Robust Metal Triazolate Frameworks for CO Capture from ...€¦ · Synthesis of ZnF(TZ): A mixture...

S1

Supporting Information (99 pages)

Robust Metal Triazolate Frameworks for CO2 Capture from Flue Gas

Zhaolin Shi,†,‡,§ Yu Tao,† Jiasheng Wu,† Cuizheng Zhang,† Hailong He,† Liuliu Long,† Yongjin Lee,†

Tao Li† and Yue-Biao Zhang*,†

†School of Physical Science and Technology, ShanghaiTech University, Shanghai 201210, China.

‡Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201210, China.

§University of Chinese Academy of Sciences, Beijing 100049, China.

*To whom correspondence should be addressed. E-mail: [email protected]

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Table of Contents

Section S1. Synthesis and Characterization ............................................................................................... 3

Section S2. Chemical Stability Test ........................................................................................................... 6

Section S3. Static and Dynamic Gas/Vapor Adsorption .......................................................................... 12

Section S4. Isosteric Heats of Adsorption ................................................................................................ 31

Section S5. Calculation of IAST Selectivity ............................................................................................ 40

Section S6. Dynamic Gas Adsorption Breakthrough Measurements ...................................................... 49

Section S7. Dynamic Vapor Sorption (DVS) Measurements .................................................................. 61

Section S8. CO2 /H2O Competitive Adsorption Kinetics ........................................................................ 70

Section S9. Cycling Mimic Flue Gas Adsorption Breakthrough Measurements ..................................... 80

Section S10. GCMC Simulations and DTF Calculations to Investigate the Adsorption Sites ................ 88

Section S11. References ........................................................................................................................... 96

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Section S1. Synthesis and Characterization

Materials. Zinc nitrate hexahydrate [Zn(NO3)2∙6H2O] (purity > 99.99%) were purchased from Aladdin;

Zinc tetrahydrate [Zn(NO3)2∙4H2O] (purity > 99%), ZnF∙4H2O (purity > 98%)were purchased from Alfa

Aesar; HTZ, HaTZ, HdaTZ and HdmTZ were purchased from TCI. All the starting materials were used as

received without further purification.

Synthesis of ZnF(TZ): A mixture of Zn(NO3)2ꞏ6H2O (223.1 mg, 0.75 mmol), HTZ (51.8 mg, 0.75

mmol), hydrofluoric acid (0.75 mmol, 40%, 34 μL) was dissolved in DMF (15 mL) under ultrasound. The

resulting mixture was filtrated and sealed into a microwave tube (25 mL), stirred magnetically for 1 h, then

the vessel was loaded into a microwave oven (BIOTAGE, Initiator+), heated from room temperature to

240 °C for 1 min and held at this temperature for 30 min, followed by cooling to room temperature. A white

powder was obtained as the major product, transferred to a centrifuge tube and washed with DMF for 3–5

times, CH3OH for 6–9 times during 2 days, finally dried under vacuum.

Synthesis of ZnF(aTZ): A mixture of Zn(NO3)2ꞏ4H2O (196.1 mg, 0.75 mmol) and hydrofluoric acid

(0.66 mmol, 40%, 30 μL) was dissolved in H2O (9 mL) under ultrasound. HaTZ (127.5 mg, 1.5 mmol) was

dissolved in 6mL EtOH, then combined with the above aqueous solution together, then the vessel was

loaded into the microwave oven, heated from room temperature to 120 °C for 1 min and held at this

temperature for 30 min, followed by cooling to room temperature. A yellowish-white powder was obtained

as the major product, transferred to a centrifuge tube and washed with EtOH for 3–5 times, CH3OH for 6–

9 times during 2 days, finally dried under vacuum.

Synthesis of ZnF(daTZ): A mixture of HdaTZ (198 mg, 2 mmol) hydrofluoric acid (0.44 mmol, 40%,

20 μL) was dissolved in H2O (10 mL) under ultrasound, the resulting mixture was filtrated into a microwave

tube (25 mL), the insoluble ZnF2ꞏ4H2O (351 mg, 2 mmol) was added, sealed, and stirred magnetically for

1 h, then the vessel was loaded into the microwave oven, heated from room temperature to 160 °C for 1

min and held at this temperature for 30 min, followed by cooling to room temperature. A reddish-white

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powder was obtained as the major product, transferred to a centrifuge tube and washed with EtOH for 3–5

times, CH3OH for 6–9 times during 2 days, then dried under vacuum.

Synthesis of ZnF(dmTZ): A mixture of Zn(NO3)2ꞏ6H2O (238 mg, 0.8 mmol), HdmTZ (77.7 mg, 0.8

mmol), hydrofluoric acid (0.8 mmol, 40%, 35 μL) was dissolved in DMF (4 mL) under ultrasound. The

resulting mixture was filtrated and sealed into a microwave tube (10 mL), stirred magnetically for 1 h, then

the vessel was loaded into the microwave oven, heated from room temperature to 120 °C for 1 min and held

at this temperature for 2 h, followed by cooling to room temperature. A white powder was obtained as the

major product, transferred to a centrifuge tube and washed with DMF for 3–5 times, CH3OH for 6–9 times

during 2 days, then dried under vacuum.

Instrumentation and Characterization. The phase purity and crystallinity of samples were determined

with a powder X-ray diffractometer (Bruker, D8 advance, Cu Kα). The crystal size and morphology were

examined using a scanning electron microscope (JEOL, JSM 7800F Prime). Thermogravimetric analyses

(TGA) were performed on a TGA instrument (Perkin-Elmer, TGA 4000) with a heating rate of 10 °Cꞏmin-

1 from ambient temperature to 700 °C under N2 flow. Gas adsorption measurements of CO2 (195 K) and

CO2, N2 (atmospheric temperatures) were carried out on a 2-Ports microporosity and specific surface area

analyzer (Quantachrome, Autosorb IQ2). Static water adsorption measurements were performed on a

precision vapor adsorption measuring system (BELSORP, Aqua3). Ultrahigh-purity (>99.999%) CO2, N2,

and He in compressed gas cylinders were used through all experiments. Dewar with a mixture of sandy dry

ice and MeOH was used to keep the sample temperatures at 195 K. Dewar connected to a Julabo F12-E0

isothermal bath filled with Ethylene glycol aqueous solution (v/v = 1:3,), for which the temperature stability

is ± 0.02 °C, was used to keep the temperature at 273, 283, and 298 K, respectively.

S5

Figure S1. SEM images of the metal triazolate frameworks showing well-defined prism-shaped

morphologies.

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Section S2. Chemical Stability Test

0.0 0.2 0.4 0.6 0.8 1.00

10

20

30

40

as synthesized HNO3

HCl H2SO4

CO

2 U

ptak

e (c

m3S

TP/g

)

Pressure (bar)

273 K

Figure S2. CO2 adsorption isotherms at 273 K (solid line: adsorption, dashed line: desorption) of

the ZnF(daTZ) after being immersed in acid solvents (pH = 4) and activated directly, which

sustained at least 83% of the adsorption capacity.

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5 10 15 20 25 30 35 40 45

pH = 12 (14 h)

pH = 11 (14 h)

pH = 10 (14 h)

pH = 8 (14 h)

pH = 6 (14 h)

pH = 4 (24 h)

pH = 3 (14 h)

pH = 2 (14 h)

pH = 1 (14 h)

ZnF(TZ)-simulated

pH = 9 (14 h)

pH = 2 (24 h)

pH = 1 (24 h)

pH = 11 (24 h)

pH = 12 (24 h)

Inte

nsity

(a.u.)

