coefficients required to adequately describe the isotherms with low uptakes. The results of the

fitting for all isotherms give R2 greater than 0.99 and the Henry constants for each component were extracted

from the virial coefficients (Tables S5).

The Henry’s constant (KH) can be extracted from the values of the virial coefficients A0 using expression (4).

)exp( 0AK H (4)

The Henry’s Law selectivity for component i(CO2 or SO2) over other gas component j(CO, CH4, N2, O2, Ar

or H2) was estimated based on the ratio of their Henry’s constants (equation 5). The results are listed in Table

S6. The selectivity data from virial fittings and Henry’s Law analysis are confined to the zero surface

coverage situations.

HjHiij KKS / (5)




34

a b

Figure S30. Linear virial fitting plots for the adsorption isotherms for (a) CO2 and (b) SO2 for NOTT-300 at273 K.

a b

c d

0.0054 0.0057 0.0060 0.0063

-16.2

-16.1

-16.0

-15.9

CO2 loading (mol/g)

ln(n

/p)l

n(m

ol/g

Pa)

ExperimentLinear Fit


Value Standard ErrorD Intercept -14.11744 0.07902D Slope -324.0341 13.31269

0.0068 0.0070 0.0072 0.0074 0.0076 0.0078

-15.5

-15.0

-14.5

-14.0

-13.5

-13.0

-12.5

SO2 loading (mol/g)

ln(n

/p)l

n(m

ol/g

Pa)

ExperimentLinear Fit


Value Standard ErrorP Intercept 6.22569 0.39984P Slope -2783.4094 54.07609

0.05 0.10 0.15 0.20 0.25

5.0

5.5

6.0

6.5

7.0

n mmol/g

lnP

(lnm

bar)

0.05 0.10 0.15 0.20 0.25

5.8

6.0

6.2

6.4

6.6

6.8

7.0

n mmol/g

lnP

(lnm

bar)

0.05 0.10 0.15 0.20 0.25

4.5

5.0

5.5

6.0

6.5

7.0

n mmol/g

lnP

(lnm

bar)

0.04 0.06 0.08 0.10 0.12 0.14 0.16

6.0

6.2

6.4

6.6

6.8

n mmol/g

lnP

(lnm

bar)




35

e

Figure S31. Non-linear virial fitting plots for the adsorption isotherms for (a) CO, (b) CH4, (c) O2, (d) N2 and(e) Ar for NOTT-300 at 273 K.

a b


0.05 0.10 0.15

5.0

5.5

6.0

6.5

7.0

n mmol/g

lnP

(lnm

bar)

0.0051 0.0054 0.0057 0.0060 0.0063

-16.6

-16.5

-16.4

-16.3

ExperimentLinear fit

ln(n

/p)l

n(m

ol/g

Pa)

CO2 loading (mol/g)


Value Standard ErrorD Intercept -14.57088 0.05384D Slope -335.08249 9.35502

0.0064 0.0068 0.0072 0.0076

-16

-15

-14

-13

-12


ln(n

/p)l

n(m

ol/g

Pa)

SO2 loading (mol/g)


Value Standard ErrorD Intercept 5.75079 0.51224D Slope -2784.98877 69.75697




36

a b

c d

eFigure S33. Non-linear virial fitting plots for the adsorption isotherms for (a) CO, (b) CH4, (c) O2, (d) N2 and(e) Ar for NOTT-300 at 283 K.

0.05 0.10 0.15 0.20 0.25

5.0

5.5

6.0

6.5

7.0

n mmol/g

lnP

(lnm

bar)

0.05 0.10 0.15 0.20 0.25 0.30

5.0

5.5

6.0

6.5

7.0

n mmol/g

lnP

(lnm

bar)

0.05 0.10 0.15 0.20 0.25

5.0

5.5

6.0

6.5

7.0

n mmol/g

lnP

(lnm

bar)

0.02 0.04 0.06 0.08 0.10 0.12 0.14

4.5

5.0

5.5

6.0

6.5

7.0

n mmol/g

lnP

(lnm

bar)

0.04 0.06 0.08 0.10 0.12 0.14 0.16

5.8

6.0

6.2

6.4

6.6

6.8

7.0

n mmol/g

lnP

(lnm

bar)




37

a b


a b

c d

0.0046 0.0048 0.0050 0.0052 0.0054

-16.80

-16.76

-16.72

-16.68

-16.64


ln(n

/p)l

n(m

ol/g

Pa)

CO2 loading (mol/g)

