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A Customized Hydrophobic Porous Shell for MOF-5

Jianhui Li,§ Puxu Liu,§ Yang Chen, Jinfei Zhou, Jingwei Li, Jiangfeng Yang, Daliang Zhang,* Jinping Li,
and Libo Li*
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ABSTRACT: The susceptibility to moisture of metal−organic

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frameworks (MOFs) is a critical bottleneck for their wider practical

application. Constructing core−shell composites has been
postulated as an effective strategy for enhancing moisture
resistance, but for fragile MOFs this has rarely been accomplished.
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We report herein, for the first time, the construction of a

customized hydrophobic porous shell, NTU-COF, on the
particularly fragile MOF-5 by a “Plug-Socket Anchoring” strategy.
Notably, the pore structure of MOF-5 was well maintained, and it
could still achieve complete CO2/N2 separation under humid
conditions. The homogeneous interface between MOF-5 and
NTU-COF has been inspected at atomic resolution by a combination of cryogenic focused ion beam (cryo-FIB) and ultralow-dose
(scanning) transmission electron microscope giving profound insight into the mechanism of assembly of the core−shell structure.
This work presents a facile strategy for the fabrication of a hydrophobic porous shell for labile MOFs, and provides a general
approach for solving the problem of moisture instability of porous materials for practical applications.

■ INTRODUCTION
Porous materials, especially metal−organic frameworks
oxygen coordinative bonds in MOF-5 are easily attacked by
water molecules, resulting in collapse of the framework.21 The
structural instability of MOFs (especially water susceptibility)
(MOFs) assembled from organic linkers and inorganic metal
is thus a critical bottleneck in their real-world applications. As
(or metal-containing cluster) nodes,1−4 have received tremen-
regards the extraordinarily labile MOF-5, it is highly desirable
dous scientific attention in the last two decades. Given the
to develop new strategies or mechanisms to enhance its
variable choices of metal and ligand combinations, MOF
hydrophobicity.
structures can be rationally designed and prepared to meet
In order to tackle this problem, enormous efforts have been
targeted requirements for diverse applications, including, but
made to obtain hydrophobic MOFs by direct or de novo
not limited to, gas storage and separation, heterogeneous
synthesis, or to decorate MOFs with hydrophobic surfaces.22 It
catalysis, chemical sensing, and drug delivery.5−12 Among the
has been demonstrated that the introduction of water-repellent
reported MOFs, MOF-5, first synthesized by Yaghi et al.13 in
functional groups by a postsynthetic modification (PSM)
1999, is one of the milestone materials, consisting of
approach can improve the moisture resistance of MOFs.23−26
tetrahedral Zn4O units connected by linear terephthalic acid
Applying this approach, Cohen and Nguyen27 reported that
(H2BDC) linkers to form a cubic network structure, and has
the introduction of hydrophobic alkyl chains by PSM could
been extensively investigated for numerous applications14−17
increase the tolerance of IRMOF-3 (NH2-MOF-5) to
due to its merit of ultrahigh Brunauer−Emmett−Teller (BET) moisture. Taking inspiration from the strong water-repelling
surface area. More importantly, from a practical perspective, effects of methyl and trifluoromethoxy groups in polymer
the ready availability of the precursors makes it possible to chemistry, Masel et al.28 synthesized a series of new MOFs
synthesize MOF-5 in a high yield. Despite being a research with a cubic topology similar to that of the MOF-5 structure.
hotspot, the applicability of MOF-5 is curtailed by its They confirmed that it was feasible to construct a water-
inadequate long-term structural and functional robustness, resistant MOF by adopting isoreticular ligands pregrafted with
particularly when recyclability under ambient conditions is
desired. For example, Long et al.18 found that atmospheric
moisture could induce a phase transformation in MOF-5 after Received: May 9, 2023
only 10 min exposure, and complete structural conversion took Published: August 14, 2023
place after 24 h, resulting in low-surface-area MOF-69c.19
Rapid and irreversible hydrolysis of the framework has been
noted upon contact with aqueous media.20 Indeed, molecular
dynamics simulations have corroborated that the weak metal−

© 2023 American Chemical Society https://doi.org/10.1021/jacs.3c04831

19707 J. Am. Chem. Soc. 2023, 145, 19707−19714
Journal of the American Chemical Society pubs.acs.org/JACS Article

Figure 1. “Plug-Socket Anchoring” strategy for the construction of a hydrophobic porous shell on MOF-5.