2 (o, = Cu K)

pH = 5 (14 h)

pH = 3 (24 h)pH = 4 (14 h)

pH = 10 (24 h)

Figure S3. PXRD patterns of ZnF(TZ) after being immersed in acid (HCl) or base (NaOH)

solvents, showing that the crystallinity can be sustained at pH = 2–12 at least for 24 h.

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Figure S4. SEM images of ZnF(TZ) before (a) and after (b) being immersed in the base solvent

(pH = 12), exerting no obvious powder size decreasing because of MOF dissolved in the base

solvent.

a)

b)

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5 10 15 20 25 30 35 40 45

4 days

3 days

Inte

nsity

(a.u.)

2 (o, = Cu K)

Simulated

1 day

ZnF(aTZ) Imersed in boiling water

Figure S5. PXRD patterns of ZnF(aTZ) after being immersed in boiling water, showing

crystallinity kept at least for four days.

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5 10 15 20 25 30 35 40 45

pH = 12 (14 h)

pH = 11 (14 h)pH = 10 (14 h)

pH = 8 (14 h)

pH = 6 (14 h)

pH = 4 (14 h)pH = 3 (14 h)

pH = 2 (14 h)

pH = 1 (14 h)

ZnF(aTZ)-simulated

pH = 9 (14 h)

pH = 2 (24 h)

pH = 1 (24 h)

pH = 11 (24 h)

pH = 12 (24 h)

Inte

nsity

(a.u.)

2 (o, = Cu K)

pH = 5 (14 h)

Figure S6. PXRD patterns of ZnF(aTZ) after being immersed in acid (HCl) or base (NaOH)

solvents, showing crystallinity sustained at pH = 2 to 12 at least for 24 h.

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Table S1. Comparison of the acid or base stability of MOFs materials.

Material pH/Concentration Temp. Time Ref.

ZnF(TZ) 3-12 rt 1 day HCl, NaOH This work

ZnF(aTZ) 2-12 rt 1 day HCl, NaOH This work

ZnF(daTZ) 1-12 rt 20 h HCl, NaOH This work

Ni3(BTP)2 2, 14 100 oC 2 weeks HCl, HNO3, NaOH S1

JUC-1000 1.5, 12.5 rt 2 days HCl, NaOH S2

MIL-101 (Cr) 0, 4, 12 rt 2 months

HCl, NaOH

S3

MIL-53 (Al) 4, 12 rt 2 months S3

NH2-MIL-53 (Al) 4, 12 rt 2 months S3

UiO-66 0, 4, 12 rt 2 months S3

NH2-UiO-66 0, 4, 12 rt 2 months S3

UiO-67 4, 12 rt 3 days S3

ZIF-8 4, 12 rt 3 days S3 H3[(Cu4Cl)3-

(BTTri)8] 3 rt 1 day S4

MAF-X27-Cl 3, 14 rt 1 week S5

ZIF-8 8 M 100 oC 1 day NaOH S6

NENU-500 1 rt 6 h H2SO4 S7

NENU-501 1 rt 6 h H2SO4 S7

Cu(dimb) 14 100 oC 7 days NaOH S8

PCN-46-Cr(III) 4M, 2 M; pH 1, 12 rt 0.5 day HCl, NaOH S9

PCN-230 0, 1, 11, 12 rt 1 day S10

PCN-225 0, 1, 2, 11, 11.5, 12 rt 0.5 day S11

PCN-250 1, 2, 3, 10, 11, 12 rt 1 day S12

UiO-66-NO2 1, 14 rt 2 h S13

FJI-H14 2, 3, 4, 10, 11, 12 100 oC 1 day S14

PCN-601 1, 2

1 M, 10 M rt

100 oC 1 day

HCl NaOH

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PCN-602(Ni) 4, 14 rt 1 day HCl, NaOH S16

BUT-12, -13 2, 6, concentrated

10 rt 1 day

HCl NaOH

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Eu-1,4-NDC-fcu-MOF

3.5, 10 100 oC 1 day HCl, NaOH S18

PCN-901(Zr)-SO2 0, 1, 3, 7, 9, 11, 12 rt 1 day S19

PCN-700-Me4 12 M, 10 M rt HCl, NaOH S20

S12

Section S3. Static and Dynamic Gas/Vapor Adsorption

The ultramicroporosity of these MOFs, their pore metrics were analyzed by the CO2 adsorption

isotherms at 195 K and 273 K.

Pore size distribution analyses. The pore volumes and the pore size distributions were all

derived from their CO2 physisorption isotherms at 273 K fitted by Monte Carlo (MC) simulation

method. Also see: Thommes, M.; Kaneko, K.; Neimark, A. V.; Olivier, J. P.; Rodriguez-Reinoso,

F.; Rouquerol, J.; Sing, K. S. W. Pure Appl. Chem. 2015, 87, 1051.

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0 20 40 60 80 1000

50

100

150

200

250

ZnF(dmTZ)

ZnF(aTZ)

Pressure (kPa)

CO

2 U

ptak

e (c

m3 S

TP/c

m3 )

195 KZnF(TZ)

ZnF(daTZ)

Figure S7. CO2 gas adsorption isotherms of the metal triazolate frameworks at 195 K showing the

permanent microporosity. The unit cm3STP g-1 is converted to cm3

STP cm-3 based on their crystal

density, which is listed in the Table S2.

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0.0 0.8 1.6 2.4 3.20

100

200

300

400

500

ZnF(TZ)

Pressure (kPa)

H2O

Upt

ake

(cm

3 ST

P/c

m3 )

298 K

ZnF(aTZ)

ZnF(daTZ)

ZnF(dmTZ)

Figure S8. Static volumetric water vapor adsorption isotherms of the metal triazolate frameworks

at 298 K for evaluating their hydrophilicity.

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0 20 40 60 80 1000

20

40

60

80

100

ZnF(aTZ)

273 K

CO

2 U

ptak

e (c

m3 S

TP/c

m3 )

Pressure (kPa)

ZnF(daTZ)ZnF(TZ)

Figure S9. CO2 gas adsorption isotherms of the metal triazolate frameworks at 273 K.

S16

3 6 9 12 150

200

400

600

800

4.8 ÅZnF(aTz)

6.0 ÅZnF(Tz)

4.2 ÅZnF(daTz)

Pore width (Å)

dS

(d)

Figure S10. Comparison of pore size distribution (PSD) of the metal triazolate frameworks. PSD

is derived from Monte-Carlo model by fitting their CO2 physisorption isotherms at 273 K.

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0 3 6 9 12 150

100

200

300

400

500

600

700

0.001 0.010

10

20

30

40

50

60

70

ZnF(TZ)

6.0 Å

dS(d

)

Pore width (Å)

P /P0

Vo

lum

e (c

c/g

)

measured fitted

Figure S11. The pore size distribution of ZnF(TZ) derived from Monte-Carlo model by fitting the

adsorption branch of its CO2 physisorption isotherm at 273 K with minimal fitting error (0.201%).

