Arabian Journal of Chemistry 16 (2023) 105343

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Arabian Journal of Chemistry

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Original article

A simple and efficient catalyst for Suzuki reaction based on ultra-low

palladium chloride supported on ZnO nanowires
Shiguang Pan a, Jia Guo b, Xue Chen c, Dan Liu a,d,⇑, Alex T. Kuvarega d, Bhekie B. Mamba d, Jianzhou Gui b,c,⇑
a
State Key Laboratory of Separation Membranes and Membrane Processes, Tianjin Key Laboratory of Green Chemical Technology and Process Engineering, School of Chemistry,
Tianjin 300387, PR China
b
State Key Laboratory of Separation Membranes and Membrane Processes, Tianjin Key Laboratory of Green Chemical Technology and Process Engineering, School of Material Science
and Engineering, Tiangong University, Tianjin 300387, PR China
c
State Key Laboratory of Separation Membranes and Membrane Processes, Tianjin Key Laboratory of Green Chemical Technology and Process Engineering, School of
Chemical Engineering & Technology, Tiangong University, Tianjin 300387, PR China
d
Institute for Nanotechnology and Water Sustainability, College of Science, Engineering and Technology, University of South Africa, Florida, 1709 Johannesburg, South Africa

a r t i c l e i n f o a b s t r a c t

Article history: Zinc oxide nanowires were synthesized and impregnated with trace amounts of palladium ions by
Received 5 July 2023 adsorption, which was then employed as a heterogeneous catalyst in the Suzuki reaction. To obtain an
Accepted 7 October 2023 in-depth understanding of the structure and properties of the ZnO nanowires and the resultant catalyst,
Available online 11 October 2023
different analysis techniques were performed. The as-synthesized catalyst demonstrated exceptional effi-
ciency in promoting the reaction between aryl halides and arylboronic acids, enabling the achievement of
Keywords: biphenyl derivatives in high yields ranging between 82% and 99%. The analysis conducted using transmis-
Catalyst Design
sion electron microscopy demonstrated the formation of palladium nanoparticles during the reaction,
Catalyst Recycling
Palladium chloride
confirming their role as the active species driving the catalytic transformation. Further investigation
Zinc Oxides was carried out to examine the effect of the support on the catalytic activity of the catalyst. The results
Heterogeneous Catalysis indicated that the morphology and crystallographic structure of zinc oxide had a significant impact on
the catalytic activity of the prepared catalyst. The catalytic performance of PdCl2/ZnONWs, where palla-
dium chloride immobilized on ZnO nanowires, was found to be exceptional. The catalyst demonstrated
the ability to be recovered and reused up to three times without a noticeable decline in its catalytic activ-
ity. Additionally, the loading of palladium species could be reduced to 7.6 mol part per million.
Remarkably, the catalyst achieved a total turnover number of 130,000 and a turnover frequency of
0.75 s 1.
Ó 2023 The Author(s). Published by Elsevier B.V. on behalf of King Saud University. This is an open access
article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction sive catalytic performance of palladium in organic reactions, the

use of palladium as a catalyst is hindered by two prominent draw-
The Suzuki-Miyaura reaction, one of the most important meth- backs: its cost and toxicity (Greenwood, and Earnshaw, 1997;
ods for the construction of carbon–carbon bonds, has been widely Abernethy et al., 2010; Kushwaha, 2021; Kovaleva et al., 2018).
used in organic synthesis as one of the most important discoveries The expense of utilizing palladium can make up a significant por-
in the field of synthetic chemistry (Miyaura and Suzuki, 1995; tion of the overall cost of a reaction, while its toxic nature can
Hassan et al., 2002; Yin and Liebscher, 2007). Despite the impres- cause contamination issues in the final product (Abernethy et al.,
2010; Kushwaha, 2021; Kovaleva et al., 2018). Hence, cross-
⇑ Corresponding authors at: School of Chemistry, Tiangong University, No.399 coupling reactions are commonly excluded in the late stages of
BinShuiXi Road, XiQing District, Tianjin 300387, PR China (Jianzhou Gui). drug synthesis due to the conventional use of catalyst loadings that
E-mail addresses: [email protected] (D. Liu), [email protected] are impractical for industrial application, requiring multiple mole
(J. Gui). percentages (Farina, 2004). By reducing the amount of catalyst
Peer review under responsibility of King Saud University. used, however, these reactions can be made more economically
feasible and safer. A catalyst loading of 100 mol ppm
(ppm = parts per million) can completely eliminate the catalyst
cost in the reaction, while a loading level of 10 mol ppm would
Production and hosting by Elsevier address any concerns regarding toxicity. Notably, this loading level