one or more repellent groups. Nevertheless, the extent of based COF family, possess highly stable structures against
modification, that is, the number of water-repelling groups, harsh chemical environments, including boiling water, strong
greatly affected the level of hydrophobicity introduced. The acids/bases, and oxidizing/reducing conditions.35−38 For the
larger steric hindrance of functionalized ligands is inevitable to improvement of the moisture resistance, hydrophobic COFs
alter the original porosity and separation properties. Moreover, are particularly reliable options. Coating of compatible COFs
postmodification or replacement of original ligands makes it on MOFs to form MOF@COF core−shell composites may be
difficult to precisely synthesize MOFs with targeted function- instrumental for improving the moisture stability of
alities. In contrast, Park and Yang29 proposed a new method MOFs.39−41 However, the construction of novel core−shell
for improving the water stability of MOF-5 without the MOF@COF composites with improved stability remains a
introduction of additional functional groups. They covered the great challenge, especially the appending of hydrophobic
MOF-5 with amorphous carbon by a simple heat treatment at porous COF shells to such vulnerable MOFs.
a specific temperature. This amorphous carbon coating on the Constructing a homogeneous and stable COF shell on the
surface of MOF-5 shielded it from direct exposure to moisture, surface of MOF-5 while maintaining the crystallinity of the
thereby preventing hydrolysis. Under the same processing underlying MOF is an indispensable prerequisite for a
conditions (such as gas flow rate, heating rate), however, successful synthesis. Based on a Schiff-base reaction and the
uneven carbonization can be expected, due to nonuniform lattice-matching principle, we propose herein a “Plug-Socket
MOF particle sizes. Zhu et al.30 also contributed a feasible Anchoring” strategy for applying a perfect covering of a COF.
solution-immersion approach to deposit a hydrophobic The obtained NTU-COF (NTU, Nanyang Technological
organosilicon (DC 1-2577) layer on the MOF surface, which University) is a rational option considering the high degree of
exhibited significant enhancement in water stability. This matching (N−N distance of 25.8 Å for -NH2 grafted on the
coating process was simple (just mixing DC 1-2577 with MOF MOF-5 surface vs N−N distance of 25.5 Å for C�N in the
powder), and heating was not involved. Jiang et al.31 developed COF) between the COF and MOF-5 (Figures 1 and S1).
a more ingenious and easy-to-operate approach by applying a Here, a uniform hydrophobic NTU-COF shell was first
polydimethylsiloxane (PDMS)-coating treatment to form a fabricated on the MOF-5 surface with unprecedentedly
protective hydrophobic layer on an MOF surface to improve enhanced water resistance (contact angle 136.3°), showing
moisture stability. However, achieving a uniform coating on excellent cyclic CO2/N2 separation performance under humid
the surface of overall MOF microcrystals by the vapor conditions. Notably, real-space imaging of the interface at
deposition technique is not easy, especially when dealing atomic resolution through a combination of cryo-FIB and
with large-scale samples for practical applications. Although ultralow-dose (S)TEM techniques confirmed successful
considerable efforts have been devoted to improving the assembly of the target core−shell structure of MOF-5 covered
moisture stability of MOF-5, there remains an urgent need to by NTU-COF. This provides experimental validation of the
develop a more facile and universal strategy from both fundamental mechanism of the “Plug-Socket Anchoring”
academic and practical perspectives. strategy for covering a labile MOF with a hydrophobic COF
Covalent organic frameworks (COFs), another emerging shell.
class of porous crystalline materials, are constructed by
covalently linking directional organic building blocks.32−34
Like MOFs, they are characterized by high porosity and
■ RESULTS AND DISCUSSION
Construction Strategy and Characterizations. The
crystallinity, a tunable pore size, and readily tailored synthesis procedure of the MOF-5@NTU-COF core−shell
functionalities. Furthermore, COFs, especially the Schiff- composite is illustrated in Figure 2a. First, MOF-5 with high
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Figure 2. (a) Schematic illustration of the preparation of core−shell MOF-5@NTU-COF composite. (b−e) SEM images and (f−i) corresponding
TEM images of MOF-5 and MOF-5@NTU-COF composites. Insets show enlarged images.