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0 3 6 9 12 150

100

200

300

400

500

600

700

0.001 0.010

10

20

30

40

50

60

70

5.7 Å

4.8 Å

dS(d

)

Pore width (Å)

ZnF(aTZ)

P /P0

Vo

lum

e (c

c/g

)

Measured DFT Fitting

Figure S12. The pore size distribution of ZnF(aTZ) derived from Monte-Carlo model by fitting

the adsorption branch of its CO2 physisorption isotherm at 273 K with minimal fitting error

(0.209%).

S19

0 3 6 9 12 150

100

200

300

400

500

600

700

1E-4 0.001 0.010

10

20

30

40

50

60

70

4.2 Å

Pore width (Å)

dS(d

)

ZnF(daTZ)

P /P0

Vo

lum

e (c

c/g

)


Figure S13. The pore size distribution of ZnF(daTZ) derived from Monte-Carlo model by fitting

the adsorption branch of its CO2 physisorption isotherm at 273 K with minimal fitting error

(0.187%).

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0 3 6 9 12 150

100

200

300

400

500

600

700

1E-4 0.001 0.010

10

20

30

40

50

60

70

4.4 Å

Pore width (Å)

dS(d

)

3.7 Å

ZnF(daTZ)@H2SO4

P /P0

Vo

lum

e (c

c/g

)


Figure S14. The pore size distribution of ZnF(daTZ)@H2SO4 derived from Monte-Carlo model

by fitting the adsorption branch of its CO2 physisorption isotherm at 273 K with with minimal

fitting error (0.443%).

S21

0 3 6 9 12 150

100

200

300

400

500

600

700

1E-4 0.001 0.010

10

20

30

40

50

60

70

4.4 Å

Pore width (Å)

dS(d

)

3.7 Å

ZnF(daTZ)@HNO3

P /P0

Vo

lum

e (c

c/g

)


Figure S15. The pore size distribution of ZnF(daTZ)@HNO3 derived from Monte-Carlo model

by fitting the adsorption branch of its CO2 physisorption isotherm at 273 K with minimal fitting

error (0.967%).

S22

0 3 6 9 12 150

100

200

300

400

500

600

700

1E-4 0.001 0.010

10

20

30

40

50

60

70

4.4 Å

Pore width (Å)

dS(d

)

3.7 Å

ZnF(daTZ)@HCl

P /P0

Vo

lum

e (c

c/g

)


Figure S16. The pore size distribution of ZnF(daTZ)@HCl derived from Monte-Carlo model by

fitting the adsorption branch of its CO2 physisorption isotherm at 273 K with minimal fitting error

(0.380%).

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3 4 5 6 7 80

200

400

600

800 ZnF(daTz)@H2SO4

ZnF(daTz)@HNO3

ZnF(daTz)@HCl ZnF(daTz)

3.7 Å4.4 Å

4.2 Å

Pore width (Å)

dS(d

)

6.3 Å

Figure S17.The PSD comparison of ZnF(daTZ) with amine protonated by H2SO4, HNO3 and HCl

at pH = 4, showing the protonation would decrease the pore size and surface area.

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Table S2. Comparison of cell parameters, crystal densities (crystal), from crystallography

data, as well as surface areas (S), pore volumes (Vp) and pore sizes distributions (PSD) from

CO2 physisorption isotherms at 273 K for ZnF(TZ) and its isoreticular MOFs.

Materials a/b c crystal S Vp PSD

Å Å gꞏcm-3 m2ꞏg-1 m2·cm-3 cm3ꞏg-1 nm

ZnF(TZ) 18.6011 9.9000 1.536 613 942 0.213 0.60

ZnF(aTZ) 18.5059 9.9168 1.691 573 969 0.168 0.48

ZnF(daTZ) 18.5080 10.0376 1.854 479 888 0.119 0.42

ZnF(daTZ)@H2SO4 N.D. N.D. N.D. 285 N.D. 0.072 0.37, 0.44

ZnF(daTZ)@HNO3 N.D. N.D. N.D. 311 N.D. 0.072 0.37, 0.44

ZnF(daTZ)@HCl N.D. N.D. N.D. 289 N.D. 0.069 0.37, 0.44

ZnF(dmTZ) 18.8698 9.7902 1.787 N.D. N.D. N.D. N.D.

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0 20 40 60 80 1000

20

40

60

80ZnF(TZ)

CO2 (273 K)

CO2 (283 K)

CO2 (298 K)

N2 (298 K)

Pressure (kPa)

Gas

Upt

ake

(cm

3 ST

P/g

)

Figure S18. CO2 and N2 adsorption isotherms of ZnF(TZ) at 273, 283, and 298 K. Solid line,

adsorption; dashed line, desorption.

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0 20 40 60 80 1000

20

40

60

80ZnF(aTz)

CO2 (273 K)

CO2 (283 K)

CO2 (298 K)

N2 (298 K)

Pressure (kPa)

Gas

Upt

ake

(cm

3 ST

P/g

)

Figure S19. CO2 and N2 adsorption isotherms of ZnF(aTZ) at 273, 283, and 298 K. Solid line,


S27

0 20 40 60 80 1000

20

40

60

80ZnF(daTZ)

CO2 (273 K)

CO2 (283 K)

CO2 (298 K)

N2 (298 K)

Pressure (kPa)

Gas

Upt

ake

(cm

3S

TP/g

)

Figure S20. CO2 and N2 adsorption isotherms of ZnF(daTZ) at 273, 283, and 298 K. Solid line,


S28

0 1 2 3 4 5 60.00

0.04

0.08

0.12

0.16

0.20

0.24

ZnF(TZ) H2O (308 K)

H2O (298 K)

Pressure (kPa)

H2O

Upt

ake

(g/g

)

Figure S21. Gravimetric dynamic water vapor adsorption isotherms of ZnF(TZ) at 298 and 308

K. Solid line, adsorption; dashed line, desorption.

S29

0 1 2 3 4 5 60.00

0.04

0.08

0.12

0.16

0.20

ZnF(aTZ) H2O (308 K)

H2O (298 K)

Pressure (kPa)

H2O

Upt

ake

(g/g

)

Figure S22. Gravimetric dynamic water vapor adsorption isotherms of ZnF(aTZ) at 298 and 308

K. Solid line, adsorption; dashed line, desorption.

S30

0 1 2 3 4 5 60.00

0.02

0.04

0.06

0.08

0.10

0.12

ZnF(daTz) H2O (308 K)

H2O (298 K)

Pressure (kPa)

H2O

Upt

ake

(g/g

)

Figure S23. Gravimetric dynamic water vapor adsorption isotherms of ZnF(daTZ) at 298 and

308 K. Solid line, adsorption; dashed line, desorption.

S31

Section S4. Isosteric Heats of Adsorption

CO2 adsorption isotherms for each MOF were then fitted with single-site Tóth Model22 (J.

Chem. and Engin. Data, 2004, 49, 4.) equations as follows, where n is the total amount adsorbed

in mmol/g, P is the pressure in Pa, nsat is the saturation capacity in mmol/g, b is the parameter in

pa−1, and t is the heterogeneity parameter of adsorbents. Also see: (a) Tóth, J. Acta Chim. Acad.

Sci. Hung. 1971, 69, 311. (b) Tóth, J. Adsorption: Theory, Modeling, and Analysis; Marcel Dekker:

New York, 2002.

𝑛𝑛

𝑏𝑝

1 𝑏𝑝

The isosteric heats can be calculated from the single-site Tóth Model fitting or Virial fitting

of adsorption isotherms for each MOF as a function of the CO2 amount using the Clausius-

Clapeyron equation: 𝑄 𝑅𝑇 .