Equation y = a + b*xAdj. R-Squar 0.99747

Value Standard ErroD Intercept -15.52311 0.02703D Slope -238.9166 5.37828

0.0070 0.0072 0.0074

-15.3

-15.0

-14.7

-14.4

-14.1

-13.8

DLinear Fit of Dln

(n/p

)ln(

mol

/gP

a)

SO2 loading (mol/g)

Equation y = a + b*xAdj. R-Squa 0.97662

Value Standard ErrD Intercept 5.46277 1.26586D Slope -2786.8186 175.69788

0.05 0.10 0.15 0.20 0.25

5.0

5.5

6.0

6.5

7.0

n mmol/g

lnP

(lnm

bar)

0.05 0.10 0.15 0.20 0.25

5.5

6.0

6.5

7.0

n mmol/g

lnP

(lnm

bar)

0.05 0.10 0.15 0.20 0.25

5.5

6.0

6.5

7.0

n mmol/g

lnP

(lnm

bar)

0.04 0.06 0.08 0.10 0.12 0.14

6.0

6.2

6.4

6.6

6.8

n mmol/g

lnP

(lnm

bar)




38


a b


0.05 0.10 0.15

5.5

6.0

6.5

7.0

n mmol/g

lnP

(lnm

bar)

0.0033 0.0036 0.0039 0.0042-17.01

-16.98

-16.95

-16.92

-16.89

-16.86


ln(n

/p)l

n(m

ol/g

Pa)

CO2

loading (mol/g)


Value Standard ErroD Intercept -16.4455 0.01413D Slope -127.0841 3.66347

0.0068 0.0070 0.0072 0.0074-15.9

-15.6

-15.3

-15.0

-14.7

-14.4

-14.1


ln(n

/p)l

n(m

ol/g

Pa)

SO2 loading (mol/g)


Value Standard ErroD Intercept 4.30094 1.00556D Slope -2707.2871 140.40608




39

a b

c d


0.05 0.10 0.15 0.20

5.5

6.0

6.5

7.0

n mmol/g

lnP

(lnm

bar)

0.05 0.10 0.15 0.20 0.25

5.5

6.0

6.5

7.0

n mmol/g

lnP

(lnm

bar)

0.05 0.10 0.15 0.20

5.0

5.5

6.0

6.5

7.0

n mmol/g

lnP

(lnm

bar)

0.02 0.04 0.06 0.08 0.10 0.12

5.0

5.5

6.0

6.5

7.0

n mmol/g

lnP

(lnm

bar)

0.04 0.06 0.08 0.10 0.12 0.14 0.16

5.5

6.0

6.5

7.0

n mmol/g

lnP

(lnm

bar)




40

Table S5. Virial fitting results and Henry’s constants KH for CO2, SO2, CH4, N2, H2, O2 and Ar in NOTT-300from isotherm data at 273 K.

CO2 SO2 CO CH4 N2 H2 O2 Ar

A0/ln(mol g-1 Pa-1) -14.11(8) 6.22(40) -20.27(3) -20.34(3) -20.81(1)

n.a.*

-20.04(2) -20.57(2)

KH/ mol g-1 Pa-1 7.45(57)

x10-7508(167) 1.57(5)

x10-91.46(4)

x10-99.14(10)

x10-101.98(2)

x10-91.16(2)

x10-9

Fitting R2 0.990 0.996 >0.999 >0.999 >0.999 >0.999 >0.999

Residual error 0.00075 0.034 0.022 0.022 0.016 0.011 0.030

* The uptake of H2 isotherm at 273 K (below 0.01 wt%) is too low to obtain a reasonable virial fitting curve, and theHenry constant is therefore considered to be approximately zero.

Table S6. Virial fitting results and Henry’s constants KH for CO2, SO2, CH4, N2, H2, O2 and Ar in NOTT-300

from isotherm data at 283 K.


