Chemically blockable transformation and ultra- …Chemically blockable transformation and...

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Supplementary informationdoi: 10.1038/nchem.254

Chemically blockable transformation and ultra-

selective low pressure adsorption in a metal

organic framework

Bo Xiao,1 Peter J. Byrne,1 Paul S. Wheatley,1 David S. Wragg,1 Xuebo Zhao,2 Ashleigh J.

Fletcher,2K. Mark Thomas,2 Lars Peters,3 John S.O. Evans,3 Russell E. Morris1

1EaStChem School of Chemistry, University of St Andrews, Purdie Building, St Andrews

KY16 9ST, UK.

2Northern Carbon Research Laboratories, School of Natural Sciences, Bedson Building

Newcastle University, Newcastle upon Tyne, NE1 7RU, UK

3Department of Chemistry, University of Durham Science Laboratories, South Road,

Durham, DH1 3LE, UK

Supplementary Information

S1 Synthesis of Cu-SIP-3

In a typical synthesis, Cu(NO3)2·3H2O (Alfa Aesar 98%) (2.42g) and 5-sulfoisophthalic

acid, sodium salt (NaH2SIP) (Aldrich, 95%) (2.68g) were dissolved in a 12mL

EtOH/H2O (50:50) solution. The mixture was heated in a 50mL Teflon lined autoclave at




383K for five days, followed by naturally cooling down to room temperature. The

yielded crystals were cleaned by sonication in a 100mL solution (EtOH/H2O) for 5

minutes and then filtrated out. The aqua blue crystals were collected and dried in air.

S2 NO adsorption/desorption isotherms

The isotherms of NO adsorption and desorption on samples were measured using a

gravimetric adsorption system composed of a CI microbalance integrated with a thermal

stabilizer, reactor, vacuum lines, thermostats and pressure transducers. The balance has

sensitivity of 0.1 µg and reproducibility of 0.01% load. ~50 mg CuSIP were degassed

under vacuum (10-4 mbar) at 423K prior to NO adsorption until no further weight loss

was observed. The dried NO gas (Air Liquide, 99.5%) was then introduced into the

adsorption system. The isotherms of NO adsorption were obtained through controlling

adsorption equilibrium at different desired pressures until up to 1 bar. Desorption was

conducted by reducing NO pressure in adsorption system to the desired values until

reaching equilibrium.

S3 TG analysis

The TG analysis of sample was carried out using a NETZSCH STA449C TG system

connected to a PFEIFFER vacuum ThermoStar mass spectrometer through a quartz glass

capillary heated at 453K. ~10mg sample was used for the TG measurement. The sample

was heated at rate of 5Kmin-1 in argon flow (45mLmin-1) from room temperature to

1073K. The species with m/z: 28 (CO), 44 (CO2), 48 (SO2) and 64 (SO3) were monitored

throughout experiment.

383K for five days, followed by naturally cooling down to room temperature. The

yielded crystals were cleaned by sonication in a 100mL solution (EtOH/H2O) for 5

minutes and then filtrated out. The aqua blue crystals were collected and dried in air.

S2 NO adsorption/desorption isotherms

The isotherms of NO adsorption and desorption on samples were measured using a

gravimetric adsorption system composed of a CI microbalance integrated with a thermal

stabilizer, reactor, vacuum lines, thermostats and pressure transducers. The balance has

sensitivity of 0.1 µg and reproducibility of 0.01% load. ~50 mg CuSIP were degassed

under vacuum (10-4 mbar) at 423K prior to NO adsorption until no further weight loss

was observed. The dried NO gas (Air Liquide, 99.5%) was then introduced into the

adsorption system. The isotherms of NO adsorption were obtained through controlling

adsorption equilibrium at different desired pressures until up to 1 bar. Desorption was

conducted by reducing NO pressure in adsorption system to the desired values until

reaching equilibrium.

S3 TG analysis

The TG analysis of sample was carried out using a NETZSCH STA449C TG system

connected to a PFEIFFER vacuum ThermoStar mass spectrometer through a quartz glass

capillary heated at 453K. ~10mg sample was used for the TG measurement. The sample

was heated at rate of 5Kmin-1 in argon flow (45mLmin-1) from room temperature to

1073K. The species with m/z: 28 (CO), 44 (CO2), 48 (SO2) and 64 (SO3) were monitored

throughout experiment.