S32

0 20000 40000 60000 80000 1000000

1

2

3

273 K 283 K 298 K Single-site Tóth Model fit

CO

2 upta

ke (

mm

ol/g

)

Pressure (Pa)

Figure S24. Single-site Tóth Model fitting (lines) of the CO2 adsorption isotherms (points) for

ZnF(TZ) measured at 273, 283, and 298 K.

R2 N b t

273 K 0.99989 3.474 1.21E-05 2.510283 K 0.99997 3.116 9.44E-06 2.797298 K 0.99999 2.675 6.57E-06 2.808

S33

0 20000 40000 60000 80000 1000000

1

2

3

273 K 283 K 298 K Single-site Tóth Model fit

CO

2 upta

ke (

mm

ol/g

)

Pressure (Pa)

Figure S25. Single-site Tóth Model fitting (lines) of the CO2 adsorption isotherms (points) for

ZnF(aTZ) measured at 273, 283, and 298 K.

R2 N b t

273 K 0.99992 3.464 4.01E-05 0.916283 K 0.99996 3.450 2.53E-05 0.959298 K 0.99994 2.861 1.48E-05 1.170

S34

0 20000 40000 60000 80000 1000000

1

2

3 273 K 283 K 298 K Single-site Tóth Model fit

CO

2 up

take

(m

mol

/g)

Pressure (Pa)

Figure S26. Single-site Tóth Model fitting (lines) of the ZnF(daTZ) CO2 adsorption isotherms

(points) measured at 273, 283, and 298 K.

R2 N b t

273 K 0.99931 2.265 1.84E-04 0.867283 K 0.99954 2.353 1.13E-04 0.835298 K 0.99989 2.242 5.54E-05 0.901

S35

0.0 0.5 1.0 1.5 2.00

10

20

30

40

50

ZnF(aTZ)

ZnF(daTZ)

CO2 uptake (mmol/g)

-Qst (

kJ/m

ol)

ZnF(TZ)

Figure S27. Coverage-dependent heats of CO2 adsorption for ZnF(TZ), ZnF(aTZ), ZnF(daTZ)

based on the Clausius-Clapeyron equation.

S36

0 2 4 6 8 10 12 144

5

6

7

8

9

298 K 308 K Viral fitting

Ln[P

ress

ure

(P

a)]

H2O uptake (mmol/g)

Figure S28. Virial fitting (lines) of the H2O adsorption isotherms (points) for ZnF(TZ) measured

at 298 and 308 K.

a0 -4669.92816 ± 376.21001a1 912.05039 ± 0a2 -624.90529 ± 178.21255a3 144.61901 ± 59.71429a4 -13.58832 ± 6.67424a5 0.44379 ± 0.24474b0 22.73838 ± 1.2402b1 -5.06778 ± 0.0816b2 2.69623 ± 0.58621b3 -0.57194 ± 0.1964b4 0.05149 ± 0.02196b5 -0.00163 ± 8.05296E-4

R2 0.99802

S37

0 2 4 6 8 104

5

6

7

8

9

298 K 308 K Viral Fitting

Ln[P

ress

ure

(P

a)]

H2O uptake (mmol/g)

Figure S29. Virial fitting (lines) of the H2O adsorption isotherms (points) for ZnF(aTZ) measured

at 298 and 308 K.

a0 -6214.08389 ± 395.08682a1 341.13019 ± 0a2 -337.03661 ± 141.08248a3 61.25022 ± 33.9498a4 -3.03092 ± 2.0961b0 28.25199 ± 1.3008b1 -3.12317 ± 0.11257b2 1.84325 ± 0.47009b3 -0.33624 ± 0.11336b4 0.02093 ± 0.00724b5 -2.91972E-4 ± 9.58703E-5

R2 0.99474

S38

0 1 2 3 4 5 6 74

5

6

7

8

9

298 K 308 K Viral fitting

Ln[P

ress

ure

(P

a)]

CH4 uptake (mmol/g)

Figure S30. Virial fitting (lines) of the H2O adsorption isotherms (points) for ZnF(daTZ) measured

at 298 and 308 K.

a0 -4277.92058 ± 145.86444a1 320.67599 ± 0a2 -311.08091 ± 134.54028a3 55.09404 ± 50.81249a4 -2.82967 ± 4.86969b0 22.03369 ± 0.48269b1 -3.44813 ± 0.07145b2 2.38928 ± 0.44663b3 -0.60408 ± 0.16914b4 0.07397 ± 0.01676b5 -0.0037 ± 3.41778E-4

R2 0.99926

S39

0 3 6 9 12 150

10

20

30

40

50

60

70

ZnF(aTZ)

ZnF(daTZ)

H2O uptake (mmol/g)

-Qst (

kJ/m

ol)

ZnF(TZ)

Figure S31. Coverage-dependent heats of H2O adsorption for ZnF(TZ), ZnF(aTZ), ZnF(daTZ)

based on the Clausius-Clapeyron equation.

S40

Section S5. Calculation of IAST Selectivity

The ideal adsorbed solution theory (IAST) (Myers, A. L.; PrausniTZ, J. M. AIChE J. 1965,

11, 121.) was used to calculate the CO2/N2 selectivity for each MOF. The adsorption isotherms

were fitted with Single-site or Dual-site Langmuir Freundlich Model equations as follows, where

there are two n is the total amount adsorbed in mmol/g, P is the pressure in pa, nL is the saturation

capacity in mmol/g, b is the parameter in Kpa−1, and t is the heterogeneity parameter of adsorbents.

𝑛𝑛

𝑏 𝑝

1 𝑏 𝑝

𝑏 𝑝

1 𝑏 𝑝

S41

0 20 40 60 80 1000.0

0.5

1.0

1.5

2.0

2.5

CO2

N2

Pressure (KPa)

Gas

Upt

ake

(cm

3 ST

P/g

)

ZnF(Tz)@298 K

Figure S32. Single-site Langmuir-Freundlich Model fitting (lines) of the CO2 and N2 adsorption

isotherms (points) for ZnF(TZ) measured at 298 K.

R2 N b t

CO2 0.99998 6.93036 0.00216 0.9328

N2 0.9999 0.61524 0.00145 0.86395

S42

0 20 40 60 80 1000.0

0.5

1.0

1.5

2.0

2.5

CO2

N2

Pressure (kPa)

Ga

s U

pta

ke (m

mol

/g)

ZnF(aTz)@298 K

Figure S33. Dual-site Langmuir Freundlich Model fitting (lines) of the CO2 and N2 adsorption

isotherms (points) for ZnF(aTZ) measured at 298 K.

R2 N b t

2.61219 0.00789 0.8872

0.3978 0.03769 0.85463

0.02586 0.00581 0.60328

0.36859 3.69E-04 0.65494

CO2

N2

1

0.99997

S43

0 20 40 60 80 1000.0

0.5

1.0

1.5

2.0 CO2

N2

Pressure (KPa)

Gas

Upta

ke (m

mol

/g)

ZnF(daTz)@298 K

Figure S34. Dual-site Langmuir Freundlich Model fitting (lines) of the CO2 and N2 adsorption

isotherms (points) for ZnF(daTZ) measured at 298 K.

