Functionalization of Zirconium-Based Metal–Organic Layers with Tailored Pore Environments for Heterogeneous Catalysis

Article abstract of DOI:10.1002/anie.202007781

Intriguing properties and functions are expected to implant into metal–organic layers (MOLs) to achieve tailored pore environments and multiple functionalities owing to the synergies among multiple components. Herein, we demonstrate a facile one-pot synthetic strategy to incorporate multiple functionalities into stable zirconium MOLs via secondary ligand pillaring. Through the combination of Zr₆-BTB (BTB=benzene-1,3,5-tribenzoate) layers and diverse secondary ligands (including ditopic and tetratopic linkers), 31 MOFs with multi-functionalities were systematically prepared. Notably, a metal–phthalocyanine fragment was successfully incorporated into this Zr-MOL system, giving rise to an ideal platform for the selective oxidation of anthracene. The organic functionalization of two-dimensional MOLs can generate tunable porous structures and environments, which may facilitate the excellent catalytic performance of as-synthesized materials.

Full text of DOI:10.1002/anie.202007781

A Journal of the Gesellschaft Deutscher Chemiker
Angewandte
Chemie
International Edition
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Accepted Article
Title: Functionalization of Zr-based Metal-Organic Layers with Tailored
Pore-Environments for Heterogeneous Catalysis
Authors: Junsheng Qin, Guan-Yu Qiao, Shuai Yuan, Jiandong Pang,
Heng Rao, Christina T. Lollar, Dongbin Dang, Hong-Cai Zhou,
and Jihong Yu
This manuscript has been accepted after peer review and appears as an
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.202007781
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Functionalization of Zr-based Metal-Organic Layers with Tailored
Pore-Environments for Heterogeneous Catalysis
Guan-Yu Qiao,[a] Shuai Yuan,[b] Jiandong Pang,[b] Heng Rao,[a,c] Christina T. Lollar,[b] Dongbin Dang,[b]
Jun-Sheng Qin,*[a,c] Hong-Cai Zhou,*[b,d] and Jihong Yu*[a,c]
Dedication ((optional))
[a]
[b]
G.-Y. Qiao, Dr. H. Rao, Prof. Dr. J.-S. Qin, Prof. Dr. J. Yu
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry
College of Chemistry
Jilin University
Changchun 130012 (China)
E-mail: qin@jlu.edu.cn, jihong@jlu.edu.cn
Dr. S. Yuan, Dr. J. Pang, C. T. Lollar, Prof. Dr. D. Dang, Prof. Dr. H.-C. Zhou
Department of Chemistry
Texas A&M University
College Station, Texas 77843-3255 (USA)
E-mail: zhou@chem.tamu.edu
[c]
[d]
Dr. H. Rao, Prof. Dr. J.-S. Qin, Prof. Dr. J. Yu
International Center of Future Science
Jilin University
Changchun 130012 (China)
Prof. Dr. H.-C. Zhou
Department of Materials Science and Engineering
Texas A&M University
College Station, Texas 77843-3003 (USA)
Supporting information for this article is given via a link at the end of the document.
Abstract: Intriguing properties and functions are expected to implant
into metal-organic layers (MOLs) to achieve tailored pore
environments and multiple functionalities owing to the synergies
among multiple components. Herein, we demonstrated a facile one-
pot synthetic strategy to incorporate multi-functionalities into stable
zirconium MOLs via secondary ligand pillaring. Through the
combination of Zr6−BTB (BTB = benzene-1,3,5-tribenzoate) layers
and diverse secondary ligands (including ditopic and tetratopic
linkers), 31 MOFs with multi-functionalities were systematically
but also alter the photophysical properties of parent materials.[6]
In this sense, intriguing properties and functions are expected to
implant into MOLs to achieve tailored pore environments and
multiple functionalities via introducing desired secondary
pillaring ligands.
Phthalocyanine derivatives that have a similar structure to
porphyrins are widely used as pigments and dyes owing to the
presence of a large aromatic ring system consisting of 18 π-
electrons.[7] Due to the substantially delocalized electronic
structure, phthalocyanines possess unique optical, physical, and
chemical features, making them prospects in many fields
including catalysis and solar cells.[8] However, phthalocyanine
derivatives suffer from poor solubility in most solvents,[9] and
thus the preparation of phthalocyanine-based materials is
severely restricted. Although water-soluble phthalocyanine
derivatives were explored as homogeneous catalysts over the
last few years, the synthesis of phthalocyanine-based
heterogeneous catalysts is still rarely reported. Therefore, it
prepared. Notably,
a
metal-phthalocyanine fragment was
successfully incorporated into this Zr-MOL system, giving rise to an
ideal platform for the selective oxidation of anthracene. We
demonstrate that the organic functionalization of two-dimensional
MOLs can generate tunable porous structures and environments,
which may facilitate the excellent catalytic performance of as-
synthesized materials.
