Supporting Information

A Porous Covalent Organic Framework with Voided Square

Grid Topology for Atmospheric Water Harvesting

Ha L. Nguyen,†,‡ Nikita Hanikel,†,‡ Steven J. Lyle,† Chenhui Zhu,§ Davide M.

Proserpio,⊥,∥ and Omar M. Yaghi*,†,Ñ

†
Department of Chemistry, University of California—Berkeley; Kavli Energy Nanoscience
Institute at UC Berkeley; Berkeley Global Science Institute; and Materials Sciences Division,
Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
§
Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California
94720, United States
⊥Dipartimento di Chimica, Università degli Studi di Milano, Milano 20133, Italy
∥Samara Center for Theoretical Materials Science (SCTMS), Samara State Technical
University, Samara 443100, Russia
Ñ
UC Berkeley-KACST Joint Center of Excellence for Nanomaterials for Clean Energy
Applications, King Abdulaziz City for Science and Technology, Riyadh 11442, Saudi Arabia

*To whom correspondence should be addressed: yaghi@berkeley.edu

‡
Equal contribution

S1

 Table of Contents

Section S1 Materials and General Methods S3

Section S2 Synthesis of COF-432 S4

Section S3 Fourier-Transform Infrared (FTIR) Spectroscopy S5

Section S4 Solid-State Nuclear Magnetic Resonance (NMR) S6

Section S5 Scanning Electron Microscopy (SEM) S7

Powder X-ray Diffraction (PXRD) Analysis, Wide-
Section S6 Angle X-ray Scattering (WAXS) Analysis and S8-S13
Structural Elucidation
Section S7 Topological Analysis S14

Section S8 N2 Sorption Analysis S15-S16

Section S9 Thermogravimetric Analysis (TGA) S17

Section S10 Hydrolytic Stability Tests S18-S19

Section S11 Water Sorption Analysis S20-S21

Section S12 Water Sorption Cycling Stability S22

Section S13 References S23

S2

Section S1: Materials and General Methods
Chemicals used in this work. Chloroform (99.8% purity, extra dry grade), tetrahydrofuran
(99.9% purity, extra dry grade), and 1,3,5-triformylbenzene (TFB, 98% purity) were purchased
from Acros Organics. Methanol (99.8% purity, extra dry grade) and acetic acid (≥98% purity)
were obtained from Merck Millipore. 1,1,2,2-Tetraphenylethylene (98% purity) was purchased
from TCI America. Hydrazine monohydrate (98% purity) and palladium on carbon (10 wt%) were
obtained from Sigma Aldrich. All chemicals were used without further purification. Ultrahigh-
purity grade N2 and He from Praxair (99.999% purity) were used for the sorption experiments.
Analytical techniques. Elemental microanalyses (EA) were performed by using a LECO CHNS-
932 CHNS elemental analyzer (Section S2). Fourier-transform infrared (FTIR) spectra were
collected using a Bruker ALPHA Platinum ATR-FTIR Spectrometer equipped with a single
reflection diamond ATR module (Section S3). Solid-state nuclear magnetic resonance (NMR)
spectra were collected using a 7.05 T magnet with a Tecmag Discovery spectrometer operating at
300.13 MHz for 1H and 75.48 MHz for 13C (Section S4). Scanning electron microscopy (SEM)
images were recorded on a FEI Quanta 3D FEG scanning electron microscope with an accelerating
voltage of 10 kV and a working distance of 10.0 mm (Section S5). Powder X-ray diffraction
(PXRD) data was collected on a Bruker D8 Advance diffractometer (Bragg-Brentano geometry)
employing Ni filtered Cu Kα1 (λ = 1.54059 Å) radiation (Section S6). Wide-angle X-ray scattering
(WAXS) patterns were acquired on beamline 7.3.3 at the Advanced Light Source (ALS) with a
Pilatus 2M detector (Section S6). N2 sorption measurements were carried out on a Micromeritics
3Flex Surface Characterization Analyzer (Section S8) and ASAP 2420 System (Section 10). A
liquid N2 bath was used for measurements at 77 K. Thermogravimetric analysis (TGA) curves
were recorded on a TA Q500 thermal analysis system under dry N2 flow (Section S9).
Water sorption isotherms were measured on a BEL Japan BELSORP-aqua3 (Section 11). The
water (analyte) was degassed through five freeze-pump-thaw cycles before the sorption
experiment. The measurement temperature was controlled using a water circulator. The water
adsorption-desorption cycling stability (Section 12) was probed with a TA Instruments SDT Q600
series thermal gravimetric analyzer (TGA). The primary gas inlet was connected to a dry nitrogen
tank. The secondary gas inlet was used to supply humidified nitrogen, which was generated by
passing dry nitrogen gas through a gas washing bottle (2 L) filled with water. The temperature and
relative humidity (RH) were monitored using high-accuracy thermocouples and humidity sensors
downstream the TGA chamber. The desired RH was achieved by adjusting the ratio of dry to
humidified nitrogen gas flow, while maintaining the sum of both flows constant at 250 mL min-1.

