Polar functional groups anchored to a 2D MOF template for the stabilization of Pd(0) nps for the catalytic C-C coupling reaction

Article abstract of DOI:10.1039/c8dt04766a

A 2D porous MOF, {[Cu(1,2,3-btc)(bpe)(H₂O)]·H₂O}_n (1), has been synthesized using a mixed linker system. The structural determination showed non-coordinated carboxylate groups decorating the pore surface. The desolvated MOF (1a) with pendant carboxylate groups was used as a template for the stabilization of Pd nps (2-3 nm) and the resulting composite Pd(0)@1a showed efficient catalytic activity for the Suzuki-Miyaura C-C coupling reaction.

Full text of DOI:10.1039/c8dt04766a

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ISSN 1477-9226
PAPER
Joseph T. Hupp, Omar K. Farha et al.
Efficient extraction of sulfate from water using
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Polar functional groups anchored 2D MOF template for
stabilization of Pd(0) nps towards catalytic C-C coupling reaction
Stephen Adie Adalikwu,a Venkata Suresh Mothika,a Arpan Hazra,a and Tapas Kumar Maji*a
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
A 2D porous MOF, {[Cu(1,2,3-btc)(bpe)(H2O)].H2O}n (1) has been ‘COOH’ functional groups facing the pore surface as an
synthesized using mixed linker system. The structure excellent scaffold for stabilization of Pd(0) nps with uniform
determination showed non-coordinated carboxylate groups size and distribution throughout the MOF matrix. Among
decorated the pore surface. The desolvated MOF (1a) with various methods reported for incorporating metal nps,
pendant carboxylate groups used as a template for stabilization of solution impregnation method is simple and facile pathway; it
Pd nps (2-3 nm) and the resulting compsite Pd(0)@1a showed provides high loading of metal nps throughout the MOF
efficient catalytic activity for Suzuki-Miyura C-C coupling reaction.
matrix.39 The desolvated framework i.e. 1a forms 2D grid-like
network structure with a window size of 4.16 x 1.33 Å2 and
free ‘COOH’ functional groups decorated on the pore surface.
It acts as an excellent scaffold for stabilization Pd(0) nps with
control over the size and appreciable monodispersity. The
resulting MOF composite, Pd(0)@1a is successfully explored
for Suzuki-Miyura C-C coupling reactions at low reaction
temperature with excellent yields.
Inorganic-organic hybrid materials particularly metal-organic
frameworks (MOFs)1-7 assembled from metal-ion or clusters
and organic linkers have seen significant development due to
potential applications in gas storage,8-12 separation,13-17 drug
delivery,18 magnetism,19-20 fluorescence21-26 and catalysis.27-34
Especially, organic transformations heterogeneously catalyzed
by MOFs or MOF composites have attracted attention due to
low reaction times, enhanced conversions and excellent
recyclability.35-38 In this context, MOFs embedded with noble
metal nanoparticles (nps) such as Pd(0), Pt(0), Au(0) and Cu2O
are special class of heterogeneous catalysts and shown to be
promising for C-C coupling, CO-oxidation or click reactions.39
Stabilization of metal nps on pore surface of MOF matrices
essentially requires free polar functional groups (-NH2, -OH, -
SH, -COOH etc) that would electrostatically interact with metal
nps.38,39 Thus MOFs with pendent polar carboxylate groups
facilitate excellent stability for metal nps through coordination
or electrostatic interaction with unsaturated metal sites of nps
and decrease the leaching or agglomeration of metal nps
during catalytic reactions. Nevertheless, it is still a challenging
task to prepare MOFs with free pendent polar functional
groups like -NH2, -OH, -SH, -COOH due to difficulties in
controlling the metal coordination of such groups toward
higher dimensional structure. Herein, we report a new MOF,
{[Cu(1,2,3-btc)(bpe)(H2O)].H2O}n,(1) (bpe = 1,2-bis(4-ypridyl)etha
ne, 1,2,3-btc=1,2,3-benzenetricarboxylate), with free pendent
Compound {[Cu(1,2,3-btc)(bpe)H2O]H2O}n, (1) has been
synthesized by liquid phase diffusion method at room
temperature (see ESI for details). 1 crystallizes in triclinic space
group P-1 and single crystal X-ray analysis showed that 1 is a
2D coordination network of Cu(II) bridged by bpe and 1,2,3-btc
linkers (Table 1 in ESI). The asymmetric unit of 1 contains a five
coordinated CuII center with square pyramidal geometry and
connected to two bpe, two 1,2,3-btc linkers and one water
molecule resulting 1 as a 2D square grid like structure (Fig. 1a).
