Transformation of Metal-Organic Frameworks into Stable Organic Frameworks with Inherited Skeletons and Catalytic Properties

Article abstract of DOI:10.1002/anie.201903367

Metal-organic frameworks (MOFs) are an emerging class of porous materials with attractive properties, however, their practical applications are heavily hindered by their fragile nature. We report herein an effective strategy to transform fragile coordinat

Full text of DOI:10.1002/anie.201903367

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Accepted Article
Title: Transformation of Metal-Organic Frameworks into Stable Organic
Frameworks with Inherited Skeletons and Catalytic Properties
Authors: Chuan-De Wu and Kai Chen
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201903367
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10.1002/anie.201903367
Angewandte Chemie International Edition
COMMUNICATION
Transformation of Metal-Organic Frameworks into Stable Organic
Frameworks with Inherited Skeletons and Catalytic Properties
Kai Chen[a] and Chuan-De Wu*[a]
Abstract: Metal-organic frameworks (MOFs) are an emerging class
of porous materials with attractive properties; however, their practical
applications are heavily hindered by the fragile nature. We report
herein an effective strategy to transform fragile coordination bonds in
MOFs into stable covalent organic bonds under mild annealing
decarboxylative coupling reaction conditions, which results in highly
stable organic framework materials. This strategy endows
successfully inherit the intrinsic framework skeletons, porosity and
properties of the parent MOFs in the daughter organic framework
materials which exhibit excellent chemical stability under harsh
catalytic conditions. Therefore, this work opens a new avenue to
synthesize stable organic framework materials derived from MOFs
for applications in different fields.
polydentate carboxylates and metal ions, would be transformed
into stable organic framework materials under suitable thermal
conditions. As expected, the metalloporphyrinic MOF CZJ-6,
constructed from paddle-wheel [Cu2(COO)4] secondary building
units (SBUs) and CuII-porphyrin ligands (Scheme S1), was
successfully transformed into an organic framework material
under mild annealing decarboxylative coupling reaction
conditions, which presents high chemical stability under harsh
catalytic conditions (Scheme 1).6 Different to NPC materials
pyrolyzed from MOFs, the resultant organic framework material
successfully inherited the structural skeleton, porosity and
catalytic properties from the parent MOF CZJ-6.
Metal-organic frameworks (MOFs) are an emerging class of
crystalline porous materials constructed from metal ions/clusters
and multidentate organic ligands that are connected by
coordination bonds.1 Different to traditional solid materials, the
structures and properties of MOFs are systematically designable
and tunable, which demonstrate great potential for applications
in many fields, including gas storage and separation, chemical
sensing and catalysis.2 However, the practical applications of
MOFs are heavily hindered by the fragile nature.3
It has been demonstrated that high temperature thermolysis
of MOFs would result in stable nanoporous carbon (NPC)
materials, consisting of in situ generated metal and/or metal
oxide nanoparticles (NPs) in the pore space. Different to those
supported in traditional porous carbon materials, the
encapsulated nanoparticles in NPC materials pyrolyzed from
MOFs are uniformly dispersed in the pore space, which exhibit
attractive properties for applications as energy conversion and
storage devices, and catalysts, etc.4 However, the extreme
thermolytic conditions (up to 1000 oC) not only broke the
coordination bonds but also wiped out most of the intrinsic
properties of MOFs.
It has been known that thermal decomposition of transition
metal benzoates or terephthalates (>300 oC) would produce
volatile molecules, including benzene, benzophenone and
biphenyl.5 The possible thermolysis mechanism evolves
decarboxylation of aromatic carboxylates to form benzoyl or
benzene radicals. Direct coupling of neighboring radicals would
result in benzophenone, biphenyl and other products. As a result,
the fragile coordination bonds between metal ions and
carboxylates would be transformed into highly stable covalent
organic bonds between decarboxylated carbon atoms. Therefore,
we could deduce that the fragile MOFs, building from
Scheme 1. Schematic representation of the synthesis procedures for MOF-
derived organic framework material and NPC material.