Chemically blockable transformation and ultra-

selective low pressure adsorption in a metal

organic framework

Bo Xiao,1 Peter J. Byrne,1 Paul S. Wheatley,1 David S. Wragg,1 Xuebo Zhao,2 Ashleigh J.

Fletcher,2K. Mark Thomas,2 Lars Peters,3 John S.O. Evans,3 Russell E. Morris1

1EaStChem School of Chemistry, University of St Andrews, Purdie Building, St Andrews

KY16 9ST, UK.

2Northern Carbon Research Laboratories, School of Natural Sciences, Bedson Building

Newcastle University, Newcastle upon Tyne, NE1 7RU, UK

3Department of Chemistry, University of Durham Science Laboratories, South Road,

Durham, DH1 3LE, UK

Supplementary Information

S1 Synthesis of Cu-SIP-3

In a typical synthesis, Cu(NO3)2·3H2O (Alfa Aesar 98%) (2.42g) and 5-sulfoisophthalic

acid, sodium salt (NaH2SIP) (Aldrich, 95%) (2.68g) were dissolved in a 12mL

EtOH/H2O (50:50) solution. The mixture was heated in a 50mL Teflon lined autoclave at




300 400 500 600 700 800 900 100040

60

80

100

Temperature/K

SO2 (30x)CO

CO2

Inte

nsity

ofsp

ecie

sde

sorb

ed

Wei

ghtl

osse

s,%

wt

Figure S1 TG analysis of sample Cu SIP-3 (5.6%wt weight loss at <423K; 5.4%wt at

423-500K).

S4 Variable Temperature X-ray Diffraction experiments on Cu-SIP MOF

Two VT experiments were performed on Cu-SIP MOF, using the same scan parameters

and heating/cooling features between 300 and 445 K (corrected temperatures), the first in

air (d8_03479.raw), the second under a constant N2 gas flow (d8_03492.raw).

20 min diffraction patterns were taken on a Bruker AXS D8 diffractometer, using

monochromatic Cu K 1 radiation. Diffracted intensities were recorded with a gas–filled

Våntec linear PSD in 0.0085° steps (0.14 s/step) in the 2 range 5-75°. Figures 1-4 show

2D “film” plots of both experiments (max T at range 36).




Figure S2: 2D “film” plot of the diffraction patterns taken under normal atmospheric

conditions. The sample de-hydrated between ~388 and 409 K. Re-hydration occurred on

cooling between ~ 329 and 320 K. During both, de-hydration and re-hydration, the lines

broaden significantly, indicating a decreasing crystallite/domain size.




Figure S3: Fragment of the 2D “film” plot from Figure 1, demonstrating a significant

shift of the reflection positions of Cu-SIP MOF in the vicinity of the de-hydration

reaction and the line-broadening during de- and re-hydration.




Figure S4: 2D “film” plot of the diffraction patterns taken under constant N2 flow. The

sample de-hydrated between ~368 and 405 K. No re-hydration was observed on cooling.




Figure S5: Fragment of the 2D “film” plot from Figure 3, demonstrating a significant

shift of the reflection positions of Cu-SIP MOF in the vicinity of the dehydration reaction.

All powder diffraction data were analysed by the Rietveld method (Rietveld, 1967)

within the TOPAS software package (Coelho, 2000). In the final 2-phase refinement cycle,

24 independent parameters were refined (9 coefficients for a background polynomial, the

sample height, 4 lattice parameters, 1 isotropic thermal displacement parameter and 1

scale factor for each phase, and 1 parameter each for a gaussian and a lorentzian

contribution to size broadening of the reflections. Prior to this final refinement cycle, a

room temperature ”instrumental” peak shape function (Thompson, Cox & Hastings,

1987), axial divergence correction and an eigth-order spherical harmonic (the latter for

each phase) modelling preferred orientation were determined and kept constant thereafter.

