Highly active Pd-Ni nanocatalysts supported on multicharged polymer matrix

Article abstract of DOI:10.1039/c7cy01797a

In this article, we report the synthesis of mono- and bimetallic Pd-Ni nanocomposites supported on a multicharged polymeric matrix for catalytic applications. The morphology and catalytic properties of the composites depend on the Pd-Ni ratio. In the Suzuki-Miyaura coupling reaction, the composite with an equal amount of palladium and nickel is the most active and the reaction occurs within six hours in water at room temperature.

Full text of DOI:10.1039/c7cy01797a

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Highly active Pd-Ni nanocatalysts supported on multicharged
polymer matrix†
Elza D. Sultanova,ab Aida I. Samigullina,a Natalya V. Nastapova,a Irek R. Nizameev,ac Kirill V.
Kholin,ad Vladimir I. Morozov,a Aidar T. Gubaidullin,a Vitaliy V. Yanilkin,a Marsil K. Kadirov,a Albina
Y. Ziganshina*ab and Alexander I. Konovalovab
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
In this article we report a synthesis of mono- and bimetallic Pd-Ni nanocomposites on a multicharged polymeric matrix for
the catalytic application. The morphology and catalytic properties of the composites depends on Pd-Ni ratio. In the Suzuki–
Miyaura coupling reaction, the composite with the equal amount of palladium and nickel is the most active and the
reaction occurs within six hours in water at room temperature.
consists of viologen-cavitands29,30 interconnected with alkyl
chains.31 The synthesis of p(MVCA-co-St) is shown in Scheme 1.
The surface of the p(MVCA-co-St) is multicharged, and
Introduction
Metal nanoparticles (MNPs) have become extremely popular
in the last few decades due to their unique properties
especially catalytic.1,2 The MNPs based catalysts play an
important role in the chemical and oil industry.3,4 Despite the
great advances made in recent years, the development of the
MNPs catalysts is still under way.5 Creation of innovative
catalysts is necessary to solve the energy and environmental
problems.6,7 One of the most important requirements for
successful operation of catalysts is its high productivity,
catalytic activity at low temperatures and minimal use of noble
metals.8,9 In meeting these challenges, the bimetallic and
therefore, it well stabilizes Pd NPs, organizing them into the
clusters. Due to the flexible structure, p(MVCA-co-St) shrinks
and adapts to the Pd NPs clusters. The clusters Pdn-p(MVCA-
co-St) show high catalytic activity in the reduction and in the
Suzuki-Miyaura reaction.28 The coupling reaction proceeds
under mild conditions: in water, at room temperature.
Continue to this work, we have developed a bimetallic Pd-Ni
and monometallic Ni composites using p(MVCA-co-St) as a
supporting matrix. The insertion of nickel allows both reduce
the amount of expensive palladium, and change the functional
properties of the composites. Moreover,32,33 composites of
various shapes and activity can be prepared by varying a ratio
of the palladium and nickel precursors. Herein, we reported
the synthesis and catalytic activity of the PdnNim-p(MVCA-co-
St) and Ni4-p(MVCA-co-St). The influence of the Pd-Ni ratio on
the structure of the composites and their catalytic activity in
the Suzuki–Miyaura coupling reaction are discussed in the
article.
polymetallic nanocomposites open
a
number of
possibilities.10,11 Polymetallic nanocomposites exhibit the
properties of the individual metals and the additional
properties appearing from the mutual influence between
metals.12 Enhanced catalytic activity of bimetallic composites is
well demonstrated in recent studies.13,14 For example, the
platinum and palladium composites with nickel have been
used in the electrochemical oxidations15-18 and reduction
reactions.19-22 The Ni−Pd NPs immobilized on a magnet silica
were applied in the hydrogenation of cyclohexene.23 The
Pd−Ni nanowires show high catalyꢀc acꢀvity for the
hydrogenation of 4-nitrophenol24 and in the Suzuki-Miyaura
coupling reaction.25-27
Previously,28 we have reported the Pd NPs clusters on a
spherical polymeric matrix (p(MVCA-co-St)). The matrix
a.A. E. Arbuzov Institute of Organic and Physical Chemistry, Russian Academy of
Sciences, Arbuzov str. 8, Kazan 420088, Russia. E-mail: az@iopc.ru
b.A. M. Butlerov Institute of Chemistry, Kazan Federal University, Kremlevskaya str.