crystallinity was prepared by a solvothermal method using of which the former can generate an imine group in the
N,N-dimethylformamide (DMF) as the solvent (Figures 2b presence of an amino group, while the latter can easily form a
and S2). Subsequently, the resultant MOF-5 microcrystals boroxine ring at high temperature. Importantly, these two
were incubated in a solution of 2-aminoterephthalic acid reactions are compatible in terms of similar reaction
(H2BDC-NH2) in DMF (10 mL), arousing the replacement of conditions, and so can be simultaneously applied in the
external H2BDC linkers with H2BDC-NH2 linkers on the construction of NTU-COF42 (Figures S6 and S7). Finally,
MOF-5 surface. Compared with the white MOF-5 sample, NTU-COF was polymerized in situ on the MOF-5 surface by
MOF-5 (NH2) turned yellow, acquiring a similar but lighter covalently linking FPBA and 1,3,5-tris(4-aminophenyl)-
color to that of IRMOF-3 (Figure S3). The bulk color change benzene (TAPB) monomers with the formation of an imine
preliminarily supported successful linker replacement (BDC → group and a boroxine ring. As shown in Figure 2b, bare MOF-5
BDC-NH2) on the surface of MOF-5. The presence of amino exhibited a cubic morphology with smooth surfaces and regular
groups on the surface of MOF-5 (NH2) was further verified by sharp edges. After the grafting of surface amino groups, MOF-5
recording the FT-IR spectrum and X-ray photoelectron (NH2) almost maintained the cubic morphology of MOF-5
spectroscopy (XPS). As depicted in Figure S4, a new peak at (Figure S8). As the NTU-COF grew uniformly on the MOF-5
1205 cm−1, characteristic of the stretching vibration of C−N surface, the MOF-5@NTU-COF hybrid presented rough
bonds, and two doublets in the region 3400−3500 cm−1, surfaces, although the cubic morphology of the pristine
characteristic of symmetric and asymmetric stretching MOF was well maintained (Figure 2c−e). Meanwhile, due to
vibrations of primary amine N−H, could be observed successful decoration with the external shell, MOF-5@NTU-
compared with the spectrum of bare MOF-5. The presence COF presented a similar yellow color to NTU-COF, and the
of C, N, and Zn elements was inspected by the XPS spectra of color gradually deepened as the coating amount of COF
MOF-5 (NH2) (Figure S5). Notably, there are distinctive increased (Figure S9). From the TEM images, it can be clearly
peaks with high intensity for N 1s corresponding to the -NH2 noted that the NTU-COF shell was homogeneously
group at 399.8 eV, indicating the presence of -NH2 on the distributed on the MOF-5 core, exhibiting a typical core−
MOF-5 (NH2) surface. The N content in MOF-5 (NH2) was shell structure (Figure 2f−i). The thickness of the COF shell
further identified to be 1.02 wt % using the element analysis proved to be highly controllable (from 38 to 160 nm) by fine-
(EA) test (N: 1.02 wt %; C: 38.34 wt %; H: 3.67 wt %). MOF- tuning the amounts of the respective COF monomers (Figures
5 (NH2) was then grafted with aldehyde groups through a 2g−i and S9). Besides, PXRD patterns acquired for the hybrid
Schiff-base reaction between the -NH2 groups on its surface composites combined the characteristic crystalline features of
and aldehyde groups from 4-formylphenylboronic acid both NTU-COF and MOF-5, which further confirmed the
(FPBA). FPBA contains both aldehyde and boronate groups, successful construction of the MOF-5@NTU-COF composite
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(Figure S10). Moreover, the peak at 4.2° seen for NTU-COF