As most industrial catalysts are heterogeneous, it is highly
desired to anchor molecular catalysts onto porous solid supports
that are suitable for industrial processes. Metal–organic
frameworks (MOFs),[1] also known as porous coordination
polymers (PCPs), possess tunable porosities and designable
functionalities that make them promising candidates for a variety
of applications such as gas adsorption and separation, sensing,
and catalysis.[2] Metal–organic layers (MOLs),[3] monolayer
versions of two-dimensional (2D) MOFs, intrinsically boast
similar advantages to MOFs and represent an emerging class of
tunable and functionalizable 2D materials.[4] According to the
functional requirement, the secondary ligand can be introduced
into MOLs, which not only tune the hydrophobic properties of the
of MOL surface to create special in-layer microenvironments,[5]
remains
a difficult challenge to introduce phthalocyanine
fragments into porous supports for the preparation of
heterogeneous catalysts in synthetic chemistry and materials
science.
Traditional zirconium phosphates as a subset of layered
materials represent
functionalization with a variety of organic substituents.[10] As an
extension of this type of material, Zr6O4(OH)4(COO)12 (Zr6) units
have been chosen as the ideal metal clusters for the preparation
of MOL platform because of their exceptional stability and the
tendency to form stable coordination bonds with carboxylates
from 6 to 12 connectivities.[11] In a previous work, the Zr6−BTB
(benzene-1,3,5-tribenzoate) layer with a (3,6)-connected kgd
a
kind of versatile substrate for
1
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Figure 1. The schematic synthesis procedure of the PCN-135 family: Zr6−BTB layer as the precursor and a series of ligands (including linear linkers (with or
without functional groups) and tetratopic ligands (with square geometries)) as the secondary pillaring ligands.
2
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topology was constructed,[12] in which six pairs of terminal
−OH−/H2O ligands on the Zr6 cluster were left above and below
the layer, poised for carboxylate linkers. Furthermore, the
Zr6−BTB layer can be extended into a 3D network using bent
ditopic or tetratopic linkers, which act as pillars to support the
layers.[13] Besides this, Zr6−BTB layers boast the following
advantages compared with inorganic zirconium phosphate
layers: (i) They are easily and reliably prepared with a high
degree of crystallinity. (ii) They are insoluble in water and
common organic solvents, demonstrate strong tolerances
toward acidity and certain alkalinity, possess high thermal
stability and mechanical strength, and benefit from high
chemical stability. Layered structures can be maintained after
secondary linkers are introduced into the layer. (iii) They have
large specific surface areas and, can act as strong solid acids
with large surface charge densities. The terminal −OH−/H2O
ligands capped on the coordinatively unsaturated sites of the Zr6
clusters can be substituted by diverse carboxylate ligands with
different functional groups via an acid−base reaction.[14] In this
context, these features make MOLs promising candidates to
implement our strategy of incorporating multi-functionalities into
stable MOFs.
procedure of the PCN-135 family, in which Zr6−BTB layers are
utilized as the precursor and a series of ligands (including linear
linkers (with or without functional groups) and tetratopic ligands
(with square geometries)) are used as the pillars. Zr-BTB layers
are preferred as the MOL to be functionalized because of their
high stability and unique structure.[12b] Furthermore, PCN-
135(Co-TCPc) (TCPc = 2,9,16,23-tetracarboxyphthalocyanine,
also noted as L4-5 in this work) was used as a highly active and
reusable solid heterogeneous catalyst for the selective oxidation
of anthracene under visible light owing to its excellent optical
properties and stability. In particular, the inclusion of cobalt-
containing phthalocyanine fragments in MOFs would be greatly
benefitted from the MOFs’ ability to prevent aggregation and
leaching. Our findings are expected to open a new avenue for
achieving high efficiency catalysis through the successful
introduction of phthalocyanine fragments.