R2 N b t

1.50813 0.02042 1.34963

1.36195 0.0595 0.89148

0.02548 0.0153 0.85903

1.19695 3.17E-04 0.81947

CO2

N2

1

0.99997

S44

Figure S35. Single-site Langmuir-Freundlich Model fitting (lines) of the H2O and CO2 adsorption

isotherms (points) for ZnF(TZ) measured at 298 K.

S45

Figure S36. Single-site Langmuir Freundlich Model fitting (lines) of the H2O and CO2 adsorption


S46

Figure S37. Single-site Langmuir Freundlich Model fitting (lines) of the H2O and CO2 adsorption


S47

0 20 40 60 80 1000

700

1400

2100

2800

3500

H2O

/CO

2 IA

ST

Sele

ctiv

ity

Relative Humidity (%)

ZnF(aTZ) ZnF(TZ) ZnF(daTZ)

Figure S38. The IAST H2O/CO2 thermodynamic selectivity for the ZnF(TZ), ZnF(aTZ) and

ZnF(daTZ) under various relative humidity.

S48

Table S3. Comparison of CO2 capture properties in this work with benchmark materials.

Materials Qst crystal CO2 uptake at 0.15 bar IAST Selectivity

Ref. (kJ mol-1) (g/cm3) (mmol/g) (mmol/cm3) N2/CO2

ZnF(daTZ) 33 1.854 0.96 1.78 85:15 120 This work ZnF(aTZ) 32.3 1.691 0.56 0.95 85:15 46

ZnF(TZ) 23.6 1.536 0.27 0.41 85:15 13 SIFSIX-2-Cu-i 31.9 1.246 2.25 2.80 90:10 140

S21 SIFSIX-3-Cu 54 1.6 2.51 4.02 90:10 >2000 [Mg2(dobdc)] 42 0.92 5:89@296 K 5.42 85:15 182

S22 USTA-16 35 1.66 2.61@296 K 4.33 85:15 315 Al-PMOF 52 N.D. 1.80@293 K N.D. N.D. N.D. S23

[Zn2(ox)(atz)2] 40.8 1.713 2.05@293 K 3.51 N.D. N.D. S24

UiO-66-NH2 28 N.D. 1.15 N.D. 75:15 66.5 (Henry’s law) S25 PCN-88 27 0.657 0.75@296 K 0.49 85:15 15.2 S26 MAF-66 26 1.128 1.29 1.46 N.D. 225 (Henry’s law) S27 mmen-

CuBTTri 96 1.059 2.38 2.52 75:15 327 S28

MAF-X27ox 124 1.354 4.10 5.55 N.D. N.D. S29

S49

Section S6. Dynamic Gas Adsorption Breakthrough Measurements

Humidity-dependent (33%, 53%, and 99% RH) CO2/N2 breakthrough measurement: A

stainless-steel column with a length of 15 cm and an internal diameter of 0.42 cm (Vcolumn = 2.1

cm3) was packed with 1.238 g of ZnF(daTZ), 0.7335 g of ZnF(aTZ) or 0.8016 g of ZnF(TZ)

powder sample respectively. The column was connected to a Quantachrome FLOVAC degasser

via 6 mm O ring and adapter, and degassed at 120 ºC overnight. Then it was transferred to the

injection and sampling ports (Scheme S1). The column was immersed in a water bath filled with

Ethylene glycol aqueous solution (1:3, v/v) circulated by a Vivo RT2 isothermal bath, for which

the temperature stability is 25 ± 0.5 °C. The volumetric flow rates (SCCM) of pure gases (N2, CO2,

He, 99.999% purity) were regulated by Alicat mass flow controllers (MFCs). Before breakthrough

experiments, the sample was purged with passing He (5 mL min–1) for 1 hour at 298 K. Pure N2

(0.85 mL min–1) and CO2 (0.15 mL min-1) were mixed and then used directly as dry (0% RH) or

passed through a saturated saltwater solution (Magnesium Chloride for 33% RH, Magnesium

Nitrate for 53% RH and pure water for 99% RH) for several hours before injected to the column

to make sure that the salt solvent is saturated with CO2. Then the dry He was switched to wet 15:85

CO2/N2 mixture to start the breakthrough experiment. The gas stream at the outlet of the column

was diluted by He (9 mL min-1) and analyzed online by PerkinElmer Clarus 580 GC equipped with

an N9305013 packed column and Thermal Conductivity Detector (TCD).

S50

Scheme S1. Setup of packed column gas adsorption breakthrough experiments.

Table S4. Control of relative humidity of mimic flue gas through saturated solution of salts.

RH% 33 53 99

saturated solution MgCl2 Mg(NO3)2 Pure water

S51

0 50 100 150 2000.0

0.2

0.4

0.6

0.8

1.0

Out

let f

low

rat

e (m

L/m

in)

Breakthrough time (min/g)

ZnF(Tz)

99% RH N2 CO2

dry N2 CO2

53% RH N2 CO2

N2 flow

CO2 flow

Figure S39. The CO2/N2 adsorption breakthrough curves of ZnF(TZ) under dry, 53% and 99%

RH at 298 K in the unit of outlet flow rate (mL/min) showing that the separation capacity keeps

persistent even under 99% RH.

S52

0 50 100 150 2000.0

0.2

0.4

0.6

0.8

1.0

1.2

C/C

0


ZnF(TZ)

99% RH N2 CO2

dry N2 CO2

53% RH N2 CO2

N2

CO2

Figure S40. The CO2/N2 adsorption breakthrough curves of ZnF(TZ) under dry, 53% and 99%

RH at 298 K, showing that the separation capacity keeps persistent even under 99% RH. C0 is the

inlet concentration, C is the outlet concentration.

S53

0 50 100 150 200 2500.0

0.2

0.4

0.6

0.8

1.0

N2 flow

Out

let f

low

rat

e (m

L/m

in)


ZnF(aTz)

99% RH N2 CO2

dry N2 CO2

53% RH N2 CO2

CO2 flow

Figure S41. The CO2/N2 adsorption breakthrough curves of ZnF(aTZ) under dry, 53% and 99%

RH at 298 K in the unit of outlet flow rate (mL/min) showing that the separation capacity keeps

persistent even under 99% RH.

S54

0 50 100 150 200 2500.0

0.2

0.4

0.6

0.8

1.0

1.2

C/C

0


ZnF(aTZ)

99% RH N2 CO2

dry N2 CO2

53% RH N2 CO2

N2

CO2


RH at 298 K, showing that the separation capacity keeps persistent even under 99% RH.

S55

0 50 100 150 200 250 3000.0

0.2

0.4

0.6

0.8

1.0

N2 flowO

utle

t flo

w r

ate

(mL/

min

)


ZnF(daTz)

99% RH N2

CO2

dry N2

CO2

53% RH N2

CO2

33% RH N2

CO2

CO2 flow

Figure S43. The CO2/N2 adsorption breakthrough curves of ZnF(daTZ) under dry, 53% and 99%

RH at 298 K in the unit of outlet flow rate (mL/min) showing that the separation capacity would

be strengthened under 33% and 53% RH.

S56

0 50 100 150 200 250 3000.0

0.2

0.4

0.6

0.8

1.0

99% RHDry53% RH33% RH

C/C

0


ZnF(daTZ) (298 K) N2

CO2


RH at 298 K, showing that the separation capacity keeps persistent even under 99% RH.