18, Kazan 420018, Russia
c. Kazan National Research Technical University, K. Marx str. 10, Kazan 420111,
Russia
d.Kazan National Research Technological University, Karl Marx str .68, Kazan
420015,Russia
Scheme 1 Synthesis of p(MVCA-co-St).
†Electronic Supplementary
DOI: 10.1039/x0xx00000x
Informaꢀon
(ESI)
available.
See
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Pd1Ni3-p(MVCA-co-St) with the excess nickel is composed of
the nm isolated nanoparticles on the nanosized
Results and discussion
5
For the synthesis of PdnNim-p(MVCA-co-St), an aqueous
solution of p(MVCA-co-St) was first mixed with sodium
tetrachloropalladate (1 ÷ 3 equivalent to viologen-cavitands of
p(MVCA-co-St)) for the complex formation between [PdCl4]2-
and viologen-cavitands of p(MVCA-co-St). Then nickel
acetylacetonate (Ni(acac)2) was added to the solution so that
the total amount of metals was 4 equal to viologen-cavitands
of p(MVCA-co-St). After that for the purpose of soft reduction
of the palladium and nickel ions, ascorbic acid (AA) was added
and the mixtures were kept at room temperature during 24
hours. The color of the solutions changed from yellow to dark
grey indicating the MNPs formation. In the UV-Vis spectra, the
disappearance of the [PdCl4]2- and Ni(acac)2 bands at 410 and
300 nm proves the complete reduction of metal ions (Fig. S1 in
the ESI†). The composites were purified by dialysis three times
to remove an excess ascorbic acid and its oxidized forms.
The monometallic composite Ni4-p(MVCA-co-St) was
prepared similarly but without addition of [PdCl4]2-. Analogous
to the PdnNim-p(MVCA-co-St), its UV-Vis spectrum does not
display absorption bands of Ni(acac)2, confirming its reduction
(Fig. S1 in the ESI†).
homogeneous surface. Ni4-p(MVCA-co-St) is present in the
form of the homogeneous cloudy spheres with average size
about 65-70 nm (Fig. 1F). Thus, the nanoparticles with size 5
nm predominate in the structure of the composites with the
excess palladium. When the nickel amount increases, the
number of the
5 nm nanoparticles decreases and the
amorphous component increases. Evidently, the palladate ions
are reduced to elemental Pd NPs with size about 5 nm while
nickel forms an amorphous solid which covers the surface of
p(MVCA-co-St).34-36 The energy dispersive X-ray analysis (EDX)
for Ni4-p(MVCA-co-St) shows the Ni lines Kα1 = 7.478 keV and
Kα2 = 7.461 keV (Fig. S2 in the ESI†). For the bimetallic
composites, along with the Ni signals, palladium lines Lα1
=
2.84 keV, Lβ1 = 2.99 keV, Lβ3 = 3.07 keV, Lγ1 = 3.32 keV, Lγ3 =
3.56 keV are observed (Fig. S3-S6 in the ESI†). With increasing
Pd amount in the composites, the integrated intensity of Pd
lines increases, while the intensity of Ni lines decreases. The
EDX spectrum of Ni4-p(MVCA-co-St) does not exhibit any Pd
lines.
Unfortunately, electron microscopy does not provide
information on amorphous or crystalline aggregate states,
except that it is possible to visually sometimes observe a facet
for crystalline components. The aggregate state can be
determined by x-ray diffraction (XRD) data.
The Pd and Ni content in the composites were determined
by inductively coupled plasma atomic emission spectrometry
(ICP-AES). For this, the purified colloids of the composites
obtained from 2 mM solution of metal ions were diluted 70-
fold and the line heights were measured. The experimentally
observed Pd and Ni concentrations (spectral lines 340.458 nm
and 231.604 nm, respectively) are summarized in Table S1 in
the ESI†. The yield of Pd and Ni in the composites varies from
74% to 88%.