https://doi.org/10.1016/j.arabjc.2023.105343
1878-5352/Ó 2023 The Author(s). Published by Elsevier B.V. on behalf of King Saud University.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
S. Pan, J. Guo, X. Chen et al. Arabian Journal of Chemistry 16 (2023) 105343

meets the requirement for palladium impurities in pharmaceutical simple and facile synthesis of Pd-based heterogeneous catalyst
drugs. was developed for the Suzuki-Miyaura reaction. The catalyst PdCl2/
The utilization of heterogeneous switching in homogeneous ZnONWs with highly catalytic efficiency (7.6–76 mol ppm Pd spe-
transition-metal catalysis has garnered increasing attention in cies) and high recyclability was achieved. The catalyst exhibited
the realm of organic synthetic chemistry. This approach offers sig- impressive performance with a total turnover number reaching
nificant advantages, including the ability to recover and reuse cat- as high as 130,000 and a turnover frequency of 0.75 s 1, respec-
alysts, as well as reducing the presence of metal contaminants in tivelyDuring the reaction, the generation of palladium nanoparti-
the final products. These benefits contribute to the realization of cles was observed through the use of transmission electron
environmentally friendly and high-throughput molecular transfor- microscopy (TEM) analyses. These nanoparticles were found to
mations (Fechete et al., 2012; Gholinejad et al., 2017; Gholinejad be the active species responsible for catalyzing the transformation.
et al., 2018; Vásquez-Céspedes et al., 2021; Deepika and Further investigation was carried out to examine the effect of the
Sethuraman, 2022; Gholinejad et al., 2023; Sheldon and van support on the catalytic activity of the catalyst. The results indi-
Bekkum, 2001; Barbaro and Liguori, 2010). To date, numerous cated that the morphology and crystallographic structure of zinc
heterogeneous catalytic systems based on palladium (Pd) have oxide had a significant impact on the catalytic activity of the syn-
been devised for the Suzuki-Miyaura reaction (Hassan et al., thesized catalyst.
2002; Yin and Liebscher, 2007). However, there is a limited num-
ber of reports on heterogeneous catalysts featuring trace amounts
of palladium loading that exhibit both high catalytic activity and 2. Experimental
high recyclability (Roy and Uozumi, 2018). Uozumi and co-
workers reported a metalloenzyme-inspired polymeric imidazole 2.1. Preparation procedure for ZnO nanowires
palladium catalyst and its application in Suzuki-Miyaura reaction
(Yamada et al., 2012). The reaction was conducted with a Zinc chloride (0.2 g), sodium dodecyl sulfate (SDS, 1.5 g) and
40 mol ppm palladium species. Additionally, they also developed sodium carbonate (20 g) were dissolved in 40 mL deionized water,
a convoluted polyvinylpyridine-palladium catalyst for Suzuki- and stirred for 30 min. Then the solution was transferred into a
Miyaura reaction with the same loading of palladium species 50 mL Teflon-lined autoclave and kept at 140 °C for 12 h. After
(Ohno et al., 2020). A new biarylamine-based substituted pallada- cooled to the room temperature, the precipitate was collected by
cycle was developed in Lipshuz group developed and was applied filtration, rinsed with deionized water and absolute ethanol for
to the Suzuki-Miyaura reaction. The reaction was carried out in three times, and finally dried at 80 °C for 12 h under vacuum, to
water under mild conditions and at a 300 mol ppm level of palla- give the desired ZnO nanowires.
dium species high recyclability (Takale et al., 2019). Meanwhile,
Zhang group has developed a palladium single-atom catalyst,
formed from bimetal oxides via an in situ co-precipitation method, 2.2. Preparation procedure for PdCl2/ZnO catalyst
for use in Suzuki-Miyaura reaction (Ding et al., 2020). This catalyst