gradually intensified as the coating content of NTU-COF was
increased. After coating the NTU-COF, the Zn content in the
MOF-5@NTU-COF(1), MOF-5@NTU-COF(2) and MOF-
5@NTU-COF(3) showed an unsurprisingly decreasing order;
they were 31.5, 26.8, and 23.4 wt %, respectively (Table S1).
Additionally, EA (element analysis) for the carbon content in
the bare MOF-5 and each composite was 37.34 wt % (MOF-
5), 46.70 wt % (MOF-5@NTU-COF(1)), 48.77 wt % (MOF-
5@NTU-COF(2)), and 53.94 wt % (MOF-5@NTU-
COF(3)), respectively (Table S2). The decreased Zn content
combined with the increased carbon content in these
composites well demonstrated the increase of the COF coating
amount. Thermogravimetric analysis (TGA) traces proved that
the MOF-5@NTU-COF composites all showed high thermal
stability up to 450 °C (Figure S11). N2-sorption at 77 K was
carried out to evaluate the surface areas and pore size
distributions of the samples (Figures S12 and S13; Table S3).
The BET surface areas of the respective MOF-5@NTU-COF
composites were calculated as 778 m2/g, 772 m2/g, and 506
m2/g, respectively, higher than that of pure NTU-COF (409
m2/g), but lower than that of MOF-5 (878 m2/g). Notably, in
comparison with that of pure MOF-5, the N2 sorption
isotherms at 77 K for the composites exhibited significant
hysteresis due to the presence of NTU-COF, confirming the
coexistence of the hetero structures. The pore size distributions
of the respective samples were estimated by a nonlocal density Figure 3. (a) HAADF-STEM image of int-MOF-5@NTU-COF, with
functional theory method, and showed that the composites a SAED pattern taken from the region of int-MOF-5 shown as an
inherited the pore distributions of MOF-5 (0.6 nm) and NTU- inset. (b) High-resolution iDPC-STEM image from the area marked
COF (1.2, 1.4 nm). in (a), showing the sharp interface between int-MOF-5 and NTU-
To better understand the relationship and formation COF. (c) Magnified iDPC-STEM image and (d) corresponding FFT
mechanism of the MOF-COF composite, real-space observa- pattern of (b). (e) Symmetry-imposed lattice-averaged image of the
int-MOF-5 region with the structural model of int-MOF-5 overlaid
tions of the interface between the two phases were conducted.
(green and blue colors indicate two interpenetrated components). (f)
However, for such a typical beam-sensitive material, MOF-5, to Real-space averaged image from a series of cropped motifs at the
achieve the atomic imaging of their local structures is a great interface. (g) Proposed intergrowth model overlaid on (f). (h) Model
challenge, since MOF-5 is easily damaged by electron of MOF-5 and NTU-COF intergrowth.
beams.43−45
Recently, a combination of cryo-FIB and the integrated
differential phase contrast (iDPC) technique has proved to be of “motifs” from the high-resolution iDPC-STEM image along
a suitable method for inspecting the interface structures of the boundary of the int-MOF-5/NTU-COF interface (Figure
beam-sensitive crystalline materials.46 In this study, randomly S16). We then calculated an averaged image with an enhanced
selected MOF-5@NTU-COF crystals were subjected to cryo- signal-to-noise ratio, as shown in Figure 3f, in which the half-
FIB processing to make thin TEM lamellae (Figures S14 and hexagonal-shaped channel of NTU-COF was aligned with Zn
S15). Selected-area electron diffraction (SAED) and HAADF clusters, as shown in Figure 3g. Since the NTU-COF
STEM imaging were first conducted for basic structural studies framework could only connect with the organic linkers in
(Figure 3a). According to the SAED data, the crystallinity of MOF-5, we could unequivocally determine the connection
the MOF crystal was well maintained during the FIB process between int-MOF-5 and NTU-COF (Figures 3h and S17−
due to the cryogenic temperature. A sharp boundary between S19). The total energy of the connection is about 934.5 kJ/
the MOF-5 and NTU-COF components could be observed in mol, as calculated on the basis of density functional theory
the high-resolution iDPC-STEM images (Figure 3b, c). We (DFT), which implies that the model should be thermody-
found that the MOF-5 crystal had an interpenetrated structure namically stable.
and so was designated as int-MOF-5. In contrast to the cubic Enhancement of Moisture Stability. To check the
crystal structure of MOF-5, that of int-MOF-5 is trigonal. The moisture stability of the MOF-5@NUT-COF, water contact
fast Fourier transform (FFT) pattern of the iDPC-STEM angles were first measured to investigate the surface properties
image could thus be indexed to the [001] zone axis of MOF-5 of pristine MOF-5 and the as-prepared hybrid composites.
or the [241] zone of int-MOF-5 (Figure 3d). The p2- According to a previous report, MOF-5 is highly susceptible to
symmetry-imposed lattice-averaged potential profile was in attack by water molecules, resulting in a collapsed framework
good agreement with the structural projection of int-MOF-5, and a water contact angle close to 0° (Figures 4a and S20).
and both the organic linkers and metal clusters could be Meanwhile, NTU-COF exhibits excellent hydrophobicity, with
directly identified, as shown in Figure 3e. The surface of the a water contact angle of 139.3°, due to its micronano flake
MOF boundary was ideally flat at the atomic level (Figure 3c). structure and aromatic-rich skeleton.47 Through the tailored
However, the contrast of the NTU-COF was too weak to be coating of NTU-COF, the water contact angles of MOF-5@
seen. In order to circumvent this problem, we cropped a series NTU-COF(1−3) were significantly increased at 107.0°,
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Figure 4. Water contact angles of (a) MOF-5 and (b) MOF-5@NTU-COF. (c) Experimental breakthrough curves for CO2/N2 (15:85, v/v) on
MOF-5 and MOF-5@NTU-COF under humid conditions at 298 K and 1 bar. (d) PXRD profiles and (e) N2 sorption isotherms at 77 K before and
after breakthrough experiments of MOF-5 and MOF-5@NTU-COF. (f) Separation performances over four consecutive breakthrough cycles for
MOF-5 and MOF-5@NTU-COF (CO2/N2, 15:85, v/v, RH = 44%).