XRD data are in agreement with the crystalline nature of
palladium and the amorphousness of nickel (Fig. 2). As the
palladium amount is increased, the intensity of the Pd
diffraction peaks increases while the amorphousness of the
samples decreases. XRD spectrum of Ni4-p(MVCA-co-St) does
not exhibit well-defined peaks in any region, which indicates
its completely amorphous structure.
According to TEM examination, the morphology of the
obtained composites depends on the ratio of Pd-Ni (Fig. 1).
The composite with excess palladium Pd3Ni1-p(MVCA-co-St) is
similar to Pd4-p(MVCA-co-St) described previously.28 It consists
of the particles with average diameter about 5 nm organized in
the flower-like clusters with size 68-75 nm (Fig. 1C). The cluster
Cyclic voltammograms (CV) analysis shows that nickel and
palladium in the monometallic composites are in zero
oxidation state. An irreversible peak associated with the Ni0
Pd2Ni2-p(MVCA-co-St) has
a size 40-50 nm and an
homogeneous film is observed in its structure.
Fig. 1 TEM images of (A) p(MVCA-co-St); (B) Pd4-p(MVCA-co-St) published in27; (C)
Pd3Ni1-p(MVCA-co-St); (D) Pd2Ni2-p(MVCA-co-St); (E) Pd1Ni3-p(MVCA-co-St); (F) Ni4-
p(MVCA-co-St).
Fig. 2 Experimental diffraction patterns of PdnNim-p(MVCA-co-St) and Ni4-p(MVCA-co-
St). Purple vertical lines show the position of the interference peaks corresponding to a
crystalline Palladium, Pd, syn., Ref. № 00-005-068 in the PDF-2 powder database.
2 | J. Name., 2012, 00, 1-3
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Fig. 3 Cyclic voltammograms for Pd4-p(MVCA-co-St), PdnNim-p(MVCA-co-St) and Ni4-
p(MVCA-co-St); C(p-MVCA-co-St) = 0.66 mg/ml, H2O/0.1 M NaCl, ʋ = 100 mV/s.
Fig. 4 EPR spectra of Pd3Ni1-p(MVCA-co-St), Pd2Ni2-p(MVCA-co-St), Pd1Ni3-p(MVCA-
co-St) and Ni4-p(MVCA-co-St), H2O, 20 °C.
oxidation appears at Ep = + 0.38 V in CV of Ni4-p(MVCA-co-St)
(Fig. 3). For Pd4-p(MVCA-co-St) an irreversible peak of the Pd0
oxidation is fixed at Ep = + 0.75 V. However, the bimetallic
composites PdnNim-p(MVCA-co-St) (where n, m = 1 ÷ 3)
exhibit a broadened peak and the current increase in the wide
range of potentials E = + 0.30 ÷ + 0.90 V. The peak of the Pd0
oxidation is manifested at + 0.75 V, whose height decreases
with the decrease in the Pd amount in the composites. The
absence of the well-defined peak of metallic nickel can be
caused by the nickel oxidation and the significant mutual
influence between palladium and nickel.15
The mutual influence between Pd, Ni and viologen in the
composites leads to a change in their electronic state and
affect their catalytic activity. 15,22,42,43
Nowadays, the Suzuki-Miyaura coupling is one of the most
popular method to obtain carbon-carbon bonds for producing
biaryls. The reaction is catalyzed by metal complexes and is
usually carried out in an organic medium at high
temperatures.44 In recent years, the number of publications on
the application of metal nanoparticles has been increasing.25-
27,45 Pd NPs are the most popular and effective, however, their
cost is quite high. In order to reduce high costs, Pd-Ni and Ni
composites began to be developed. In the article,44 the
authors reported the ligand stabilized Ni NPs which catalyze
the Suzuki-Miyaura reaction under mild conditions.46 Pd-Ni
nanoalloy catalysed the Suzuki--Miyaura reaction in water is
described in.25 The results showed that the Pd-Ni alloys are
more active than Pd.25 In the article,26 the authors employed
Pd and Pd-Ni nanoparticles deposited on carbon nanotubes.