S57

0.7

0.8

0.9

1.0

1.1

1.2

1.3

ZnF(TZ)

UC

O2(h

umid

)/UC

O2(

dry)

ZnF(aTZ) ZnF(daTZ)

99% RH

53% RH

Dry

33% RH

Dry

53% RH

99% RH

Dry

99% RH

53% RH

298 K

Figure S45. The ratio of the UCO2(humid) obtained from the humid (33%, 53%, 99% RH) dynamic

CO2 capacity to the UCO2(dry ) obtained from dry dynamic CO2 capacity [UCO2(humid)/UCO2(dry )] is

plotted for ZnF(TZ), ZnF(aTZ) and ZnF(daTZ), calculated from the value of Table S4.

S58

Table S5. Comparison of the CO2 uptake capacities at 0.15 bar from the static isotherms

and dynamic breakthrough measurements in the unit of cm3 g-1.

Materials Static Dynamic Uptake

Uptake dry 33% RH 53% RH 99% RH

ZnF(TZ) 6.0 6.9 N.D. 7.3 8.0

ZnF(aTZ) 12.6 11.7 N.D. 11.9 11.2

ZnF(daTZ) 21.5 21.5 25.7 23.8 21.1

S59

Water (75% RH) breakthrough measurement: The breakthrough instrument CT-3

equipped with GC-9860 and Thermal Conductivity Detector (TCD) was purchased from Xuzhou

North Gaorui Electronic Equipment Co., Ltd. CN. A stainless-steel column with a length of 8 cm

and an internal diameter of 0.42 cm (Vcolumn = 0.35 cm3) was packed with 0.38 g of ZnF(daTZ)

powder sample. The column was connected to a Quantachrome FLOVAC degasser via 6 mm O

ring and adapter, and degassed at 120 ºC overnight. Then it was transferred to the injection and

sampling ports. The column was heated with a heating bag, for which the temperature stability is

25 ± 0.5 °C. Before breakthrough experiments, the sample was purged with passing He (15 mL

min–1) for 1 hour at 298 K. Premixed N2 and CO2 (15%) (5 mL/min) purchased from commercial

resource were used directly as dry (0% RH) or passed through a pure water for several hours before

injected to the column to make sure that the water is saturated with CO2. Then the dry He was

switched to wet 15:85 CO2/N2 mixture to start the breakthrough experiment. The water signal was

recorded with a commercial hygrometer.

S60

0 10 20 30 40 150 160 170 180 190 200

0

1

2

3

4

5

6

CO2 Flow

N2 Flow O

utle

t Flo

w R

ate

(mL/

min

)


ZnF(daTz)Inlet: N2/CO2 (v/v = 15/85), 75 RH%, 298 K

Outlet R

elative Hum

idity

H2O Signal

Figure S46. The CO2/N2/H2O(75% RH) adsorption breakthrough curves of ZnF(daTZ) at 298 K.

S61

Section S7. Dynamic Vapor Sorption (DVS) Measurements

DVS from Surface Measurement Systems (UK) is a gravimetric apparatus to measure the mass

change of the sample using continuously and constant nitrogen flow to bring the vapor to the

sample. By varying the flow rates of two mass flow controllers (one passing through the liquid and

the other one does not), different relative humidity (from 0-95%) or vapor partial pressure can be

achieved and maintained. The carrier gas can be changed to CO2 (15%), N2 mixture gas to measure

the CO2 kinetics.

Scheme S2. Instrumentation setup of the DVS experiment.

S62

0 300 600 900 12000

50

100

150

200

250

H2O

Up

take

(m

g/g

)

Time (min)

ZnF(TZ) (298 K)

0

20

40

60

80

100

Re

lative H

umidity

Figure S47. The time-dependent water adsorption at 33%, 53% and 95% RH under dynamic

conditions of ZnF(TZ).

S63

0 100 200 300 400 500 6000

50

100

150

200

H2O

Upta

ke (

mg/g

)

Time (min)

ZnF(aTZ) (298 K)

0

20

40

60

80

100

Rela

tive Hum

idity


conditions of ZnF(aTZ).

S64

0 100 200 300 400 500 6000

20

40

60

80

100

120

H2O

Up

take

(m

g/g

)

Time (min)

ZnF(daTZ) (298 K)

0

20

40

60

80

100

Re

lative H

umidity


conditions of ZnF(daTZ).

S65

0 20 40 60 80 100 1200.0

0.2

0.4

0.6

0.8

1.0

Mt/M

∞

t1/2 (s1/2)

R2 = 0.994

ZnF(daTZ) (298 K) CO2(15%) + N2

H2O(95% RH) + N2

H2O(53% RH) + N2

H2O(33% RH) + N2

R2 = 0.999

R2 = 0.999

R2 = 0.999

Figure S50. The CO2 (15%) and water adsorption kinetics of ZnF(daTZ) at 298 K for various

relative humidity obtained by dynamic vapor sorption.

S66

0 30 60 90 1200.0

0.2

0.4

0.6

0.8

1.0

ZnF(TZ) (298 K) CO2(15%) + N2

H2O(95% RH) + N2

H2O(53% RH) + N2

H2O(33% RH) + N2

Mt/M

∞

t1/2 (s1/2)

R2 = 0.994

R2 = 0.999R2 = 0.999

R2 = 0.999

Figure S51. The CO2 (15%) and water adsorption kinetics of ZnF(TZ) at 298 K for various relative

humidity obtained by dynamic vapor sorption.

S67

0 20 40 60 800.0

0.2

0.4

0.6

0.8

1.0

ZnF(aTz) (298 K) CO2(15%) + N2

H2O(95% RH) + N2

H2O(53% RH) + N2

H2O(33% RH) + N2

Mt/M

∞

t1/2 (s1/2)

R2 = 0.996

R2 = 0.999

R2 = 0.999

R2 = 0.999

Figure S52. The CO2 (15%) and water adsorption kinetics of ZnF(aTZ) at 298 K for various

relative humidity obtained by dynamic vapor sorption.

S68

Table S6. The slope obtained from the kinetic curves by linear fitting and the CO2/H2O

kinetic curves of the series isoreticular materials.

Material Slope Kinetic Selectivity

ZnF(TZ) CO2 (15%) 0.11135 / 95% RH 0.02792 15.9 53% RH 0.02027 30.2 33% RH 0.01419 61.6

ZnF(aTZ) CO2 (15%) 0.16376 / 95% RH 0.04647 12.4 53% RH 0.03294 24.7 33% RH 0.02144 58.3

ZnF(daTZ) CO2 (15%) 0.14755 / 95% RH 0.03337 19.6 53% RH 0.02582 32.7 33% RH 0.01753 70.8

S69

0

15

30

45

60

75

90

RH

(%)

298 K

0 500 1000 1500 2000 25000.00

0.02

0.04

0.06

0.08

0.10

0.12

Time (min)

Wat

er

Upt

ake

(g/

g)

Figure S53. The circling dynamic water sorption between 0-75% RH at 298 K for 25 cycles,

showing no loss of the H2O capacity and only the dry N2 without heating can gain the 99% of the

water capacity.

S70

Section S8. CO2 /H2O Competitive Adsorption Kinetics

To investigate the co-adsorption sites and kinetics of CO2 and H2O within the pore of

ZnF(daTZ), the carrier gas would be switched to the CO2/N2 mixture. Firstly, after activated the

sample under dry N2 flow at 100 ºC, the carrier gas was switched to CO2/N2 mixture with 33, 53

or 95% RH H2O vapor to observe the mass change of the sample, which means the CO2 and H2O

were injected to the sample at the same time. Secondly, the sample was treated with 10, 15, 20, 25

ro 30% RH water vapor until equilibrium was reached, then the carrier gas was switched to CO2/N2

mixture without changing the humidity of gas mixture. Finally, the sample was treated with dry

CO2/N2 mixture until equilibrium was reached and then adjusted the water content to 33, 53 or 95%

RH respectively.