exhibits high catalytic activity (37 mol ppm Pd) and high recycla- The catalyst PdCl2/ZnONWs was prepared by adsorption method:
bility. However, the availability of heterogeneous catalysts that Firstly, take 1.8 mg of palladium chloride and dissolve it in a small
exhibit both high activity and high recyclability, while also being amount of concentrated hydrochloric acid, and then dilute it to a
simple and low-cost to prepare, is scarce. Therefore, designing a 20 mL solution. Secondly, weigh 0.1 g of zinc oxide nanowires
heterogeneous catalyst with excellent catalytic activity and high and disperse them in 1 mL of water. Then add 2 mL of the above
recyclability, while being synthesized through a cost-effective prepared palladium chloride solvent and stir at room temperature
and facile method, is highly desired. for 3 h. The precipitate was separated by centrifugation, washed
On the other hand, adsorption is a technique widely used for three times with water and ethanol separately, and dried under
removing heavy metal ions due to its simple design as well as its vacuum to give the desired PdCl2/ZnONWs catalyst. The catalysts,
economical and eco-friendly nature (Renu et al., 2017). Last dec- PdCl2/ZnONPs and PdCl2/ZnOCA, were prepared with the same
ades, nanoadsorbents have become increasingly popular for miti- procedure.
gating heavy metal pollution in water sources due to their high
surface area-to-volume ratios, which provide numerous sites for
heavy metal adhesion (Kyzas and Matis, 2015; Ali et al., 2020). 2.3. General procedure for the Suzuki-Miyaura reaction
Among the various nanoadsorbent materials, zinc oxide (ZnO)
exhibits significant potential for heavy metal remediation as it dis- A mixture of aryl halide (0.25 mmol), arylboronic acid
plays exceptional biocompatibility and low toxicity (Mahdavi et al., (0.375 mmol), PdCl2/ZnONWs (1.0 mg, 76 mol ppm Pd species),
2012; Al-Mur, 2023; Le et al., 2019; Dhiman and Kondal, 2021; and Na2CO3 (0.5 mmol) in EtOH/H2O (1.0 mL/1.0 mL) were stirred
Deepika and Sethuraman, 2023). Despite several reports on the at 80 °C for 12 h (24 h for aryl bromides). After completion of the
application of palladium catalysts supported on zinc oxide for reaction, the reaction mixture was cooled to room temperature,
the Suzuki-Miyaura reaction (Del Zotto and Zuccaccia, 2017; Kim the mixture was extracted with ethyl acetate (3 mL x3). The com-
and Choi, 2009; Hosseini-Sarvari and Razmi, 2015; Bao et al., bined organic phases were concentrated in vacuo and the crude
2017; Hu et al., 2017; Hosseini-Sarvari and Bazyar, 2018; Rezaei products were purified by column chromatography (hexane/
et al., 2020), using zinc oxide to adsorb trace amounts of palladium AcOEt) to give the corresponding products.
ions and employing them as heterogeneous catalysts for organic
synthesis remains a challenging task.
Recently, our group has successfully synthesized a highly effi- 2.4. Recycling experiment for the Suzuki-Miyaura reaction
cient hierarchical TiO2 microsphere-supported palladium catalyst
and applied it in the Suzuki-Miyaura reaction (Pan et al., 2023). After the Suzuki-Miyaura reaction discussed previously, the
The catalyst exhibited exceptional qualities in promoting the reac- supported catalyst was recovered by centrifugation and washed
tion, utilizing a 10–200 mol ppm loading of palladium species. As a twice with EtOAc and water. The recovered catalyst was dried in
continuation of our efforts in the development of a greener syn- vacuo and reused in a subsequent reaction without an additional
thetic pathway for organic transformation, in the present work, a charge of palladium.
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S. Pan, J. Guo, X. Chen et al. Arabian Journal of Chemistry 16 (2023) 105343