To the best of our knowledge, one major advantage of MOFs
is the synthetic versatility derived from the rational design of
diverse ligands compared with other conventional porous
materials. With this in mind, we intend to incorporate a broad
scope of functionalities into the MOF through judicious selection
of
linkers
with
BPDC
moieties
(BPDC
=
4,4’-
In this work, 31 MOFs (PCN-135 series, Figure 1) with
multiple functionalities were constructed through the
combinations of Zr6−BTB layers and various carboxylate ligands
(including ditopic and tetratopic linkers). This approach utilized
2D MOLs with coordinatively unsaturated Zr6 clusters as
precursors followed by pillaring with linear linkers (with or
without functional groups) or tetratopic ligands (with square
geometries) onto the Zr6 clusters by replacing the terminal –
OH/H2O with carboxylate groups. Experimentally, solvothermal
reactions of ZrCl4, H3BTB, the secondary ligands, and benzoic
acid (BA) in N,Nʹ-dimethylformamide (DMF) yielded crystalline
powders of the PCN-135 series (Supporting Information, Section
S2). The secondary ligands include ditopic and tetratopic
carboxylate linkers, noted as Lm-n (m = 2 and 4, corresponding
to the number of carboxylate ends, and n = index number to
identify each linker). Figure 1 describes the typical synthesis
biphenyldicarboxylate, see Figure 1, from L2-9 to L2-18). BPDC
modified with methyl groups, methoxyl groups, cyano groups,
hydroxy groups and iodine substituents were selected, as well
as relevant fragments like perylene and 2,2’-bipyridine. MOFs
with these functional groups can be easily modified with further
functionalization. In addition, PCN-135 series with BDC fragment
(BDC = benzene dicarboxylate, from L2-2 to L2-6), and NDC
(NDC = naphthalene dicarboxylate, L2-7 and L2-8) were also
constructed. These results offer a convenient mean to modulate
the pore microenvironments and pore volume of MOFs. These
results suggest that our approach is promising to introduce
desired functionality into stable MOFs by one-pot synthesis,
which can in turn extensively promote the potential applications
of MOFs.
Figure 2. The PXRD patterns of the PCN-135 family compared with the experimental and simulated XRD patterns of Zr-BTB. The characteristic peaks of Zr-BTB
layer structure and PCN-135 series are highlighted in blue.
3
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The powder X-ray diffraction (PXRD) patterns of the PCN-135
series all possess the characteristic peak of Zr6-BTB layer
structure at 2θ = ~5º (Figure 2 and S1). The crystallinity of as-
synthesized MOFs is well maintained after the organic
functionalization, taking advantage of the acid stability of high
valence metal-based MOLs and their strong tolerance towards
defects.[13] Small shifts in the PXRD patterns can be observed,
which could be assigned to a change in the interlayer distance.
In addition, their crystalline structures were also confirmed by
scanning electron microscopy (SEM). As shown in Figure S2,
PCN-135(Co-TCPc) exhibits a similar lamellar structure with Zr-
BTB after the introduction of phthalocyanine fragments. The
corresponding elemental mapping analysis obtained from
In order to evaluate the porosity and the architectural stability
of the PCN-135 series, nitrogen gas adsorption measurements
at 77 K were carried out. Before gas sorption experiment, the
as-synthesized samples were washed with DMF and immersed
in acetone for 3 d, during which the solvent was decanted and
freshly replenished three times. The solvent was removed under
vacuum at 100 °C, yielding the porous material. Nitrogen
adsorption isotherms were recorded on the activated samples of
PCN-135(L2-n, n = 1, 2, 9, 17 and 22 (Figure 3a) and L4-n, n =
2, 3, 4 and 5 (Figure 3b)). All the profiles of these isotherms
reveal reversible type I behavior (P/P0 < 0.9) that is typical for
microporous materials.[15] The plateau occurs at relatively low
pressure and shows no significantly accompanied hysteresis. In
addition, a prompt capillary condensation resulted from meso- or
macropores at relative high pressure (P/P0 > 0.9) is observed,
which can be ascribed to dense packing of surface-bound MOF
crystals.[16]
In general, the UV–Vis signals of metal phthalocyanines
mainly derive from π → π* transitions of the strong Q-band (600
– 750 nm) and the broad B-band (300 – 450 nm) with weaker
transitions near those bands.[17] Correspondingly, PCN-135(Co-
TCPc) exhibits specific Q-band absorption at λmax = 687 nm and
B-band absorption at λmax = 293 nm (Figure S35), which is
similar to the absorption behavior of the central phthalocyanine
aromatic ring of TCPc. On the basis of the above
energy dispersive X-ray spectroscopy (EDS) provides
a
homogeneous distribution of all the elements (especially Zr and
N) over the entire structure of PCN-135(Co-TCPc) (Figure S3),
implying the integration of phthalocyanine into the framework.