S3

Section S2: Synthesis of COF-432

Synthesis of 1,1,2,2-Tetrakis(4-aminophenyl) ethene (ETTA)

1,1,2,2-Tetrakis(4-aminophenyl)ethene (ETTA) was synthesized according to a previously

reported procedure.1

Synthesis and activation of COF-432

A Pyrex tube measuring 10 × 8 mm (o.d × i.d) was charged with ETTA (12 mg, 0.031 mmol),
TFB (7.3 mg, 0.046 mmol), and a mixture of chloroform/methanol (0.6:0.4 mL). The solution was
then sonicated for 5 min before addition of aqueous acetic acid (0.2 mL, 6M). The tube was flash-
frozen at 77 K under liquid N2, evacuated to an internal pressure of 100 mTorr and flame-sealed
to a length of ca. 15 cm. The reaction was heated to 120 °C for 3 d yielding a yellow solid, namely
COF-432, that was isolated by filtration, washed 5 times with methanol, and solvent-exchanged
with chloroform in a Soxhlet extractor for 24 h. COF-432 was then activated under dynamic
vacuum at room temperature for 3 h followed by dynamic vacuum at 85 °C for 12 h. EA of COF-
432: Calcd. for C114H72N12·6H2O: C, 79.70; H, 4.93; N, 9.78%. Found: C, 78.35; H, 4.94; N,
10.01%.

S4

Section S3: Fourier-Transform Infrared Spectroscopy (FTIR)

COF-432

Transmittance / a.u. O-H = 3428 cm-1

TFB C=N = 1628 cm-1

ETTA C=O = 1692 cm-1

N-H = 3352 cm-1

4000 3500 3000 2500 2000 1500 1000 500

Wave number / cm -1

Figure S1. FTIR spectra of COF-432, TFB, and ETTA, colored in red, blue, and black,
respectively.

S5

Section S4: Solid-State Nuclear Magnetic Resonance (NMR)

Figure S2. Solid-state 13C cross-polarization magic angle spinning nuclear magnetic resonance
spectrum of COF-432. The assignments of 13C chemical shifts are indicated next to the atoms in
the chemical structure and the respective peaks in the spectrum.

S6

Section S5: Scanning Electron Microscopy (SEM)

Figure S3. SEM micrograph indicating phase-purity and uniform morphology (a) of COF-432.
The crystal size of COF-432 is ca. 100 × 100 × 300 nm3 (b).

S7

Section S6: Powder X-ray Diffraction (PXRD) Analysis, Wide-Angle X-ray Scattering
(WAXS) Analysis and Structural Elucidation
PXRD data collection
PXRD measurements were carried out using a Bruker D8 Advance diffractometer in reflectance
Bragg-Brentano geometry employing Ni filtered Cu Kα1 focused radiation (1.54059 Å) at 1600 W
(40 kV, 40 mA) power, which was equipped with a LynxEye detector. The best counting statistics
were achieved by collecting samples using a 0.02° 2θ step scan from 3 – 50° with an exposure
time of 10 s per step. The measurement was performed at room temperature and atmospheric
pressure.