S71

0 5000 10000 15000 200000.00

0.02

0.04

0.06

0.08

0.10

0% 10% 15% 20% 25% 30%

Gas

/Va

por

Up

take

(g

/g)

Time (s)

298 KPretreated with water at specific RH

0%

Figure S54. The time-dependent adsorption uptake of two-step treating: the first step was H2O/N2

adsorption at 0, 10, 15, 20, 25, 30% RH, the second was CO2/N2/H2O adsorption comparison at 0,

10, 15, 20, 25, 30% RH respectively, showing that there were sharp mass increment of CO2

adsorption even the pore volume was 57% occupied by H2O at 30% RH.

S72

0 500 1000 1500 20000.00

0.01

0.02

0.03

CO

2 U

pta

ke (

g/g

)

Time (s)

298 K Pretreated with water at specific RH%0%

10%

15%

20%

25%

30%

Figure S55. The CO2 time-dependent adsorption uptake after water adsorption intercepted from

Figure S54.

S73

0 5 10 15 20 25 30 35 40 450.0

0.2

0.4

0.6

0.8

1.0

0% 10% 15% 20% 25% 30%

Mt/M

∞

t1/2 (s1/2)

CO2 (298 K)

Pretreated with waterat specific RH%

Figure S56. The CO2 adsorption kinetics of ZnF(daTZ) pretreated with water at specific RH%.

S74

0 3000 6000 9000 12000 15000 180000.00

0.03

0.06

0.09

0.12

CO2 + H2O(95%)

CO2 + H2O(53%)

CO2 + H2O(33%)

Ga

s/V

ap

or

Up

take

(g/

g)

Time (s)

298 K

Pretreated with CO2(15%)/N2;

then CO2(15%)/N2/H2O(RH%)

Figure S57. The time-dependent adsorption uptake of two-step treating: the first step was dry

CO2/N2 adsorption, the second was CO2/N2/H2O adsorption at 33, 53, 95% RH respectively.

S75

0 3000 6000 9000 12000 150000.00

0.03

0.06

0.09

0.12

H2O(95%)

CO2 + H2O(95%)

H2O(53%)

CO2 + H2O(53%)

H2O(33%)

CO2 + H2O(33%)

H2O

Upta

ke (

g/g

)

Time (s)

298 K Pretreated with CO2(15%)/N2;

then CO2(15%)/N2/H2O(RH%)

Figure S58. The H2O time-dependent adsorption uptake of CO2-pre-adsorbed sample compared

with the activated sample at 33, 53, 95% RH respectively.

S76

0 20 40 60 80 100 1200.0

0.2

0.4

0.6

0.8

1.0

CO2 + H2O(95%)

H2O(95%)

CO2 + H2O(53%)

H2O(53%)

CO2 + H2O(33%)

H2O(33%)

Linear Fitting

Mt/M

∞

t1/2 (s1/2)

H2O (298 K)

Figure S59. The water kinetics of CO2-pre-adsorbed sample compared with the activated sample

at 33, 53, 95% RH respectively, showing that pre-adsorbed CO2 would decrease the water kinetics.

S77

0 100 200 300 400 5000

10

20

30

40ZnF(daTz) (298 K)H2O + N2 + CO2(15%)

33% RH 53% RH 95% RH

Gas

/Vap

or U

ptak

e (m

g/g)

Time (s)

Figure S60. The CO2/N2/H2O (33, 53, 95% RH) time-dependent adsorption uptake at 298 K,

showing that under different humidity there were sharp mass increment resulted from CO2

adsorption compared with H2O/N2 adsorption.

S78

Table S7. H2O uptake, CO2/H2O uptake at 0, 10, 15, 20, 25, 30% RH. Vp% is the pore

volume occupied percent (water uptake at 0, 10, 15, 20, 25, 30% RH /water-saturated

uptake). Uhumid/Udry is the CO2 uptake percent (CO2 uptake at 0, 10, 15, 20, 25, 30% RH /

CO2-saturated uptake).

RH% H2O g/g

Vp% CO2

g/g Uhumid/Udry

0% 0 0.00% 0.02473 100.00%

10% 0.004404 3.90% 0.02399 97.01%

15% 0.01045 9.26% 0.02171 87.79%

20% 0.02558 22.68% 0.01751 70.80%

25% 0.04659 41.30% 0.01104 44.64%

30% 0.06467 57.33% 0.00687 27.78%

S79

Table S8. Comparison of the water kinetics of CO2-pre-adsorbed sample and activated

sample at 33, 53, 95% RH respectively.

H2O CO2 + H2O kCO2+H2O/kH2O

slope slope

95% RH 0.0334 0.02519 57.0%

53% RH 0.0258 0.0201 60.6%

33% RH 0.0175 0.01532 76.4%

S80

Section S9. Cycling Mimic Flue Gas Adsorption Breakthrough Measurements

Cycling mimic flue gas (0.67 g powder samples), ternary N2/CO2 (15%)/H2O(85% RH) (0.880 g

powder or 1.168 g pellet ZnF(daTZ), 1.565 g pellet 13 X) column breakthrough were carried out

using an automated breakthrough analyser-ABR systems (Scheme S3, manufactured by Hiden

Isochema, Warrington, U.K.). There are four inlet gas lines, one is the purge gas (usually Ar or

He) and the others are working gas. Firstly the four-way valve is on position B to control the purge

gas pass through the column to activate the sample, then the four-way valve is switched to position

A to let the working gas flow into the sample. The stream at the outlet of the column is monitored

by an online mass spectrum. The sample holder is a stainless-steel column with a length of 7 cm

and an internal diameter of 0.6 cm (Vcolumn = 2.1 cm3). The mimic flue gas (N2 80%, 15% CO2, 5%

O2, 1000 ppm SO2, 500 ppm NO2) was purchased from commercial resources. Between the cycles

Ar flow was used to purge the sample for 0.5 h at 298 K. The ternary N2/CO2 (15%)/H2O(85% RH)

component was gained by N2 flow (8.5 mL/min) passing through the pure water mixed with dry

CO2 (1.5 mL/min). Between the 5 cycles the sample was reactivated by Ar flow (10 mL/min) for

25 min.

S81

Scheme S3. Apparatus setup of cycling packed column gas adsorption breakthrough

experiments.

S82

0 20 40 60 80 100 1200.0

0.2

0.4

0.6

0.8

1.0

1.2

C/C

0

Breakthrough Time (min/g)

Mimic Flue Gas(with SO2 and NO2)

Cycle 1 Cycle 10 Cycle 20 Cycle 30 Cycle 40 Cycle 50

CO2

N2 + O2ZnF(daTZ)(298 K)

Column: 7 cm*0.3 cm2

Figure S61. Cycling gas adsorption breakthrough curves of ZnF(daTZ) for mimic flue gas at 298

K and flow rate of 2.3 mL/min.