In none of the refinements, fractional atomic coordinates were allowed to vary due to the




limited number of observations, the complexity of the structures, and the dominance of

Cu in scattering power, with respect to the other elements in the material.

Figure S6: Plot of the refinement result for the hydrated phase at ~ 300 K (range 1,

experiment under N2).

Figure S7: Plot of the refinement result for the de-hydrated phase at ~ 445 K (range 36,

experiment under N2).

Figure S8: Plot of the refinement result for the re-hydrated phase at ~ 302 K (range 70,

experiment under air). The lines are considerably broadened with respect to those

displayed in Fig. 5.




Figure S9: Refined grain/domain size of Cu-SIP MOF as function of temperature for the

data series collected under air. Grain size decreases significantly during dehydration

(from ~4500nm to ~ 40nm) and again during rehydration (to ~15nm), probably

explaining the observed peak-broadening effects.

In addition to the fact that the material re-hydrates on cooling under air, which was not

observed under nitrogen, the lattice parameters of the hydrated material behave slightly

differently in both experiments, mainly such that the de-hydration under nitrogen occurs

at a ~20K lower temperature. This can be derived from Figs. 9-13 for a, b, c, and the

cell volume. The pronounced changes in these parameters, shortly before the actual

dehydration takes place, correspond to the significant shift of the reflection positions of

Cu-SIP MOF in the vicinity of the dehydration reaction as depicted in Figures 2 and 4.

0.00

10.00

20.00

30.00

40.00

50.00

60.00

70.00

80.00

300 310 320 330 340 350 360 370 380

T / K

size

/nm

Air

0.00

500.00

1000.00

1500.00

2000.00

2500.00

3000.00

3500.00

4000.00

4500.00

5000.00

300 310 320 330 340 350 360 370 380 390 400 410 420 430 440 450

T / K

size

/nm

Air




The difference in the dehydration temperatures possibly indicates a shift of the univariant

reaction curve towards higher T with increasing water partial pressure.

7.22

7.24

7.26

7.28

7.30

7.32

7.34

7.36

7.38

300 310 320 330 340 350 360 370 380 390 400 410

T / K

a/Å

N2Air

Figure S10: Variation of the lattice parameter a of Cu-SIP MOF with T.

17.90

18.00

18.10

18.20

18.30

18.40

18.50

18.60

18.70

300 310 320 330 340 350 360 370 380 390 400 410

T / K

b/Å

N2Air

Figure S11: Variation of the lattice parameter b of Cu-SIP MOF with T.




9.70

9.80

9.90

10.00

10.10

10.20

10.30

10.40

300 310 320 330 340 350 360 370 380 390 400 410

T / K

c/Å

N2Air

Figure S12: Variation of the lattice parameter c of Cu-SIP MOF with T.

92.20

92.40

92.60

92.80

93.00

93.20

93.40

93.60

93.80

94.00

94.20

94.40

300 310 320 330 340 350 360 370 380 390 400 410

T / K

beta

/°

N2Air

Figure S13: Variation of the lattice parameter of Cu-SIP MOF with T.




1310.00

1315.00

1320.00

1325.00

1330.00

1335.00

1340.00

1345.00

1350.00

1355.00

1360.00

300 310 320 330 340 350 360 370 380 390 400 410

T / K

V/Å

^3

N2Air

Figure S14: Variation of the cell volume of Cu-SIP MOF with T.

In contrast to the above, the lattice parameters of the dehydrated phase behave very

similarly in both experiments, under air and nitrogen. However, the behaviour of lattice

parameter a possibly indicates that some water initially remains trapped in the structure

and is then gradually released on further heating.




0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

0 10 20 30 40 50 60 70

range No

Pha

sefra

ctio

n

% hydr% dehydr

Figure S15: Phase fraction of the hydrated and dehydrated phases as function of the

range number, experiment under N2.

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

0 10 20 30 40 50 60 70

range No

Pha

sefra

ctio

n

% hydr% dehydr

Figure S16: Phase fraction of the hydrated and dehydrated phases as function of the

range number, experiment under air.