The thermal behaviors of CZJ-6 were monitored by TG-MS
plots under N2 atmosphere. As shown in Figure 1A, a weight loss
o
(16.0%) between room temperature and 150 C is attributed to
the release of encapsulated solvent molecules and water ligands
in CZJ-6, which are consistent well with the release of water at
99 oC in the H2O-MS plot. Another weight loss (16.0%) from 250
to 400 oC is very close to the calculated value (15.7 wt%) for the
carboxylate groups in CZJ-6, indicating that CuII-porphyrin
ligands were almost fully decarboxylated in this temperature
range. There appear three peaks in both DTG and CO2-MS plots,
suggesting that the pyrolytic process consists of multiple steps
for the destruction of [Cu2(COO)4] SBUs at elevated temperature.
When the temperature is raised above 500 oC, continuous slight
decay of TG curve occurs, which should be resulted from
dehydrogenation and further carbonization of the organic
residue. The residual mass at 800 oC (58.3 wt%) is much higher
than the calculated values for pure metallic Cu (14.2 wt%) or
Cu2O (16.0 wt%) as the final products. Such a high residual
mass indicates that the residue should consist of significant
amount of nonvolatile organic matter.
[a]
K. Chen and Prof. Dr. C.-D. Wu
State Key Laboratory of Silicon Materials
Department of Chemistry
Zhejiang University
Hangzhou, 310027, P. R. China
E-mail: cdwu@zju.edu.cn
Supporting information for this article is given via a link at the end of
the document.
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10.1002/anie.201903367
Angewandte Chemie International Edition
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of CZJ-6-250 suggests that the structure of CuII-porphyrin and
Cu-O bonds remain intact. When the annealing temperature was
raised to 300 oC, the stretching vibration intensities for
carboxylate groups are significantly weakened, indicating that
decarboxylation reaction occurred. It is worth noting that the
typical C=C stretching vibration bands at 1590 cm-1 for phenyl
moieties and at 1493 cm-1 for CuII-porphyrin are almost intact.
o
Upon raising the annealing temperature to 350 C, the vibration
bands for carboxylate groups almost disappeared, while CuII-
porphyrin remained intact when the temperature was raised to
400 oC. Additionally, the characteristic out-of-plane bending
vibration bands of substituted phenyl groups at 760 and 696 cm-
1
became predominant, which further confirmed the occurrence
of decarboxylation reaction. There is almost no valuable peak in
the FT-IR spectrum of CZJ-6-800, which should be a result of
complete carbonization of the organic moieties. In the Raman
spectra, all thermally treated samples, except for CZJ-6-800,
exhibit similar vibration peaks at 1580, 1386 and 402 cm-1, which
are assigned to the phenyl ring vibration, pyrrolic C-N symmetric
stretching vibration and Cu-N stretching vibration, respectively
(Figure 1D).8 In contrast, the presence of D and G bands
centered at 1345 and 1596 cm-1 indicates that CZJ-6-800 was
highly graphitized.9
The thermal decarboxylation process was further monitored
by PXRD patterns. When a sample of CZJ-6 was thermally
treated at 250 C for 4 h, the diffraction peaks are significantly
Figure 1. (A) TG-MS and DTG plots for CZJ-6. (B) SEM images (scale bar, 5
μm), (C) FT-IR and (D) Raman spectra, and (E) PXRD patterns for CZJ-6 and
the pyrolyzed samples of CZJ-6 at different temperatures.
o
weakened. When the annealing temperature was raised to 300
oC, the low-angle diffraction peaks almost disappeared,
indicating that the long-range order of the structure of CZJ-6 did
not retain. Meanwhile, there appear the characteristic diffraction
peaks for Cu2O (JCPDS, Card No. 05-0667, 36.4, 42.3 and
61.4o) and metallic Cu (JCPDS, Card No. 04-0836, 43.2 and
50.5o) in the PXRD pattern. When the temperature was raised to
800 oC, there appears a broad peak centered at 24o for the (002)
planes of graphite carbon, indicating that CuII-porphyrin moieties
were carbonized.10 Induced by the uniform distribution of
[Cu2(COO)4] SBUs in CZJ-6, the cupreous particles are
homogeneously dispersed in the annealed samples with
diameters of 10-20 nm as revealed by TEM images, except for
CZJ-6-800 (Figure S2).