The Suzuki reaction was carried out by using 0.1 mol% Pd in
water at 120 °C.26 The authors of the publication27 report on
the creation of Pd-Ni catalysts having a core-shell structure.
The activity of the catalysts increases with increasing the Ni
percentage.27
In the cathodic region of CVs, a pair of peaks of the
reduction and re-oxidation of viologen groups of p(MVCA-co-
St) is observed. As it was shown before,31 the free p(MVCA-co-
St) is reduced in two steps with the formation of multi(cation-
radical) and neutral species. However, in PdnNim-p(MVCA-co-
St) the first reduction peak is not clearly expressed whereas
the background reduction occurs at the potential of the
second reduction stage. This is apparently due to the reduction
of water with hydrogen evolution at the catalytically active Pd
and Ni NPs.
EPR spectra of the composites manifest several signals (Fig.
4). For Ni4-p(MVCA-co-St), the signals at 500-1000 and 2000 G
are attributed to the ferromagnetic nickel. In the area of 3000
G, a signal of the paramagnetic Ni+ is displayed. The bimetallic
composites exhibit the Ni+ signal at 3000 G while the
ferromagnetic nickel is not detected.37,38 All the bimetallic
composites display a signal at 3400 G with g = 2.010
corresponded to a viologen cation radical of MVCA. Its
intensity increases with increasing in Pd content (Fig. 4). In
Ni4-p(MVCA-co-St), the viologen appears at 3445 G (g =
2.004). The narrowness of the signal indicates the exchange
narrowing of the lines, which usually corresponds to an
ordered intermolecular structure of viologen.39-41 From the
obtained data it can be assumed that Ni4-p(MVCA-co-St)
consists of the amorphous Ni/Ni+ film coating p(MVCA-co-St).
The bimetallic composites have a more complex structure.
p(MVCA-co-St) is covered with the amorphous oxidized nickel
with nanoparticles of metallic palladium.
The composites PdnNim-p(MVCA-co-St) and Ni4-p(MVCA-
co-St) were applied as catalysts in the coupling between
phenylboronic acid and iodobenzene. The results obtained
show that, similar to Pd4-p(MVCA-co-St),28 the composites
show good activity and the reaction proceeds under mild
conditions: in water, at room temperature (Table 1). The
bimetallic composites exhibit better catalytic activity than the
monometallic ones. The most active is Pd2Ni2-p(MVCA-co-St).
In its presence, the coupling reaction occurs in six hours. An
increasing amount of nickel or palladium in PdnNim-p(MVCA-
co-St) leads to decreasing the catalytic activity. The
monometallic composite Ni4-p(MVCA-co-St) shows the lowest
activity. Pd3Ni-p(MVCA-co-St) and Pd2Ni2-p(MVCA-co-St) have
a structure with a flower like shape where Pd NPs are
adsorped on the Ni contained amorphous surface. Apparently,
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Table 1 Suzuki–Miyaura coupling reaction catalyzed by PdnNim-p(MVCA-co-St), Ni4-
p(MVCA-co-St).a
Table 2. Suzuki–Miyaura coupling reaction catalyzed by Pd2Ni2-p(MVCA-co-St)a
Aryl halide
Yield after 13 h (%)
100b
89
-
Catalyst
Yield after 6 h, %
Yield after 20 h, %
Pd3Ni1-p(MVCA-co-St)
Pd2Ni2-p(MVCA-co-St)
Pd1Ni3-p(MVCA-co-St)
Ni4-p(MVCA-co-St)
82
100
33
-
100
100
34
74
47
7
a
a
C(iodobenzene) = C(phenylboronic acid) = 5 mM, C(K2CO3) = 15 mM, C(M in
C(aryl halide) = C(phenylboronic acid) = 5 mM, C(K2CO3) = 15 mM, C(M in
PdnNim-p(MVCA-co-St)) = 0.05 mM, V = 15 ml, H2O, 25 ⁰C.