3. Results and discussion

The catalyst of ZnO nanowires-supported palladium chloride

(PdCl2/ZnONWs) was prepared as shown in Scheme 1. First, zinc
oxide nanowires (ZnONWs) were synthesized by a one-step reaction
using a facile hydrothermal method. A mixture containing zinc
chloride, sodium dodecyl sulfate (SDS), sodium carbonate, and
water was stirred at room temperature for 30 min. The resulting
mixture was then transferred to a Teflon autoclave and subjected
to an oven temperature of 140 °C for a duration of 12 h. This pro-
cess ultimately yielded the desired ZnO nanowires. Subsequently,
the PdCl2/ZnONWs catalyst was prepared by employing the adsorp-
tion method to support palladium chloride onto the as-synthesized
ZnO nanowires. The mixture of as-synthesized ZnO nanowires and
palladium chloride was stirred at room temperature for a duration
of 2 h, resulting in the desired catalyst denoted as PdCl2/ZnONWs.
The ZnO nanowires and the catalyst were characterized by dif-
ferent technologies. In Fig. 1a and 1b, it can be clearly seen that the
as-synthesized ZnO nanowires have a typical linear structure with Fig. 1. SEM images of ZnONWs (a and b) and PdCl2/ZnONWs (c and d).
uniform size and smooth surface. After loading of palladium spe-
cies, the morphology and structure of the resulting PdCl2/ZnONWs
catalyst remain essentially unchanged. Fig. 2 displays the results After obtaining the as-synthesized catalyst, bromobenzene (1a)
of an Energy-dispersive X-ray (EDX) analysis conducted on the and phenylboronic acid (2a) were chosen as model substrates to
PdCl2/ZnONWs catalyst, confirming the presence of palladium optimize the reaction conditions, and the results were summarized
within the catalyst. This analysis provides strong evidence that pal- in Table 1. Initially, several carbonates were evaluated in this
ladium species have been successfully immobilized onto the ZnO transformation, and the use of Na2CO3 resulted in a 99% GC yield
nanowires. Through an ICP-OES analysis of PdCl2/ZnONWs, it has of biphenyl 3a (Entries 1–4). Although other bases, such as potas-
been further verified that the immobilization of Pd onto ZnO nano- sium phosphate and triethylamine were also investigated, their
wires was successful. The analysis determined a palladium loading yields were lower than Na2CO3 (Entries 5 and 6). Under the same
of 0.019 mmol g 1, providing quantitative confirmation of the reaction conditions, iodobenzene reacted with 2a yielded the
amount of palladium present on the nanowires. desired biphenyl with outstanding GC yield (entry 7). When nei-
The XRD technique was employed to characterize the structure ther a catalyst nor a base was present, the desired product 3a did
of the crystals. The as-synthesized ZnO nanowires exhibited char- not form (Entries 8 and 9). To verify that a trace amount of palla-
acteristic peaks in their X-ray diffraction pattern, indicating the dium species effectively facilitated this conversion, the same
presence of the crystalline phase of ZnO (JCPDS 36-1451). These amount of the as-synthesized ZnO nanowires was used only in
peaks were observed at angles of 31.52°, 34.42°, 36.24°, 47.52°, the reaction. However, none of 3a was observed (Entry 10).
and so on. It can be seen that the XRD pattern of the as- A comparative study was conducted to assess the catalytic
synthesized PdCl2/ZnO NWs have the same characteristic peaks activity of homogenous and heterogeneous PdCl2 catalysts
with ZnO nanowires, indicating that the crystal structure of ZnO (Scheme 2). When the reaction performed with 76 mol ppm of
nanowire has no change after loading of palladium species. In PdCl2, the product 3a was only obtained in 64% yield. These results
the XRD patterns of the as-synthesized catalyst, no presence of indicated that the catalyst of PdCl2 immobilized on ZnO showed
the Pd(0) phase was detected. This result was corroborated by higher catalytic activity than that of a homogeneous PdCl2 catalyst.
TEM analysis, which revealed the absence of any palladium In order to determine the active species involved in this conversion
nanoparticles. To gain further insights into the state of palladium process, we conducted a transmission electron microscopy (TEM)
in the as-synthesized catalyst, X-ray photoelectron spectroscopy analysis on the catalyst. This catalyst was obtained through the
(XPS) analyses of ZnO nanowires and PdCl2/ZnONWs were per- treatment of PdCl2/ZnONWs with phenylboronic acid, in the pres-
formed (Fig. 3b-3e). Fig. 3e showed binding energies (BEs) of Pd ence of Na2CO3, using a mixture of ethanol and water (v/v = 1:1)
3d5/2 and 3d3/2 at 337.6 and 343.2 eV, respectively, indicating the at a temperature of 80 °C for a duration of 30 min. The TEM image
presence of Pd(II) species in the catalyst (Shin et al., 2019) These revealed that palladium nanoparticles were generated and dis-
results indicated that the adsorption of palladium species onto persed on ZnO nanowires (Fig. 4a). The size of the particles was
the surface of ZnO nanowires occurred through physical adsorp- distributed in the range 1.5–3.0 nm, and the calculated lattice dis-
tion. This can be attributed to the negatively charged surface, tance of 0.225 nm corresponds to the (1 1 1) planes of Pd(0) species.
which was generated by the presence of OH– groups during the The generation of palladium nanoparticles is likely attributed to
growth process of ZnO nanowires (Renu et al., 2017). the oxidation of two molecules of arylboronic acid, resulting in
the formation of self-coupling products through the loss of two