S4 Cu-SIP-3-pyridine

It was obtained using Cu(NO3)2·3H2O (Alfa Aesar 98%) (2.42g), 5-sulfoisophthalic acid,

sodium salt (NaH2SIP) (Aldrich, 95%) (2.68g) and pyridine (Py) (Alfa Aesar 98%)(0.41g)

mixed with a 12mL EtOH/H2O solution (50:50) in a 50mL Teflon linned autoclave. The

mixture was heated at 383K for five days and then naturally cooled down to room

temperature. The yields were sonicated in a 100mL EtOH/H2O solution for 5 minutes,

then filtrated under vacuum. The blue crystals were collected and dried in air.

S5 TGA Analysis

303 400 500 600 700 800 900 100030

40

50

60

70

80

90

100

Wei

ghtl

osse

s/%

wt

Temperature/K

SO3

NO2

NO

SO2

Inte

nsity

Figure S17. Thermal gravimetric analysis of CuSIP-pyridine (weight loss:3.75%wt at <

473K. Sample is decomposed and releases species containing NO and NO at >566K).

S6 HRTEM

Experimental




HRTEM was performed using a JEOL JEM-2011 electron microscope operating at 200

kV, with a point resolution of 0.19 nm. Most MOF samples are electron beam sensitive.

This is why very few electron microscopic results from these materials were reported. In

our work, several operations were carried out in order to obtain reasonably good HRTEM

images. For example, the specimen was tried and inserted into the microscope, kept in the

vacuum system for one hour or so. The microscopic conditions were pre-tuned. The

orientation of the crystal was adjusted at low magnification. Images were recorded at

200,000× to 300,000× using a Gatan 794 CCD camera with a very low beam irradiation

dose, e.g., < 2 pA/cm2. This method we applied for many zeolites and other beam

sensitive materials [P. A. Wright, W. Z. Zhou, J. Perez-Pariente, M. Arranz, J. Am. Chem.

Soc. 127, 494–495 (2005); J. F. Geng, W. Z. Zhou, P. Skelton, W. B. Yue, I. A. Kinloch,

A. H. Windle, B. F. G. Johnson, J. Am. Chem. Soc. 130, 2527-2534 (2008)].

Without a cryo-specimen stage, even the above operations are performed, some samples

are still too sensitive to electron beam and HRTEM imaging is nearly impossible. It was

found that the specimen of Cu-SIP-3 was extremely unstable under the electron beam and

no HRTEM images were successfully obtained. However, when the sample was

dehydrated the water molecules were replaced by pyridine, the sample Cu-SIP-3-pyridine

was reasonably stable under the beam irradiation. Figure S18 shows HRTEM of this

sample viewed down the [-130] zone axis. On this projection, the structure shows Cu-rich

(dark) and pyridine (bright) alternative fringes along the [001] axis. In the area marked by

a circle, a defect was observed, which looks like an antiphase defect where the Cu-rich

and pyridine fringes change their locations. In other words, the structure shifts along the

[001] axis by a quarter unit cell dimension. This type of defect often implies some new

building units in the antiphase boundary. The boundary is not clear and does not show a

dark image contrast as we normally observed from antiphase defects [A. C. McLaughlin,

W. Z. Zhou, J. P. Attfield, A. N. Fitch, J. L. Tallon, Phys. Rev. B 60, 7512–7516 (1999)],

indicating that the antiphase defect plane is not parallel to the view direction.

Crystal defects often give us information about the crystal growth mechanism [W. Z.

Zhou, J. Mater. Chem., (2008) DOI: 10.1039/B808158A]. In other particles, we often

observe layered defects. Figure S19 is a typical image showing a large number of layered

defects. The lattice d-spacing measured from the image is 3.0 A, which can be indexed








S5 TGA Analysis

303 400 500 600 700 800 900 100030

40

50

60

70

80

90

100

Wei

ghtl

osse

s/%

wt

Temperature/K

SO3

NO2

NO

SO2

Inte

nsity



S6 HRTEM

Experimental








S5 TGA Analysis

303 400 500 600 700 800 900 100030

40

50

60

70

80

90

100

Wei

ghtl

osse

s/%

wt

Temperature/K

SO3

NO2

NO

SO2

Inte

nsity



S6 HRTEM

Experimental




onto (212) of the crystal structure. The atomic plan normal to the disordered direction can

be identified to be close to (010), which has an interplane angle with (212) of 80°. This

defect indicates that the crystal growth route follows a layer-by-layer manner along the

[010] direction. On the (010) plane, the structure shifting often takes place.