Figure 5. SEM images of (a) UiO-66, (b) UiO-66@NTU-COF, (c) MIL-125, and (d) MIL-125@NTU-COF. (e, f) N2 sorption isotherms of UiO-
66, UiO-66@NTU-COF, MIL-125, MIL-125@NTU-COF, and NTU-COF at 77 K.

124.6°, and 136.3°, respectively (Figures 4b and S21), showing of the prepared MOF-5@NTU-COF composites, the
excellent water-repellent behavior. The hydrophobicity im- adsorptive separation performance of MOF-5@NTU-
parted to MOF-5@NTU-COF motivated us to further COF(2) (abbreviated as MOF-5@NTU-COF below) toward
investigate its moisture stability under humid conditions CO2/N2 (15:85, v/v) in flue gas under humid conditions was
(Tables S4 and S5). Given the remarkable textural properties investigated (Figures 4c−f, S22, and S41). In the case of
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pristine MOF-5, CO2 was selectively adsorbed and retained on exhibited obvious hysteresis for both composites (Figure 5e,
the adsorption column under dynamic conditions, while N2 f), indicating their distinctive textural properties, and the
eluted from the column without a noticeable retention time calculated BET surface areas of the composites lay between
delay. The separation time interval for the binary CO2/N2 those of the pure MOF and pure COF (Table S6). Through
mixture was over 12 min (Figure 4c). However, under humid the tailored coating with a hydrophobic NTU-COF shell, water
conditions (RH = 44%), the separation performance of MOF- contact angles increased from 30.9° to 122.1° for UiO-66 and
5 was dramatically decreased (5 min), consistent with collapse from 32.8° to 127.2° for MIL-125 (Figures 5b, d and S40). It is
of the framework, as corroborated by PXRD and BET results conceivable that if MOFs can be modified with amino groups
after adsorption and separation (Figure 4d, e). As expected, in using the aforementioned methods, whatever the MOFs
the case of the MOF-5@NTU-COF composite, its CO2/N2 synthesized with a small isonicotinic acid ligand or a longer
separation performance was fully maintained under humid 4,4′-bipyridine ligand, the “Plug-Socket Anchoring” strategy
conditions (RH = 44%) (Figure 4c), indicating that such an can be well applied to the preparation of corresponding core−
MOF@COF hybrid provides a hydrophobic interface for shell composites. These results demonstrate that our “Plug-
MOF-5, which protects the framework from collapse. Socket Anchoring” strategy is a universal protocol for
Normally, the degradation of M(II) MOFs involves two fabricating a porous hydrophobic COF layer on the surface
steps: ligand displacement followed by hydrolysis.48 Here, of a MOF, which can significantly enhance the moisture
water molecules cannot directly attack the MOF-5 surface due resistance of unstable MOFs.
to the hydrophobic shell armor, thus avoiding the insertion of
water molecules into metal-linker coordinative bonds of the
MOF (the ligand displacement reaction), which inhibits the
initial step of carboxylate reduction (hydrolysis). To further
■ CONCLUSIONS
In summary, we developed a general and universal strategy for
confirm the cycling stability of the MOF-5@NTU-COF hybrid constructing a hydrophobic porous shell for moisture-sensitive
composites, consecutive breakthrough cycles were carried out MOFs. For the particularly fragile MOF-5, the “Plug-Socket
under humid conditions (RH = 44%) (Figures 4f, S23, and Anchoring” strategy has been utilized for the construction of a
S24). The separation performance of MOF-5 was completely customized NTU-COF shell with controllable thickness, which
lost by the fourth run, whereas no discernible separation could effectively protect MOF-5 from attack by water
capacity reduction was observed over four consecutive molecules and realize efficient CO2/N2 separation under
breakthrough cycles on MOF-5@NTU-COF, suggesting humid conditions (RH = 44%). Remarkably, by utilizing a
excellent cyclability for the CO2/N2 separation under practical combination of cryogenic focused ion beam (cryo-FIB) and
flue gas conditions. Excitingly, the separation performance of ultralow-dose (scanning) transmission electron microscope,
MOF-5@NTU-COF was also fully maintained under higher the crystal lattice of MOF-5 and the well-matched crystal
humid conditions (RH = 75%, 100%) and no discernible lattice at the homogeneous interface of MOF-5@NTU-COF
separation capacity reduction was observed over three have been inspected at atomic resolution for the first time. We
consecutive breakthrough cycles on MOF-5@NTU-COF envisage that the described “Plug-Socket Anchoring” strategy
(Figure S25). These results verified well the good potential should provide a feasible methodology for significantly
of MOF-5@NTU-COF composites for capturing CO2 under increasing the moisture stability of MOFs in general, thus
high-humidity conditions. opening broader opportunities for their practical application in
Versatility of Strategy. To explore the versatility of this the near future.
coating strategy, MIL-125 (Ti-MOF) and UiO-66 (Zr-MOF)
were chosen for further investigations (Figures S26 and S27).
By using the same solvent-assisted linker exchange (SALE)
method, amino-grafted MIL-125 (MIL-125 (NH2)) and
■
*
ASSOCIATED CONTENT
sı Supporting Information