A0/ln(mol g-1 Pa-1) -14.57(5) 5.75(50) -20.38(2) -20.29(2) -20.84(1)

n.a.*

-20.11(2) -20.70(3)

KH/ mol g-1 Pa-1 4.70(24)

x10-7314(123) 1.41(3)x1

0-91.54(3)

x10-98.88(9)

x10-101.85(4)

x10-91.03(4)

x10-9

Fitting R2 0.994 0.991 >0.999 >0.999 >0.999 >0.999 >0.999

Residual error 0.00050 0.141 0.021 0.013 0.024 0.023 0.012





41




A0/ln(mol g-1 Pa-1) -15.52(3) 5.46(126) -20.37(2) -20.23(3) -20.78(3)

n.a.*

-19.98(2) -20.69(2)

KH/ mol g-1 Pa-1 1.82(6)

x10-7235(168) 1.42(2)

x10-91.63(4)

x10-99.42(22)

x10-102.10(5)

x10-91.03(2)

x10-9

Fitting R2 0.997 0.977 >0.999 >0.999 >0.999 >0.999 >0.999

Residual error 0.000030 0.024 0.020 0.013 0.011 0.017 0.015





A0/ln(mol g-1 Pa-1) -16.44(1) 4.30(100) -20.27(2) -20.15(2) -20.73(1)

n.a.*

-20.01(1) -20.42(2)

KH/ mol g-1 Pa-1 7.25(8)

x10-873.7(465) 1.57(2)

x10-91.77(4)

x10-99.89(10)

x10-102.04(1)

x10-91.35(2)

x10-9

Fitting R2 0.994 0.976 >0.999 >0.999 >0.999 >0.999 >0.999

Residual error 0.000072 0.050 0.016 0.016 0.0048 0.022 0.013





42

Table S9. Summary of gas adsorption selectivity data obtained by two methods: (i)a the ratio of slopes ofinitial adsorption isotherm plot; (ii)b Henry’s Law analysis at 273 K.

Selectivity ratio Isotherm plot slop Henry’s Law analysis

CO2/CO 86 475

CO2/CH4 100 510

CO2/N2 180 815

CO2/H2 >105 >105

CO2/O2 70 376

CO2/Ar 137 642

SO2/CO 3105 >105

SO2/CH4 3620 >105

SO2/N2 6522 >105

SO2/H2 >105 >105

SO2/O2 2518 >105

SO2/Ar 4974 >105

a This method represents the selectivity at low pressure region (50-350 mbar) and is close to the situationfrom the direct comparison of gas uptakes. b This method represents the extreme selectivity at zerosurface coverage of a given material, and therefore is higher than the values from method (i). Selectivitydata obtained from method (i) are reported in the main text.



CO2/CO 67 333

CO2/CH4 57 305

CO2/N2 110 529

CO2/H2 >105 >105

CO2/O2 54 254

CO2/Ar 90 456

SO2/CO 3586 >105

SO2/CH4 3061 >105

SO2/N2 5864 >105

SO2/H2 >105 >105

SO2/O2 2880 >105

SO2/Ar 4831 >105

a This method represents the selectivity at low pressure region (50-350 mbar) and is close to the situationfrom the direct comparison of gas uptakes. bThis method represents the extreme selectivity at zero surfacecoverage of a given material, and therefore is higher than the values from method (i).




43



CO2/CO 45 128

CO2/CH4 39 112

CO2/N2 72 193

CO2/H2 >105 >105

CO2/O2 39 87

CO2/Ar 64 177

SO2/CO 2854 >105

SO2/CH4 2464 >105

SO2/N2 4545 >105

SO2/H2 >105 >105

SO2/O2 2490 >105

SO2/Ar 4070 >105




CO2/CO 32 46

CO2/CH4 31 41

CO2/N2 46 73

CO2/H2 >105 >105

CO2/O2 30 36

CO2/Ar 41 54

SO2/CO 1586 >105

SO2/CH4 1510 >105

SO2/N2 2252 >105

SO2/H2 >105 >105

SO2/O2 1458 >105

SO2/Ar 2002 >105





44

13. Summary of the hydrogen bond interaction.

A hydrogen bond system is conventionally represented as a linear A—H…B arrangement of a hydrogen

donor (A—H) and an acceptor (B). Relevant properties of the different strengths of hydrogen bonds are

given in Table C1. In this system, the hydrogen bond length H···O is around 2.3 Å (Figure 4d), and therefore

it can be classed as a moderate-to-weak hydrogen bond. The four C-H supramolecular contacts are likely to

be of lower energies. Based on this analysis, we view the observed value of Qst as entirely reasonable and

consistent with the likely hydrogen bond energies. In addition, there is the possibility of electrostatic

Al(III)/XO2 interactions. The high CO2 uptakes also reflect the relatively narrow pore size of the host which

provides strong overlap potentials.

Table S13. Properties of strong, moderate and weak H-bonds.7,8

Properties Strong H-bonds Moderate H-bonds Weak H-bondsBond energy (kJ mol-1) 4–10 1–3

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