Figure S18. HRTEM image of Cu-SIP-3-pyridine viewed down the [-130] zone axis. The

botton right inset is a FFT diffraction pattern indexed to the unit cell determined by single

crystal XRD. The top left inset shows computer created image from the FFT diffraction

pattern by removing the noise. The area marked by the circle shows an antiphase-like

defect.

onto (212) of the crystal structure. The atomic plan normal to the disordered direction can

be identified to be close to (010), which has an interplane angle with (212) of 80°. This

defect indicates that the crystal growth route follows a layer-by-layer manner along the

[010] direction. On the (010) plane, the structure shifting often takes place.

Figure S18. HRTEM image of Cu-SIP-3-pyridine viewed down the [-130] zone axis. The

botton right inset is a FFT diffraction pattern indexed to the unit cell determined by single

crystal XRD. The top left inset shows computer created image from the FFT diffraction

pattern by removing the noise. The area marked by the circle shows an antiphase-like

defect.

HRTEM was performed using a JEOL JEM-2011 electron microscope operating at 200

kV, with a point resolution of 0.19 nm. Most MOF samples are electron beam sensitive.

This is why very few electron microscopic results from these materials were reported. In

our work, several operations were carried out in order to obtain reasonably good HRTEM

images. For example, the specimen was tried and inserted into the microscope, kept in the

vacuum system for one hour or so. The microscopic conditions were pre-tuned. The

orientation of the crystal was adjusted at low magnification. Images were recorded at

200,000× to 300,000× using a Gatan 794 CCD camera with a very low beam irradiation

dose, e.g., < 2 pA/cm2. This method we applied for many zeolites and other beam

sensitive materials [P. A. Wright, W. Z. Zhou, J. Perez-Pariente, M. Arranz, J. Am. Chem.

Soc. 127, 494–495 (2005); J. F. Geng, W. Z. Zhou, P. Skelton, W. B. Yue, I. A. Kinloch,

A. H. Windle, B. F. G. Johnson, J. Am. Chem. Soc. 130, 2527-2534 (2008)].

Without a cryo-specimen stage, even the above operations are performed, some samples

are still too sensitive to electron beam and HRTEM imaging is nearly impossible. It was

found that the specimen of Cu-SIP-3 was extremely unstable under the electron beam and

no HRTEM images were successfully obtained. However, when the sample was

dehydrated the water molecules were replaced by pyridine, the sample Cu-SIP-3-pyridine

was reasonably stable under the beam irradiation. Figure S18 shows HRTEM of this

sample viewed down the [-130] zone axis. On this projection, the structure shows Cu-rich

(dark) and pyridine (bright) alternative fringes along the [001] axis. In the area marked by

a circle, a defect was observed, which looks like an antiphase defect where the Cu-rich

and pyridine fringes change their locations. In other words, the structure shifts along the

[001] axis by a quarter unit cell dimension. This type of defect often implies some new

building units in the antiphase boundary. The boundary is not clear and does not show a

dark image contrast as we normally observed from antiphase defects [A. C. McLaughlin,

W. Z. Zhou, J. P. Attfield, A. N. Fitch, J. L. Tallon, Phys. Rev. B 60, 7512–7516 (1999)],

indicating that the antiphase defect plane is not parallel to the view direction.

Crystal defects often give us information about the crystal growth mechanism [W. Z.

Zhou, J. Mater. Chem., (2008) DOI: 10.1039/B808158A]. In other particles, we often

observe layered defects. Figure S19 is a typical image showing a large number of layered

defects. The lattice d-spacing measured from the image is 3.0 A, which can be indexed




Figure S19 HRTEM image of Cu-SIP-3-pyridine showing a large number of layereddefects along the [010] axis.

Figure S19 HRTEM image of Cu-SIP-3-pyridine showing a large number of layereddefects along the [010] axis.

Chemically blockable transformation and ultra- …Chemically blockable transformation and...

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