Each CuII center is bridged by two monodentate oxygen (O2
and O3) atoms from 1 and 3 carboxylate groups of the 1,2,3-
btc linkers and form a 1D {Cu(1,2,3-btc)}n chain whereas the
carboxylic acid group at 2 position of 1,2,3-btc remain pendent
in one side. These 1D chains are linked by the bpe pillars (N1
and N2) along the c- axis resulting in a 2D rectangular grid-like
structure along the ac plane (Fig. 1b). Bond distances of Cu1-
N1, Cu1-N2, Cu1-O2, Cu1-O3 and Cu1-O1W are 2.006(8),
1.983(7), 1.940(5), 1.955(5) and 2.378(7) Å, respectively (Table
2 in ESI). It is interesting to note that alternatively two
successive 1D chains {Cu(1,2,3-btc)}n with one-sided pendent
carboxylic acid groups are facing each other in the 2D
rectangular grid. Such an arrangement provide two different
type of coordination spaces in the 2D grid; one oval shaped
pore where two free ‘COOH’ groups are facing each other and
other rectangular pore decorated by the -(CH2)2- part of bpe
a. Molecular Materials Laboratory, Chemistry & Physics of Materials Unit, JNCASR,
Jakkur, Bangalore-560064
†Electronic Supplementary Information (ESI) available: CCDC 1881659. For ESI and
crystallographic data in CIF or other electronic format see DOI:10.1039/
x0xx00000x
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Fig. 1 (a) Asymmetric unit of 1, (b) 2D grid like structure. (c) 3D-framework with water molecules of 1. Red balls indicate guest water molecules.
and benzene rings of 1,2,3-btc linkers (Fig. 1c). The former one molecule of CO2 per formula unit. It is interesting to note
pore is hydrophilic in nature and occupied by the guest water that, CO2 profile has substantial hysteresis in the desorption
molecules while the later one is rather hydrophobic. 2D sheets resembling strong interaction of CO2 with 1a and it is also
are packed in an ABCD…ABCD (Fig. S1) manner which is reflected in the high value of the isosteric heat of adsorption
reinforced by … interaction between the bpe pillars and (qst’Ф found to be 27.66 kJmol-1) as calculated by Dubinin–
hydrogen bonding via coordinated water molecules O1W….O4 Radushkevich (DR) equation.40 This strong interaction may be
from a free carboxylate and also through the guest water attributed to the interaction of CO2 with unsaturated Cu(II)
molecules O4w which connect O1…O6 to form a 3D structure. sites and free carboxylic oxygen atoms decorated the pore
In the network CuII….CuII separation along the bpe and 1,2,3- surface. MOF, 1a is non-porous to N2 as evident from the type-
btc linking part are 13.300(2) Å and 10.025(2) Å respectively, II N2 gas adsorption isotherm measured at 77 K. Thus, the
and the longest neighbour CuII…CuII separation between the standard method of BET surface area calculation using N2
2D sheet is 16.159(2) Å.
adsorption isotherms was not possible.
To determine the framework stability and phase purity of 1, Regular and periodic arrangements of square grid like
thermogravimetric analysis (TGA) and X-ray powder diffraction nanopores with free carboxylic acid groups of 1,2,3-btc makes
(PXRD) studies were carried out. TGA shows about 6.94 % 1a a potential template for stabilization of metal nps such as
weight loss in the temperature range of 87-157 oC, Pd(0) for fabrication of np@MOF composite materials.