To identify the composition of the organic residues in the
annealed products, the annealed samples were eluted with
CHCl3. Brown eluates were obtained from the samples of CZJ-6-
300, 350, 400 and 450, and no colored product was extracted
from the samples of CZJ-6-250, 500 and 800 (Figure S4). UV-
vis absorption spectroscopy analysis revealed that the
absorption peaks of the brown eluates are identical to the
characteristic absorption peaks of copper(II)-5,10,15,20-
According to the TG-MS results, CZJ-6 was heated at
different elevated temperatures under N2 atmosphere (denoted
as CZJ-6-T; T = temperature) (Figure S1). After heating at 250
oC for 4 hours, brown solid sample of CZJ-6 was transformed
into dark brown solid, which should be ascribed to the loss of
water ligands and the partial reduction of copper(II) nodes.
When the temperature was raised from 300 to 450 oC, the color
of the solid sample was gradually changed from light violet to
dark purple. Above 500 oC, the metalloporphyrin moieties began
dehydrogenation and further carbonization, which was almost
fully carbonized at 800 oC. These results are consistent well with
the TG-MS results. SEM and TEM images showed that the
octahedral morphology of CZJ-6 was well reserved under
different thermal conditions (Figures 1B and S2).
UV-visible diffuse reflectance spectrum of CZJ-6 showed
that the characteristic Soret band of porphyrin is located at 425
nm with two Q bands centered at 553 and 593 nm (Figure S3).
The porphyrin moieties in the annealed sample remain intact
o
under thermal treatment at 450 C. Additionally, the broad band
assigned to the aromatic moieties on CuII-porphyrin gradually
shifted from 272 to 258 nm in the near-UV region upon raising
the annealing temperature, which should be resulted from the
loss of the carboxylate groups on benzene rings.
tetrakis[(3,5-diphenyl)phenyl]-porphyrin
(Cu-TDPPP),
the
decarboxylated analog of CuII-porphyrin ligand (Scheme S2 and
Figure S5). The concentration of CuII-porphyrin in the eluates
gradually decreased upon raising the annealing temperature.
These results indicate that decarboxylation reaction occurred at
FT-IR spectroscopy was used to monitor the organic
residual moieties in the annealed products of CZJ-6 (Figure 1C).
Broad bands at 1535 and 1398 cm-1 are ascribed to the
asymmetric and symmetric stretching vibrations of carboxylate
groups, and the peak centered at 1003 cm-1 is corresponding to
the characteristic Cu-N vibration band for CuII-porphyrin.7 No
obvious change of the absorption peaks in the FT-IR spectrum
o
low temperature (300 C) but decarboxylative coupling reaction
requires higher temperature. Upon raising the annealing
temperature, CuII-porphyrin concentration in the eluate gradually
decreased. In contrast, there are intense peaks for porphyrins in
the FT-IR, UV-vis and Raman spectra of the CHCl3-eluted
samples of CZJ-6-350, 400 and 450 (denoted as CZJ-6-TA)
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10.1002/anie.201903367
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(Figures S6-S8). These results indicate that annealing treatment
of CZJ-6 resulted in organic polymers, and the polymerization
degree is highly dependent on the annealing temperature.