These results suggested that the phases of the as-synthesized
1
Zr-MOF materials are uniform. Furthermore, H NMR analyses
were carried out to quantify the amounts of the secondary
ligands in the as-synthesized materials (Supporting Information,
1
Section S5). H NMR spectra of the digested products clearly
show the resonance signals of the secondary ligands (Figures
S4 – S34). The linkers ratios of BTB:Lm-n are listed in Table S1.
characterizations
and
analyses,
the
stable
Zr-MOL
functionalized by phthalocyanine fragments has been
successfully obtained, while maintaining the crystalline structure,
morphology, and chemical stability of the Zr-BTB layer, as well
as the photoresponsivity of the phthalocyanine moiety. Our work
highlights new opportunity in utilizing MOLs as highly tunable 2D
materials for the synthesis of stable multi-functional MOFs.
Table 1: Heterogeneous catalytic oxidation of anthracene to anthraquinone.[a]
Entry
R
Catalyst
Yield [%][b]
95
1
2
3
4
5
6
7
8
H
PCN-135(Co-TCPc)
PCN-135(Co-TCPc)
PCN-135(Co-TCPc)[c]
PCN-135(Co-TCPc)[d]
PCN-135(Co-TCPc)[f]
Co-TCPc
Me
H
92
92
H
NR[e]
NR
H
H
60
H
Co-TCPc[g]
26
[h]
H
—
NR
[a] Reaction conditions: anthracene (1 mmol), catalyst (0.001 mmol), MeCN
(10 mL), room temperature, visible light (300 W xenon lamp), 6 h, air. [b] Yield
was determined by 1H NMR spectroscopy. [c] After three catalytic cycles. [d]
Without visible light. [e] No reaction. [f] 100 ºC without visible light. [g] After
three catalytic cycles. [h] No catalyst.
Figure 3. (a) The nitrogen isotherms of select PCN-135(L2-n)-type MOFs
(dark yellow, L2-1; red, L2-2; blue, L2-9; magenta, L2-17; and olive, L2-22). (b)
The nitrogen isotherms of select PCN-135(L4-n)-type MOFs (dark yellow, L4-
2; red, L4-3; blue, L4-4; and olive, L4-5). Solid circle, adsorption; and open
circle, desorption.
As is known, metal phthalocyanine complexes are structurally
related to metal porphyrin complexes, which are widely used by
4
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10.1002/anie.202007781
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nature in the active sites of enzymes responsible for catalytic
aerobic oxidation, reduction and transport of dioxygen and the
tetramethylpiperidine (TEMP, 50 mM) solution, which could
identify the formation of singlet oxygen (1O2) and superoxide ion
(O2·–). Then, the mixture was monitored using a Bruker EMX
plus model spectrometer operating at the X-band frequency (9.4
GHz) at room temperature after being illuminated for 2 min.
destruction of peroxides. Although phthalocyanine is
completely synthetic compound, its properties in the chemical
and biological fields are most similar to those of porphyrin. The
a
structure of phthalocyanine has a strong π-π accumulation effect, Secondly, similar procedures were performed except with
so it is difficult to introduce metal phthalocyanine into MOFs by
conventional means. In our work, we used Zr-BTB as the 2D
MOL and Co-TCPc (Co-TCPc = tetracarboxyphthalocyaninato
cobalt(II)) as an auxiliary linker to achieve a stable TCPc-based
MOF material, namely PCN-135(Co-TCPc). With Zr-BTB layer
as the support, the agglomeration and loss of Co-TCPc in the
catalytic system would be minimized. In this context, to evaluate
the catalytic performance of PCN-135(Co-TCPc), we selected
anthracene as a model compound for anthraquinone conversion,
in which only air was required as an oxidizing agent. The
general strategy for the catalytic reaction is to use anthracene as
the reaction substrate, air as the oxidant, and acetonitrile as the
solvent at room temperature under visible light (Table 1). It was
utilization of 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) as the
spin-trapping agent, which could identify the formation of
hydroxyl radical (·OH). The EPR-trapping results show that the
standard capture signal appears under visible light illumination
when using TEMP as a capture agent (Figure S39a, g = 2.0092),
verifying the generation of the nitroxide radical adduct, which
1
·– [18]
proves the formation of O2 or O2
.