Pd2Ni2-p(MVCA-co-St)) = 0.05 mM, V = 15 ml, H2O, 25 ⁰C.
b Yield after 6 h.
that this kind of structures is the most preferred in
catalysis.10,11,19
TEM-EDX experiments were conducted on Hitachi HT7700
transmission electron microscope with energy-dispersive X-ray
detector from Thermo Scientific.
As the most effective catalyst, Pd2Ni2-p(MVCA-co-St) was
applied in the Suzuki-Miyaura reactions with a range of aryl
halides. The coupling reaction was carried out in similar
conditions using 1 mol % metals in Pd2Ni2-p(MVCA-co-St)
(Table 2). Halogens attached directly to the benzene ring,
demonstrate a low reactivity because of the conjugation of
their electron pair with benzene ring. The changing of the
more active iodine to bromine results in the reaction slowing
and the yield decreasing to 89 % (Table 2). Chlorobenzene
almost does not react in these conditions. Electron-donating
substituents in the benzene ring reduce the mobility of
halogens, as is observed for 4-iodotoluene. The yield of 4-
methylbiphenyl is only a 74 % after 13 h of reaction while the
reaction with iodobenzene finishes after 6 h. In the case of 4-
chlorophenol, a hydroxyl group shows a positive mesomeric
effect (+M) and negative inductive effect (-I). The -I effect
decreases the electron density in chlorine, whereby chlorine
becomes much mobile, and 4-chlorophenol is more reactive
than chlorobenzene. Whereas, chlorophenol reacts with
phenylboronic acid in 13 h to provide a 47 % yield of 4-
hydroxybiphenyl.
X-ray powder diffraction (XRPD) measurements were
performed on a Bruker D8 Advance diffractometer equipped
with Vario attachment and Vantec linear PSD, using Cu
radiation (40 kV, 40 mA) monochromated by the curved
Johansson monochromator (λ CuKα1 1.5406 Å). Room-
temperature data were collected in the reflection mode with a
flat-plate sample. Sample was applied in liquid form on the
surface of standard zero diffraction silicon plate. After drying
the layer, on top of it a few more layers were applied to
increase the total amount of sample. The sample was kept
spinning (15 rpm) throughout the data collection. Patterns
were recorded in the 2θ range between 3⁰ and 100⁰, in 0.008⁰
steps, with a step time of 0.1–0.5 s. Several diffraction
patterns in various experimental modes were collected for the
samples. Processing of the obtained data performed using
EVA47 and TOPAS48 software packages. Powder X-ray
diffraction database PDF-2 (ICDD PDF-2, Release 2005–2009)
was used to identify the crystalline phase.
Cyclic voltammograms were recorded by using potentiostat
P-30S (without the IR-compensation) in argon atmosphere at
potential scan rate ʋ = 100 mV/s in 0.1 M NaCl/H2O at 295 K. A
glassy carbon electrode (ð = 2 mm) embedded in Teflon was
used as a working electrode. Before each measurement the
surface of the working electrode was mechanically polished. A
platinum wire was used as an auxiliary electrode. The
potentials were measured versus an aqueous saturated
calomel electrode (SCE) connected to the solution through a
bridge with the supporting electrolyte and having the potential
of - 0.41 V relative to ꢀꢁ, (Fc+ / Fc0).
Experimental
Pd and Ni were identified in the colloids using simultaneous
inductively coupled plasma atomic emission spectrometry
(ICP-AES) model iCAP 6300 DUO by Varian Thermo Scientific
Company equipped with a CID detector. This spectrometer
enables the simultaneous measurement of peak heights. The
optical resolution is less than 0.007 nm to 200 nm. The
working frequency is 27.12 MHz. Together, the radial and axial
view configurations enable optimal peak height measurements
with suppressed spectral noises. The concentration of Pd and
Ni were determined from the spectral lines height at 340.458
nm and 231.604 nm, respectively.
EPR spectra were recorded with Elexsys E500 spectrometer
Bruker.