amino-grafted UiO-66 (UiO-66 (NH2)) were prepared, the The Supporting Information is available free of charge at
structures and morphologies of which were seen to be well https://pubs.acs.org/doi/10.1021/jacs.3c04831.
maintained by PXRD and SEM (Figures S28−S31). The
pristine UiO-66 exhibited an octahedral morphology with a Additional experimental details, PXRD, FT-IR, XPS
smooth surface and a uniform average crystallite size of 500 nm spectra, ICP and EA analysis, TGA curves, SEM, TEM,
(Figure 5a). After coating with NTU-COF, its octahedral iDPC-STEM images, DFT calculations, hydrophobic
morphology was retained, but it showed a rough surface performance, stability investigations (PDF)
compared to that of pristine UiO-66 (Figure 5b). Likewise,
following the modification of MIL-125, SEM observation
revealed that the MIL-125@NTU-COF composite had almost
inherited the columnar structure, while the smooth surface of
■ AUTHOR INFORMATION
Corresponding Authors
pristine MIL-125 became rough (Figure 5c and d), which Libo Li − College of Chemical Engineering and Technology,
confirmed successful grafting of the COF shell on the MOF Shanxi Key Laboratory of Gas Energy Efficient and Clean
core. The acquired PXRD patterns featured peaks consistent Utilization, Taiyuan University of Technology, Taiyuan
with those of the parent MOF and NTU-COF (Figures S32 030024 Shanxi, P. R. China; orcid.org/0000-0001-7147-
and S33). The bulk color of each sample changed 9838; Email: [email protected]
simultaneously (Figures S34−S37), consistent with MOF-5@ Daliang Zhang − Multi-scale Porous Materials Center,
NTU-COF as described above. Both UiO-66@NTU-COF and Institute of Advanced Interdisciplinary Studies & School of
MIL-125@NTU-COF exhibited excellent thermal stability, as Chemistry and Chemical Engineering, Chongqing University,
evidenced by their TGA traces (Figures S38 and S39). After Chongqing 400044, P. R. China; Email: daliang.zhang@
coating with NTU-COF, N2 sorption isotherms (77 K) cqu.edu.cn
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030024 Shanxi, P. R. China
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Utilization, Taiyuan University of Technology, Taiyuan Redfern Louis, R.; Moribe, S.; Islamoglu, T.; Gómez-Gualdrón Diego,
030024 Shanxi, P. R. China A.; Yildirim, T.; Stoddart, J. F.; Farha Omar, K. Balancing volumetric
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Taiyuan 030024 Shanxi, P. R. China; orcid.org/0000- Jia, J.; Li, J.; Bhatt, P. M.; Huang, Z.; Jiang, H.; Jin, T.; Maurin, G.;
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§
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■ ACKNOWLEDGMENTS
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