S83

0 5 10 15 20 25 300.0

5.0x10-10

1.0x10-9

1.5x10-9

2.0x10-9

2.5x10-9

3.0x10-9

Ar 14 mL/min N2

CO2

O2

MS

sig

nals

(T

orr)

Purge Time (min)

Figure S62. The representative purge process between the 50 cycles of simulated flue gas

breakthrough showing the mild host-guest physisorption interactions and reactivation condition.

S84

0 10 20 30 400

1x10-8

2x10-8

3x10-8

4x10-8

5x10-8

CO2

N2 O

utle

t Gas

Sig

nals

(T

orr)


ZnF(daTz)Inlet: N2/CO2 (v/v = 15/85), 85 RH%, 298 K

Outlet H

2 O S

ignal (Torr)

H2O

0E+00

1E-10

2E-10

3E-10

4E-10

5E-10

Figure S63. The N2/CO2(15%)/H2O(85% RH) ternary breakthrough curves, the water signal is

amplified because of its lower content (about 2%).

S85

0 5 10 15 20 250.0

0.2

0.4

0.6

0.8

1.0

C/C

0


85% RH, 298 K Cycle 1 Cycle 2 Cycle 3 Cycle 4 Cycle 5

CO2

ZnF(daTZ) N2

Figure S64. Cycling gas adsorption breakthrough curves of ZnF(daTZ) pellets for CO2/N2 (v:v =

15:85) mixed gas under 85% RH at 298 K and flow rate of 10 mL/min.

S86

0 5 10 15 20 250.0

5.0x10-9

1.0x10-8

1.5x10-8

2.0x10-8

0 5 10 15 20 250

1x10-10

2x10-10

3x10-10

4x10-10

5x10-10

Purge Time (min)

Wate

r S

igna

l (T

orr

)

Ar 10 mL/min N2

CO2

H2O

MS

sig

nal (

Tor

r)

Purge Time (min)

Figure S65. The represent purge process between the 5 cycles (Figure 2e) of N2/CO2 (15%)/H2O(85%

RH) ternary breakthrough with pellet ZnF(daTZ), showing no signal of water when regeneration.

S87

0 5 10 15 20 25 30 35 400.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

C/C

0


85% RH, 298 K

CO2

13X

N2

Figure S66. Cycling gas adsorption breakthrough curves of zeolite 13X pellets for CO2/N2 (v:v =

15:85) mixed gas under 85% RH at 298 K and flow rate of 10 mL/min, showing obvious decreasing

of its CO2 capacity.

S88

Section S10. GCMC Simulations and DTF Calculations to Investigate the Adsorption Sites

We performed density functional theory (DFT) calculation within the GGA of Perdew, Burke,

and Ernzerhof (PBE)30 and the DFT-D3 dispersion correction method31. The Vienna Ab initio

Simulation Package (VASP) code32 with a plane-wave basis set and projector-augmented-wave33

pseudopotentials were used for all calculations. To obtain a fully relaxed structure of the ZnF(daTZ)

framework, we use a plane-wave cutoff energy of 800 eV for the basis set and a Γ-point sampling

for the Brillouin zone integration using PBE. During relaxation, the atomic positions are optimized

until the residual forces are smaller than 0.05 eV/Å.

The initial adsorption site geometries were generated by performing Monte Carlo (MC)

simulations using classical force fields. We perform NVT simulations at 298K to obtain density

maps about the center of mass of molecules within the ZnF(daTZ) framework. In each simulation,

a single H2O or CO2 molecule is placed inside a simulation box that is composed of multiple unit

cells to ensure that the dimension along each perpendicular direction is larger than twice the cutoff

radius. A total of 1033 MC cycles with random translation, rotation, and regrow moves were used

in each simulation. From the density maps about the center of masses of a molecule, we identified

the high-density points; 5 or 12 adsorption sites for CO2 or H2O (Figures S47 and S48) in the unit

of ZnF(daTZ), respectively. Using the point as the center of masses, CO2 or H2O molecule is

inserted with the orientation giving the minimum energy. Each configuration with a molecule for

each site was chosen to be the initial configuration for further DFT binding geometry optimization.

Both in the classical calculation and the following DFT calculations, the framework was regarded

as rigid. The long-range Coulomb interactions were computed with an Ewald summation technique.

Point charges assigned to the framework atoms were determined from the DFT calculations by the

REPEAT scheme34. The obtained point charges for atom types of the framework are summarized

S89

in Figure S67 and Table S9. Dispersion interaction energies for the framework were computed

from a Lennard-Jones (LJ) potential form with parameters from the universal force field (UFF)35.

Trappe forcefield36 or SPCE model37 was used for CO2 or H2O, respectively. The

Lorentz−Berthelot mixing rule was used for the pairwise interaction parameters between two

different atomic species. In addition, all pairwise non-electrostatic interactions were truncated and

shifted to zero at a distance of the cutoff radius. The red columns in Figure S71 show the adsorption

energy estimated using DFT calculation of 5 CO2 sites. The adsorption energy of CO2 is estimated

as:

𝐸 , 𝐸 𝐸 𝐸

Where 𝐸 indicates the energy of MOF with a CO2 molecule adsorbed, 𝐸 is the

energy of MOF, and 𝐸 means the energy of a single CO2 molecule.

Figure S67. The types of atoms in the framework.

S90

Table S9. DFT derived atomic charges for framework atoms.

Atom Type Charge C 0.847

H_1 0.154 H_2 0.292 N_1 -0.770 N_2 -0.625 N_3 -0.625 Zn 1.338 F -0.509

S91

Figure S68. The COM (Center of Mass) of CO2 molecules, showing that the CO2 was adsorbed

in the center of the channel.

S92

Figure S69. The COM of H2O molecules, showing that the H2O was adsorbed in the one side of

the channel.

S93

To check the effect of H2O on the adsorption of CO2 in ZnF(daTZ), we investigated the

changes in binding energies of CO2 in the ZnF(daTZ) due to the existence of H2O. For each CO2

adsorption site, we found the most strongly interacting combination of CO2 and H2O by switching

an H2O molecule at 12 different H2O adsorption sites while fixing CO2 molecule at the site. For

each possible combination, the adsorption energy of CO2 is estimated using the DFT calculation

as 𝐸 , 𝐸 𝐸 𝐸 where 𝐸 indicates the energy of

MOF with CO2 and H2O adsorbed, 𝐸 is the energy of MOF with only H2O adsorbed,

𝐸 means the energy of a single CO2 molecule.

S94

Figure S70. The most energetically favorable H2O and CO2 configurations for the five different

CO2 adsorption sites in ZnF(daTZ). A ZnF(daTZ) framework is partially shown for clarity.

Distances are in Å unit.

S95

Figure S71. Comparison between CO2 adsorption energies without H2O and with H2O for five

different CO2 adsorption sites. The number index at the x-axis corresponds to the CO2 adsorption

sites shown in Figure S70.

The adsorption heats calculated by DFT simulations are 27.9-33.8 and 28.1-36.0 kJ/mol for

CO2 and H2O, respectively, which are consistent with the experimental results (32.9 and 35.3

kJ/mol). The adsorption energies with H2O and without H2O cases are compared in Fig. S50. When

a H2O exists, the adsorption energies of CO2 increased prominently, which indicates that the CO2

molecule is more strongly adsorbed in the humid condition. This result would demonstrate that the

interaction between H2O and CO2 molecules plays a role in enhancing the adsorption of CO2

molecules in ZnF(daTZ), which is in agreement with our experimental observation.

S96

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