corresponding to the loss of two water molecules (calculated Schematic representation of a stabilization of Pd(0) nps
weight loss 7.12 %) (Fig. S2). The desolvated compound 1a is through electrostatic interaction of free carboxylic acid groups
o
stable up to 190 C without further weight loss. PXRD pattern of 1a is shown in Fig. 3. K2PdCl4 salt was adsorbed in 1a
of as-synthesized, 1 shows identical peaks corresponding to through solution impregnation method (see ESI for details) and
the simulated pattern indicating the phase purity of sample reduced using NaBH4 to result in Pd(0)@1a composite. TEM of
(Fig. 2a). Further, diffraction patterns of dehydrated and Pd(0)@1a shows uniform coverage of Pd(0) nps with size
rehydrated samples are observed to be similar, suggesting the ranging from 2-3 nm (determined using DigitalMicrograph
and thermal hydrolytic stability of framework (Fig. 2a). To software) throughout the MOF matrix (Fig. 4a, b). Energy-
investigate the permanent porosity of 1, the desolvated dispersive X-ray analysis (EDAX) of Pd(0)@1a composite
framework 1a was subjected to gas adsorption studies. N2 indicates the presence of both Pd(0) and Cu(II) in the
adsorption measurement for 1a at 77 K show type-II composite (Fig. S4). PXRD pattern of Pd(0)@1a shows (Fig. 4c)
adsorption profile (Fig. S3), whereas CO2 adsorption study at all the characteristic peaks of 1a are retained in the composite
195 K reveals a gradual uptake up to P= 1 atm (Fig. 2b). Both suggesting that the framework is intact after stabilization of
the sorption profiles suggest diffusion barrier for the Pd(0) nps and also reveals high stability of 1a in aqueous
adsorbate molecules due to smaller pore size. Final uptake solutions. Additional peak at 6.8° observed in Pd(0)@1a may
amount for CO2 found to be ⁓50 mLg-1, which corresponds to
be due to slight rearrangement in structure. Further, CO2
adsorption measurements of Pd(0)@1a at 195 K show lower
uptake of CO2 in comparison to 1a, this may be attributed to
the filling of some of the pores of 1a with Pd(0) nps and
reducing the available pores of CO2 adsorption (Fig. 2b). These
results clearly indicate that 1a is a robust and efficient scaffold
for stabilization of metal nps. X-ray photoelectron spectrum
(XPS) of Pd(0)@1a shows transitions correspond to Pd(3d5/2
)
and Pd(3d3/2) at 339.3 and 344.25 eV, respectively, suggesting
the zero-valent oxidation state of Pd(0) nps in Pd(0)@1a (Fig.
4d).39 Diffraction of Pd(0) nps in the composite is observed to
be very weak due to very small size of the nps and high
crystallinity of 1a in comparison (Fig 4c inset). Loading of Pd(0)
Fig. 2 (a) PXRD patterns of 1; (i) simulated, (ii) assynthesized, (iii) dehydrated and
(iv) rehydrated. (b) CO2 adsorption isotherm of 1a (red) and Pd(0)@1a(black) at
195 K upto 1 atm.
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Table 1. Catalytic Suzuki Miyura C-C coupling reaction of varVioieuws AarrtiycllehOalnidlinees
DOI: 10.1039/C8DT04766A
with aryl boronic acid in presence of Pd(0)@1a.
Fig. 3 Schematic showing the interaction of pendent ‘COOH’ groups with Pd(0) nps in
MOF pore and stabilization.
nps in the MOF is found to be 3.2 wt% determined from
inductively coupled plasma–optical emission spectrometry
(ICP-OES) investigation. Uniformly distributed Pd(0) nps of
sizes 2-3 nm in Pd(0)@1a composite would be a potential
candidate for heterogeneously catalysed industrially important
organic reaction such as Suzuki-Miyura C-C coupling.41 Initial
experiments were done with iodobenzene and phenylboronic
acid as aryl halide and aryl boronic acid in the presence of a
mild base such as Cs2CO3. (Table1). In a typical reaction,
mixture of iodobenzene (aryl halide) (0.098 mmol),
phenylboronic acid (aryl boronic acid) (0.147 mmol), Cs2CO3
(0.294mmol), and Pd(0)@1a catalyst (1.5 mg) are stirred in
tetrahydrofuran (THF) at 60 °C for 24 hrs. The reaction mixture
is filtered and washed with water; the filtrate is extracted with
dichlormethane concentrated under reduced pressure and
analyzed using GC-MS and 1H-NMR spectroscopy.
Interestingly, GC-MS reveals the complete conversion of
iodobenzene into biphenyl, no other peaks corresponding to
precursors or impurities are observed (Fig. S5 & S6).