UV/Vis experiments were recorded with a Perkin–Elmer
Lambda 25 UV/Vis spectrometer. The NMR experiments were
carried out with an Avance-600 (Bruker, Germany).
The transmission electron microscopy (TEM) images were
obtained with Hitachi HT7700, Japan. The images were
acquired at an accelerating voltage of 100 kV. Samples were
deposited on 300 mesh copper grid with continuous carbon-
formvar support films.
Sodium tetrachloropalladate (II) (approx. 36% Pd), nickel
acetylacetonate (96 %), sodium borohydride (98+%, powder)
and ascorbic acid (99 %) were purchased from Acros Organics
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and used as received without further purification. p(MVCA-co- This study was supported by the Russian Foundation for Basic
St) was synthesized as described in.31 Regenerated cellulose Research (Grant No. 15-03-04999) and by the subsidy
tubular dialysis membranes (MWCO: Nominal: 1000) were allocated to Kazan Federal University for the state assignment
acquired from Cellu•Sep. All the solutions were prepared with in the sphere of scientific activities.
deionized water treated in a Millipore water purification
system (Millipore Corp.).
Elza Sultanova thanks the Haldor Topsøe A/S for PhD
scholarship.
We are grateful to the "SMTA" labarotary of Kazan
National Research Technological University for access to
Synthesis of PdnNim-p(MVCA-co-St)
An aqueous solution of p(MVCA-co-St) (4 mg/ml, 0.5 ml) was microscopic and spectroscopic equipment.
mixed with 0.3 ml of 3.33 - 10 mM Na2PdCl4. Then 0.4 ml of 2.5
– 7.5 mM Ni(acac)2 was added so that the total concentration
Notes and references
of salts was 3.33 mM and the ratio of Pd:Ni was 3:1, 2:2, 1:3.
After 1 minute 0.8 ml of 25 mM ascorbic acid was added. The
mixture was kept at room temperature for 24 hours. The
control of the reduction of Pd and Ni was performed by the
disappearance of an absorption band at 410 and 300 nm in the
UV/Vis spectra. The final colloidal solution was dialyzed (2 ml
versus 3×800 ml water).
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An aqueous solution of р(MVCA-со-St) (4 mg/ml, 0.5 ml) was
mixed with a solution of Ni(acac)2 (5.33 mM, 0.75 ml). After 1
minute, ascorbic acid (26 mM, 0.75 ml) was added. The
mixture was kept at room temperature for 24 hours. The final
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uzuki-Miyaura coupling reaction
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To an aqueous dispersion (10 ml) containing 7.5 mM aryl
halide, 7.5 mM phenylboronic acid and 22.5 mM K2CO3, 0.75
ml of colloidal solution of PdnNim-p(MVCA-co-St) (C(M) = 2
mM) was added. The volume of the mixture was adjusted to
15 ml. The mixture was stirred at room temperature. Aliquots
of the solution were taken after 6, 13 and 20 hours for the
determining of the products. The products were extracted
with hexane and then with ethyl acetate. The organic solutions
were combined, washed with water and dried with MgSO4.
The solvents were removed and to get a product. The
structure of products was determined by 1H NMR spectra.
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Conclusions
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We have described the synthesis of the monometallic Ni and
bimetallic Pd-Ni composites with different size and structure
stabilized on the flexible multicharged matrix. The
monometallic composite Ni4-p(MVCA-co-St) consists of the
amorphous nickel covered the surface of p(MVCA-co-St). The
morphology of the bimetallic composites PdnNim-p(MVCA-co-
St) depends on the ration of Pd-Ni and varieties from the
flower-like clusters to the separated particles on the
amorphous surface. The composite Pd2Ni2-p(MVCA-co-St)
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best catalytic activity in Suzuki–Miyaura coupling reaction
which proceeds in water at room temperature in 6 hours.
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DOI: 10.1039/C7CY01797A
We report a synthesis of mono- and bimetallic Pd-Ni nanocomposites on a multicharged polymeric matrix for
catalysis of the Suzuki–Miyaura reaction.
38x22mm (300 x 300 DPI)