Structural elucidation of COF-432

Unit cell determination
The unit cell parameters were determined by indexing the PXRD pattern with TOPAS 4.2.2 A
body-centered tetragonal lattice with the space group I41/a (No. 88) was found for COF-432.
Whole pattern profile fitting and extraction of the integrated intensities was carried out using data
from 2θ = 5 – 50°. A background correction was performed using a 20-parameter Chebyschev
polynomial function.
Electron density map calculation
A charge flipping method executed via Superflip3 was used to calculate the electron density map
of COF-432. A calculation was first made by assuming that the observed intensities were extracted
from single-crystal data using the indexed integrated intensities obtained from the Pawley fit.
Later, a calculation was performed adapting the powder pattern routine with the histogram
generated by considering the electron density map which was calculated assuming the use of
single-crystal data. An electron density map was also calculated with the intensities extracted in
the space group P1. The converged results were obtained validating the I41/a space group with a
success rate of 70%.

S8

Figure S4. Electron density map of COF-432 showing regions of high electron density which can
be assigned to the ETTA fragments.
Structural model and Le Bail fit
A structural model of COF-432 was generated by using the Materials Visualizer module within
Materials Studio (Material Studio ver. 7.0, Accelrys Software Inc.) as follows: The ETTA linker
was first located at the positions indicated by the electron density map. ETTA linkers were then
linked by the TFB building units. To comply to the symmetry of I41/a, one of the ETTA building
units was modeled as disordered. Upon completion of the structural model, an energetic
minimization was performed using a universal force field implemented in the Forcite module of
Materials Studio. During this process, the unit cell parameters were also optimized until proper
convergence was achieved (energy convergence criteria were set at 10-4 kcal mol-1).
At last, a full profile pattern fitting based on the Le Bail method was performed on the experimental
WAXS pattern from 2θ = 2 – 45° to yield the final unit cell parameters (a = 30.65 Å, c = 12.85 Å)
with the residual values of Rp = 2.88% and Rwp = 3.96%.
The fractional atomic coordinates and refined unit cell parameters for COF-432 can be found in
Table S1. Further crystallographic information is provided in Table S2.

S9

Figure S5. Le Bail fit for COF-432 against the experimental WAXS pattern displaying the
experimental pattern (black) and the refined fit (red). The background (blue), difference plot
(green), and Bragg positions (pink) are also provided.

Figure S6. Comparison of the simulated (orange) pattern with the experimental WAXS pattern
(black) of COF-432. Bragg positions (pink) are also provided. We note that the relative peak
intensities of the simulated and experimental PXRD patterns of COF-432 deviate, which could be
explained by the presence of guest molecules (likely water in this case, as evidenced by EA and
FTIR, SI, Section S2 and S3) in the pores.4–6

S10

Table S1. Atomic coordinates and refined unit cell parameters of COF-432.
Name COF-432
Space Group I41/a (No. 88)
a (Å) 30.65
c (Å) 12.85
Unit Cell Volume
12075
(Å3)
Atom Name Occupancy x y z
H1 1 0.3760 0.9299 0.5974
H2 1 0.2126 1.0317 0.6280
H3 1 0.2599 0.8984 0.5919
H4 1 0.1549 0.9622 0.6199
H5 1 0.3334 1.1720 0.7559
H6 1 0.3850 1.2318 0.7836
H7 1 0.4825 1.1624 0.6172
H8 1 0.4339 1.0993 0.6095
H9 1 0.1521 0.8160 0.4797
H10 1 0.0881 0.7685 0.4654
H11 1 0.0162 0.8608 0.6440
H12 1 0.0776 0.9096 0.6475
H13 1 0.2849 1.1056 0.6673
H14 1 0.3542 1.0068 0.6198
H15 1 0.4787 0.8270 0.5155
H16 1 0.4241 0.8832 0.5223
H17 1 0.3398 0.7964 0.6876
H18 1 0.3986 0.7451 0.7058
C1 1 0.3438 0.9161 0.6028
C2 1 0.3065 0.9463 0.6100
C3 1 0.2399 1.0068 0.6266
C4 1 0.2660 0.9327 0.6030
C5 1 0.2301 0.9609 0.6097
C6 1 0.1809 0.9399 0.6016
C7 1 0.3657 1.1686 0.7239
C8 1 0.3968 1.2046 0.7390
C9 1 0.4409 1.2069 0.6978
C10 1 0.4509 1.1661 0.6500
C11 1 0.4211 1.1290 0.6419
C12 1 0.3763 1.1288 0.6723
C13 1 0.1235 0.8690 0.5665