Encouraged by the results, further experiments were carried
out to check the effect of electronic groups on aryl halide
keeping phenylboronic acid constant. All the reactions were
smooth and went to near completion both in the case of
electron withdrawing and electron donating groups, and the
results are
summarized in Table1, (Fig. S7-S11). To check the importance
of Pd(0) nps in catalysis reaction, we have performed blank
reactions using 1a under identical conditions. However, no
products were observed suggesting the importance of Pd(0)
nps present over MOF matrix, 1a in catalyzing the reaction. We
have studied the time dependent progress of the reaction
towards formation of biphenyl using Pd(0)@1a catalyst. As
seen in Fig. S12, a gradual increase in the product formation
was observed. To check the leaching of Pd(0) nps into the
solution, filtrate after the fourth catalytic reaction (24 hrs) is
studied for ICP-MAS analysis. ICP data suggest the presence of
a feeble amount of ‘Pd’ in the solution (2 ppm), suggesting
very slight leaching of ‘Pd’ during the catalytic reaction.
Apparently, a homogeneous reaction mechanism through
leached Pd(0) nps may contribute in parallel to dominant
Pd(0)@1a assisted heterogeneous catalytic process. Pd(0)@1a
is observed to show excellent conversion of aryl halide to
biphenyl with no apparent decrease in yields up to four
catalytic cycles suggesting high recyclability of the catalyst (Fig.
S13). Moreover, no considerable agglomeration of Pd(0) nps is
observed even after four catalytic cycles. As seen in Fig. S14,
the particle size ranges from 2-3 nm, however, very few
particles of 5 nm size are observed suggesting insignificant nps
agglomeration during the catalytic reaction. Further the
stability of Pd(0)@1a after four catalytic cycles were studied
by using PXRD measurements. As seen in Fig. S15, all the
diffraction peaks characteristic of 1a are retained in recycled
catalyst with only slight broadening or changed intensities
suggesting considerable stability of the framework. These
results suggest that 1a acts as an efficient scaffold for
stabilization of Pd(0) nps through pendant carboylate oxgen
atom with reduced leaching or agglomeration effect which
Fig. 4 Electron microscopy images of Pd(0)@1a (a) at low magnification (b) at
higher magnification (Inset: ED pattern showing the planes of Pd(0) nps). (c)
PXRD patterns of (i) 1a, (ii) Pd(0)@1a; Inset: powder (orange) and simulated
(black) diffraction patterns of Pd(0)@1a and Pd nps, respectively. (d) XPS
transitions of Pd(0)@1a for 3d5/2 and 3d3/2.
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M. Head-Gordon and J. R. Long, J. Am. Chem. Soc., 2013,
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Conclusions
In summary, we have demonstrated a new MOF with free
carboxylate groups appended polar pore surface which act as
an efficient template for stabilization of Pd(0) metal nps with
uniform size 2-3 nm. Electrostatic interaction between Pd(0)
nps and free carboxylate oxygen atoms enhance the stability
of nps on MOF matrix and reduce agglomeration or leaching
during catalytic reactions if compared to free colloidal Pd(0)
nps. The composite Pd(0)@1a act as an efficient
heterogeneous catalyst for Suzuki-Miyura coupling reaction
with no alteration in its catalytic activity even after four cycles.
We believe that MOF 1a with polar anchoring groups on its
pore surface can be an efficient template for other metal nps
towards fabrication of novel composite materials with
potential applications in SERS activity and electrocatalysis.
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Conflicts of Interest
There are no conflicts to declare.
Acknowledgements
We thank Prof. C. N. R. Rao, Prof. Offiong E Offiong for
encouragement, Mrs. Usha for TEM measurements. S. A. A.
acknowledges Third World Academics of Sciences (TWAS
Exchanges) for Fellowship, ICMS-JNCASR for research facilities,
VMS thank CSIR for fellowship, T.K.M. is grateful to the SERB,
Department of Science and Technology (DST, Project no. MR-
2015/001019 and Project no. TRC-DST/C.14.10/16-2724,
JNCASR), Govt. of India and JNCASR for financial support.
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DOI: 10.1039/C8DT04766A
Polar functional groups anchored 2D MOF template for stabilization of
Pd(0) nps towards catalytic C-C coupling reaction
Stephen Adie Adalikwu,a, Venkata Suresh Mothika,a Arpan Hazra,a and Tapas Kumar Maji* a
Table of Contents (TOC): A 2D MOF with polar pendant carboxylate functional groups has
been successfully employed for stabilization of Pd-nps and the resulting composite exhibited
excellent catalytic performance towards Suzuki-Miyura ‘C-C’ coupling reactions.