As described in Figure
S39b, no obvious EPR signals are detected under similar
conditions in the presence of DMPO, proving the absence
of ·OH in the system. Therefore, we speculated that the reaction
mechanism could be that the phthalocyanine ligand captures
oxygen in the air to form singlet oxygen or superoxide ion under
visible light irradiation, which in turn causes the metal Co(II)
center to become a high valence oxide, there-by oxidizing
anthracene to anthraquinone.
In conclusion, we developed a facile one-pot synthetic
strategy to incorporate multi-functionalities into MOLs via
secondary ligand pillaring to form stable Zr-MOFs. Through the
combination of Zr6−BTB layer and diverse secondary ligands, 31
MOFs with multi-functionalities were obtained. Significantly,
metal-phthalocyanine ligands were successfully incorporated
into this Zr-MOL system as a heterogeneous catalyst for the
selective oxidation of anthracene. This work not only provides a
strategy for the design of heterogeneous catalysts that
immobilized phthalocyanine fragments, but also opens the door
to a new class of 2D coordination materials with molecular
functionalities. We expect our strategy to offer a facile route to
found that the PCN-135(Co-TCPc) exhibited
a
high
anthraquinone yield of 95% (Table 1, Entry 1). When the
reaction substrate was replaced with 2,6-dimethylanthracene,
the methyl group was retained without being oxidized (Table 1,
Entry 2), suggesting the highly selective catalytic oxidation
activity. Additionally, a series of control experiments were also
performed under the given conditions, for instance, without
visible light at room temperature or at 100 ºC in the dark (Table
1, Entries 4 and 5). The results suggest that visible light
illumination is a key factor for this catalytic system. Meanwhile,
the control experiment without the addition of PCN-135(Co-
TCPc) was also carried out, and the oxidation reaction of
anthracene was not observed to occur (Table 1, Entry 8). By
using Co-TCPc as the catalyst under similar conditions, only
about 60% of anthraquinone yield was obtained after the first run, introduce multi-functionalities into stable Zr-MOFs for an
and the catalytic performance decreased significantly after three
cycles (Table 1, Entries 6 and 7). When Co-TCPc is inserted into
the layered Zr-MOL as an auxiliary linker, the ordering of the
phthalocyanine ligand is likely enhanced and the packing effect
is eliminated, meaning the light energy of the phthalocyanine
structure can be fully utilized. Moreover, the structure becomes
more stable and is less susceptible to damage during the
catalytic process. Compared to the traditional synthesis of
anthraquinone, highly toxic oxidants, high pressure oxygen, and
high temperature are unnecessary, establishing a green and
efficient synthesis strategy. Therefore, we have developed a
truly heterogeneous high-efficiency catalytic oxidation system
using PCN-135(Co-TCPc) as a catalyst. Our synthetic strategy
provides a facile route to introduce desired functionality into
stable MOFs with potential for a wide variety of applications.
Furthermore, the cycling performance of PCN-135(Co-TCPc)
was investigated to examine its photocatalytic durability. After
three continuous catalytic cycles, the yield can still exceed 90%,
demonstrating the good recyclability of PCN-135(Co-TCPc) as a
catalyst (Table 1, Entry 3). The PXRD pattern, Infrared and
thermogravimetric analysis of the tested sample was further
recorded after the photocatalytic reactions, and indicated that no
framework collapse or phase transition occurred during the
experiment and the structure of PCN-135(Co-TCPc) was
maintained after cycling (Figures S36 – S38).
extensive variety of potential applications in the near future.
Acknowledgements
The authors acknowledge the financial supports from the
National Natural Science Foundation of China (Grant No.
21901084 and 21621001) and the 111 Project (Grant No.
B17020). This work was also supported by the Robert A. Welch
Foundation through a Welch Endowed Chair to H.-C.Z. (A-0030).
Keywords: metal-organic layers • zirconium • pore
environments • heterogeneous catalysis
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10.1002/anie.202007781
Angewandte Chemie International Edition
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A facile one-pot synthetic strategy was explored to incorporate multi-functionalities into stable zirconium metal-organic layers (MOLs)
through the functionalization of Zr6−BTB (BTB = benzene-1,3,5-tribenzoate) layers via secondary ligand pillaring. Significantly, a
metal-phthalocyanine fragment was successfully incorporated into this Zr-MOL system, giving rise to an ideal platform for the
selective oxidation of anthracene.
7
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