S11

 C14 1 0.1226 0.8269 0.5166
C15 1 0.0845 0.7978 0.5103
C16 1 0.0430 0.8054 0.5592
C17 1 0.0445 0.8486 0.6062
C18 1 0.0817 0.8788 0.6084
C19 1 0.3075 1.0767 0.6563
C20 1 0.2860 1.0243 0.6429
C21 1 0.3192 0.9949 0.6242
C22 1 0.0024 0.7742 0.5500
C24 1 0.4460 0.7820 0.6169
C25 1 0.4505 0.8211 0.5613
C26 1 0.4183 0.8532 0.5637
C27 1 0.3779 0.8448 0.6105
C28 1 0.3712 0.8045 0.6557
C29 1 0.4053 0.7749 0.6647
N1 1 0.3393 0.8744 0.6113
N2 1 0.3471 1.0881 0.6554
N3 1 0.1657 0.8969 0.5758
C30 0.5 0.4977 0.7727 0.6120

S12

Table S2. Important crystallographic information for COF-432.

Parameters COF-432
Empirical formula C114H72N12
Calculated density (g cm-3) 0.875
Symmetry Tetragonal
Space group I41/a
a (Å) 30.65
c (Å) 12.85
Unit Cell Volume (Å3) 12075
Rp factor (%) 2.88
Rwp factor (%) 3.96
Wavelength (Å) 1.2389
Temperature (K) 298
Angular range 2θ (°) 2 – 45
Refining method Le Bail
Refined background model Chebyschev polynomial of degree 20
Profile shape function Pearson VII
Correction Zero-shift

S13

Section S7: Topological Analysis
The topology of COF-432 was determined by using the ToposPro software.7 TFB and ETTA
represent a 3-c and a 4-c node, respectively, which are linked to generate the two-dimensional mtf
network. This net has three kind of vertices and two kind of edges, and the vertices are linked into
4- and 8-membered rings.

Figure S7. The augmented mtf net of COF-432.

We note that this 2D net topology deviates from a possibly expected 3D net8 or recently reported
2D bex topology9 for the combination of a triangular and a rectangular tetratopic linker, thus
extending the scope of observed topologies in COF chemistry.

S14

Section S8: N2 Sorption Analysis

Permanent porosity of activated COF-432 was shown by N2 sorption analysis at 77 K.

400
Ads
Des
300
N2 uptake / cm3 g-1

200
Surface area (BET) = 895 m2 g-1

100

0
0.0 0.2 0.4 0.6 0.8 1.0
P/P0

Figure S8. N2 sorption isotherm of activated COF-432 at 77 K. The filled and open circles
represent the adsorption and desorption branch, respectively. The connecting line in the N2
isotherm is provided as a guide for the eye.

400

Ads
300 Des
N2 uptake / cm3 g-1

200

100

10-7 10-6 10-5 10-4 10-3 0.01 0.1 1

log 10 (P/P0)

Figure S9. N2 sorption isotherm of activated COF-432 at 77 K. The filled and open circles
represent the adsorption and desorption branch, respectively. The connecting line in the N2
isotherm is provided as a guide for the eye.

S15

Figure S10. Pore size distribution of COF-432 based on the N2-DFT fit indicates the presence of
a single pore with a width of ca. 8.0 Å.

S16

Section S9: Thermogravimetric Analysis (TGA)

Thermal stability of COF-432 was examined by thermogravimetric analysis. COF-432 (4 mg) was
heated under nitrogen flow (60 mL min-1) from 30 to 800 °C with a gradient of 5 °C min-1.

100

80
Weight / %

60

40

100 200 300 400 500 600 700 800

Temperature / oC

Figure S11. Thermogravimetric analysis of COF-432 under nitrogen flow.