and Cu2O NPs were etched with FeCl3/HCl solution, which
resulted in mesopores in the etched samples (denoted as CZJ-
6-TB; Figures S10 and 11). The surface chemical compositions
of the etched samples were characterized by monitoring the
electronic states of Cu, N and C in XPS spectra (Figure 3). The
calculated atomic ratios of N/Cu in CZJ-6-350B and 400B are
very close to 4:1, which are consistent well with the value in CuII-
porphyrin (Table S1). The N/Cu ratio increased under higher
temperature due to partial decomposition of CuII-porphyrin. In
the high-resolution Cu2p XPS spectra, the absence of Cu2p3/2
peaks for metallic Cu (932.7 eV) and Cu2O (932.5 eV) further
proved sufficient etching of the metallic Cu and Cu2O species.11
Additionally, except for CZJ-6-800B, all samples exhibit a
dominant peak at 935.2 eV for Cu2p3/2, associating with a broad
satellite peak centered at ~943 eV, which match well with those
signals for CuII-porphyrin.12 The missing of the Cu2p3/2 peak at
935.2 eV in the XPS of CZJ-6-800B indicates that CuII-porphyrin
To identify the pyrolyzed fragments, we analyzed the
eluates by MALDI-TOF MS (Figure 2). The m/z signals centered
at 1283, 2568 and 3852 are very close to the molecular mass of
mono-, di- and trimer of the decarboxylated analog Cu-TDPPP
(Mw = 1283.4) for CZJ-6-300. These results provided solid
evidences to prove that decarboxylative coupling reaction took
place between CuII-porphyrin moieties in CZJ-6 at 300 oC. Upon
raising the annealing temperature, the peak areas for highly
polymerized oligomers gradually increased (Figure S9). These
results suggest that the decarboxylative coupling reaction
between metalloporphyrins is depending on the annealing
temperature. However, excessively higher temperature resulted
in partial bond breaking between the aromatic substituents and
porphyrin cores. This conclusion was proved by monitoring the
shoulder peaks with difference of m/z 229, which were derived
from the loss of the aromatic substituents on CuII-porphyrin. The
shoulder peaks become stronger in the MALDI-TOF MS for CZJ-
6-450, indicating that there occurred severe cracking of the
metalloporphyrin residues at higher temperature. These results
proved that CuII-porphyrin ligands in CZJ-6 underwent
decarboxylative coupling reaction to form cross-linked organic
polymers under annealing treatment conditions, and the
optimized temperature should be 400 oC for CZJ-6.
o
was completely carbonated at 800 C. In the N1s XPS spectra,
two peaks centered at 398.7 and 399.9 eV are corresponding to
Cu-N4 and pyrrolic nitrogen species, respectively.13 As expected,
the pyrrolic nitrogen became the predominant species at 800 oC,
along with a new peak at 398.4 eV that belongs to the pyridinic
nitrogen. The C1s deconvoluted scan showed two
representative domains with binding energies at 284.8 and
286.7 eV, which attribute to the C-C and C-N bonds in CuII-
porphyrin, respectively.14 The shift of the binding energy of C-C
bonds to 284.6 eV implies the formation of carbonized material
at 800 oC. These conclusions were further proved by FT-IR, UV-
vis and Raman spectroscopy (Figures S12-S14).
Figure 3. (A) XPS survey spectra, high-resolution (B) Cu2p, (C) N1s and (D)
C1s XPS spectra of CZJ-6-TB.
Figure 2. MALDI-TOF MS spectra of the eluates extracted from the annealed
samples of CZJ-6 at different temperatures.
Transformation of MOFs into organic framework materials
would result in tuning the hydrophilic/hydrophobic nature. The
contact angle of a water droplet on pristine CZJ-6 was estimated
to be 17o, which was dramatically increased to 102o for CZJ-6-
400B, indicating that the annealing treatment overturned the
surface properties from hydrophilic CZJ-6 to hydrophobic
To get detailed information of the metalloporphyrin residues
in the annealed samples of CZJ-6, the encapsulated metallic Cu
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10.1002/anie.201903367
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COMMUNICATION
organic framework material CZJ-6-400B (Figure S15). The
hydrophobic nature is important in catalysis, which would protect
the active sites from toxic hydrophilic species.15
and the catalytic properties are much superior to those of the
carbonized material.
In summary, we developed an effective strategy to transform
instable MOFs into stable organic framework materials under
decarboxylative coupling reaction conditions. As an illustrated
example of CZJ-6, the fragile coordination bonds were replaced
with stable covalent C-C bonds under mild annealing conditions,
which resulted in a highly stable organic framework material with
inherited framework skeleton, porosity and catalytic properties
from the parent MOF. Enlightened by the results of this work, we
expect that numerous highly stable organic framework materials
with inherited properties from the parent MOFs will be created
for applications in various fields.
