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TEM techniques. As presented in Fig. 2c, the XRD pat-
broadening or shifting of peaks when compared with the
XRD pattern of the fresh catalyst. Furthermore, the XPS
spectrum of the 6th recycled catalyst clearly showed the
presence of peaks at 335.4 eV and 340.7, corresponding
to 3d5/2 and 3d3/2 for Pd(0) species, respectively (Fig. 3b).
These results suggested that the oxidation state of the
immobilized Pd did not change after repeated reactions.
Also, comparison of SEM and TEM images of sixth
reused nanocatalyst (Fig. 4c, d, g, h) with the fresh ones
(Fig. 4a, b, e, f) indicated that the morphology and struc-
ture of ZrO2@AEPH2-PPh2-pd(0) remained intact after
six recoveries. As shown in Fig. 4g, h, due to the slightly
of Pd species can be found in the structure of nanocata-
lyst. In spite of this, obtained results from various char-
acterization analysis of the reused nanocatalyst revealed
that the recovered ZrO2@AEPH2-PPh2-Pd(0) had not sig-
nificantly lost its activity after six cycles.
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In summary, ZrO2@AEPH2-PPh2-Pd(0) as a new and effi-
cient heterogeneous nanocatalyst was synthesized and char-
acterized by FT-IR, XRD, XPS, SEM, EDS, TEM, TGA
and ICP techniques. Characterization results showed that
ZrO2@AEPH2-PPh2-Pd(0) had spherical morphology with
an average size ranging of 10–40 nm. The catalytic activity
of this new aminophosphine nanocatalyst has been proved
for Suzuki–Miyaura and Heck–Mizoroki cross-coupling
reactions. A series of aryl iodides and bromides were cou-
pled with phenylboronic acid and alkyl acrylates to pro-
duce the corresponding products in short reaction times
and excellent yields. Applying green solvents such as H2O
and PEG 600 are also the predominant features supporting
this approach in a movement towards the green chemistry.
Moreover, this catalyst can be easily recovered and reused
for at least six cycles without deterioration in catalytic
activity.
Acknowledgements The authors gratefully acknowledge the partial
support of this study by Ferdowsi University of Mashhad Research
Council (Grant No. p/3/32111).
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