S17

Section S10: Hydrolytic Stability Tests

Activated COF-432 was soaked in water at room temperature. PXRD analyses were conducted at
different time intervals (3, 6, 10 and 20 days). Comparison of the respective PXRD patterns
indicates that COF-432 maintains its crystallinity in water for at least 20 d.

20 d in water
Intensity / a.u.

10 d in water

6 d in water

3 d in water

before water treatment

5 10 15 20 25 30
2 / º, CuK

Figure S12. PXRD analyses of COF-432 after immersing it in water for different amounts of time
(3, 6, 10 and 20 days).

S18

 500
COF-432
COF-432 in water 90 h
400

N2 uptake / cm3 g-1 300

200

100

0 0.2 0.4 0.6 0.8 1.0

P/P0

Figure S13. N2 sorption analysis at 77 K of activated COF-432 before and after immersion in
water for 90 hours. The filled and open circles represent the adsorption and desorption branch,
respectively. The connecting line is provided as a guide for the eye.

S19

Section S11: Water Sorption Analysis

Figure S14. Four consecutive water sorption measurements on COF-432 at 25 °C. P: Water vapor
pressure. Psat: Saturation vapor pressure of water at 25 °C.

Figure S15. Water sorption analysis on COF-432 at different temperatures (10, 25, 40 °C).
P: Water vapor pressure. Psat: Saturation vapor pressure of water at the respective temperature.

S20

 50

45
Qst / kJ mol-1

40

35
0 0.04 0.08 0.12 0.16 0.20 0.24 0.28 0.32
Water uptake / g g -1

Figure S16. Isosteric heat of adsorption of COF-432, as determined by the Clausius-Clapeyron

relation applied to the water sorption isotherms measured at different temperatures (10, 25, 40 °C).

Table S3. Water sorption properties of selected COFs.

COF Pore Water uptake Working capacity Major BET (m2 g–1) BET (m2 g–1) Ref.
diameter (g g–1) at (g g–1) at P/Psat = hysteresis (before water (after water
(nm) P/Psat = 0.40 0.20–0.40 and loop sorption) sorption)
and 298 K 298 K
TpPa-1 1.8 0.32 0.15 yes 984 855 10
TpPa-2 1.5 0.12 0.08 yes 460 452 10
TpPa-NO2 1.6 0.15 0.01 yes 457 415 10
TpPa-F4 1.7 0.02 0.01 yes 529 440 10
TpBD-(OMe)2 2.3 0.06 0.03 yes 365 248 10
TpBD-(NO2)2 2.2 0.02 0.01 yes 90 70 10
2,5-DhaTph 2.0 0.01 0.00 yes 1112 1058 10
2,3-DhaTph 2.0 0.06 0.02 yes 659 580 10
a a b
AB-COF 1.3 0.32 0.26 yes 1120 1080 11
a a b
ATFG-COF 1.2 0.15 0.02 yes 520 506 11
TpBD 2.4 0.10 0.04 yes 341 265 12
TpBpy 2.4 0.22 0.18 yes 942 921 12
c,d
COF-432 0.75 0.23 0.23 no 895 895 This
work
a
Measured at 288 K. bSurface area measured after soaking the COF in water for 3 h. cBET surface area measured after
soaking the COF in water for 90 h and dafter 7 cycles of water sorption.

S21

Section S12: Water Sorption Cycling Stability

400

Before water uptake

After 7 cycles of water uptake
N2 uptake / cm3 g-1 300

200
Surface area (BET) = 895 m2 g-1

100

0 0.2 0.4 0.6 0.8 1.0

P/P0

Figure S17. N2 sorption analysis at 77 K of activated COF-432 before and after 7 consecutive
water sorption measurements. The filled and open circles represent the adsorption and desorption
branch, respectively. The connecting line is provided as a guide for the eye.

Figure S18. Water cycling stability test for 300 adsorption-desorption cycles conducted on COF-
432 at constant water vapor pressure (1.7 kPa). Adsorption and desorption are carried out at 30 °C
(40% relative humidity, RH) and 35 °C (30% RH), respectively.

S22

Section S13: References

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