N2 sorption measurements were carried out to study the
textual characters of MOF CZJ-6, organic framework material
CZJ-6-400B and NPC material CZJ-6-800B (Figure S16). CZJ-6,
CZJ-6-400B and CZJ-6-800B take up 530, 103 and 134 cm3 g-1
N2 at 77 K and 1 bar, resulting microporous BET surface areas
of 394, 145 and 415 m2/g, respectively. Pore size distribution
analysis showed that there are two kinds of micropores for CZJ-
6-400B (1.15 and 1.30 nm) and CZJ-6-800B (1.05 and 1.25 nm)
(Figure S17). These values are very close to those of MOF CZJ-
6 (1.20 and 1.35 nm), which suggest that the pore characters of
CZJ-6 were successfully inherited in the daughter materials
CZJ-6-400 and CZJ-6-800. The slight shrinkage of pore sizes
should be resulted from decarboxylation of metalloporphyrin
ligands and further carbonization at elevated temperature. CO2
adsorption isotherms showed that CZJ-6, CZJ-6-400B and CZJ-
6-800B take up 51.9, 68.3 and 110.2 mg/g CO2 at 273K,
respectively (Figure S18). To get better understanding of the
adsorption behaviors, isosteric heats of CO2 adsorption (Qst) for
these materials were calculated based on Clausius−Clapeyron
equation from CO2 adsorption isotherms at 273 and 298 K.16 At
the initial stage, the Qst value for CZJ-6-400B (26.4 KJ/mol) is
higher than those for CZJ-6 (21.5 KJ/mol) and CZJ-6-800B (22.9
KJ/mol). These results indicate that there are stronger
interactions between the pore surfaces of CZJ-6-400B and CO2
molecules at low pressure, which might be ascribed to the
hydrophobic pore nature and the binding affinity of CO2 for the
open porphyrin copper(II) sites.12
Acknowledgements
We are grateful for the financial support of the National Natural
Science Foundation of China (grant nos. 21373180, 21525312
and 21872122).
Keywords: Metal-organic frameworks • Organic framework
materials • Decarboxylative coupling reaction • Coordination
bonds • Covalent bonds
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To evaluate the stability and the accessibility of CuII-
porphyrin sites in the organic framework materials, we examined
the catalytic properties of CZJ-6-TB in cross dehydrogenative
coupling (CDC) esterification reaction between C(sp3)-H and
carboxylic acid.17 As shown in Table S2, molecular Cu-TDPPP
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400B (92% ester yield) is also much higher than that of MOF
catalyst CZJ-6 (73% yield). Because low annealing temperature
would result in low-degree polymerization, CZJ-6-350B was
partially decomposed when catalyzing the CDC reaction, leading
to low ester yield (44%). However, excessively higher
temperature let CuII-porphyrin suffer from severe decomposition,
resulting in decreased ester yields (46-62%), while the
carbonized material CZJ-6-800 only resulted in 8% ester yield.
No obvious leaching of CuII-porphyrin was observed in the
supernatants for CZJ-6-TB (T ≥ 400 oC) after catalysis as
confirmed by UV-vis spectra and ICP-OES (Figures S19 and
S20). FT-IR spectrum showed that CuII-porphyrin in CZJ-6-400B
remained intact after catalysis (Figure S21). The above results
revealed that the chemical stability of organic framework
material CZJ-6-400B is much higher than that of the parent MOF
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10.1002/anie.201903367
Angewandte Chemie International Edition
COMMUNICATION
Entry for the Table of Contents
COMMUNICATION
An effective strategy is developed to
transform fragile coordination bonds in
metal-organic frameworks (MOFs) into
stable covalent organic bonds under
Kai Chen and Chuan-De Wu*
Page No. – Page No.
Transformation of Metal-Organic
Frameworks into Stable Organic
Frameworks with Inherited Skeletons
and Catalytic Properties
mild
annealing
decarboxylative
coupling reaction conditions, which
results in highly stable organic
framework materials with inherited
framework skeletons, porosity and
properties from the parent MOFs for
catalytic applications under harsh
conditions.
((Insert TOC Graphic here))
This article is protected by copyright. All rights reserved.