Scheme 1. Schematic illustration for the synthesis process of PdCl2/ZnONWs.

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S. Pan, J. Guo, X. Chen et al. Arabian Journal of Chemistry 16 (2023) 105343

Fig. 2. EDX mappings of PdCl2/ZnONWs.

Fig. 3. (a) XRD study of PdCl2/ZnONWs catalyst, and (b-e) XPS spectra of ZnO NWs and PdCl2/ZnONWs catalyst.

electrons. In contrast, the palladium(II) species acquire two elec- completion of the reaction. In Fig. 4b, we observed the presence
trons and undergo reduction to palladium(0) (Moreno-Mañas of palladium nanoparticles in the selected region. These experi-
et al., 1996). Furthermore, we conducted a transmission electron mental findings confirm that the palladium nanoparticles indeed
microscopy (TEM) analysis on the reaction mixture following the serve as the active catalytic species in this reaction.

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S. Pan, J. Guo, X. Chen et al. Arabian Journal of Chemistry 16 (2023) 105343

Table 1
Optimization of reaction conditions.a

Entry Pd cat. Base GC Yield (%)b

1 PdCl2/ZnONWs Li2CO3 71
2 PdCl2/ZnONWs Na2CO3 99
3 PdCl2/ZnONWs K2CO3 95
4 PdCl2/ZnONWs Cs2CO3 94
5 PdCl2/ZnONWs K3PO4 76
6 PdCl2/ZnONWs NEt3 22
7c PdCl2/ZnONWs Na2CO3 99
8 – Na2CO3 0
9 PdCl2/ZnONWs – 0
10 ZnONWs Na2CO3 0
a
Reaction conditions: bromobenzene (1a, 0.25 mmol), phenylboronic acid (2a, 0.375 mmol), PdCl2/ZnONWs (1.0 mg, 76 mol ppm Pd species), base (0.5 mmol), EtOH/H2O
(1.0 mL/1.0 mL), otherwise other noted. b Determined by GC analysis using n-hexadecane as internal standard. c Iodobenzene instead of bromobenzene.

cles and commercially available zinc oxide yielded lower results

(90% and 75% respectively). These findings clearly demonstrate
that the ZnO nanowires synthesized in this study outperforms both
the ZnO nanoparticles and commercial ZnO as a support. Further-
more, the reusability of various PdCl2/ZnO catalysts was evaluated
for synthesizing of biphenyl. After the reaction, the catalyst was
recovered by centrifugation, washed three times with EtOAc and
H2O, dried in a vacuum oven and placed in the next use. ICP anal-
ysis shown that 5.1% of palladium species was leached to the solu-
tion. As shown in Fig. 5, the catalyst PdCl2/ZnONWs exhibited the
capability of being recovered and reused for up to three cycles with
Scheme 2. A comparative study between homogenous and heterogeneous PdCl2
only a minor decrease in catalytic activity, while the catalysts of
catalysts.
PdCl2/ZnONPs and PdCl2/ZnOCA showed a poor reusability
(According to the ICP analyses). These results further indicated that
Next, a comparative study was conducted on the catalytic activ- the as-synthesized ZnO nanowire sample was superior to commer-
ity and recyclability of palladium chloride supported on various cial ZnO as the support.
ZnO supports. Using the same method as the one employed for pal- Finally, the optimized conditions specified in entry 2 of Table 1
ladium chloride immobilization on zinc oxide nanowires, we pre- were utilized to explore the range of substrates, and the results
pared catalysts by loading palladium chloride onto zinc oxide were consolidated and presented in Scheme 3. The products 3a-
nanoparticles (sizes: 20–40 nm) and commercially available zinc 3d obtained from the reaction of iodobenzene with different aryl-
oxide. The catalytic performance of these catalysts was then com- boronic acids were all in 99% yield. Iodobenzenes containing a 4-
pared. However, the catalysts prepared with zinc oxide nanoparti- position methoxy, methyl, or acetyl group underwent reactions

Fig. 4. (a) TEM image of the reaction mixture without 1a in entry 2 in Table 1, 80 °C for 30 min (average size of Pd NPs 2.1 nm); (b) TEM image analysis on the reaction
mixture (Table 1, entry 2).

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S. Pan, J. Guo, X. Chen et al. Arabian Journal of Chemistry 16 (2023) 105343

the reaction of bromobenzene with phenylboronic acid resulted

in the formation of 3a in an impressive yield of 99%. Phenylboronic
acid bearing an electron-denoting group (OCH3) in the 4-position
facilitated this transformation, and the desired product 3b derived
from bromobenzene was obtained in 99% yield. No electronic effect
was observed for aryl bromides, as bromobenzene bearing a meth-
oxy, methyl, or acetyl group in the 4-position gave the products
(3h-3k, 3b’, 3d’ and 3f’) in 83–99% yields. Under the catalytic con-
ditions, functional groups, including halo, cyano, and acetyl groups,
demonstrated good compatibility and stability.
Lowering the catalyst loading makes the reactions safer and
cost-efficient for synthetic chemistry. The loading of palladium
species in this transformation can be further reduced to a level
as low as 10 mol ppm. In scheme 4a, the reaction between
iodobenzene and phenylboronic acid was carried out using a mere
7.6 mol ppm of Pd species, resulting in the formation of product 3a
with an exceptional yield of 99% within a reaction time of 48 h.
Similarly, product 3b was obtained in a 99% yield using the same
reaction conditions, as depicted in Scheme 4b. As high as 130,000
turnover number (TON) and 0.75 s 1 turnover frequency (TOF)
Fig. 5. Recycle and reuse of various PdCl2/ZnO catalysts. were achieved in this transformation. In Scheme 4c, when bro-
mobenzene was subjected to this transformation, the reaction
necessitated an extended reaction time, resulting in the isolation
with various arylboronic acids to yield the desired products 3e-3i
of biphenyl 3a’ in a yield of 92%.
and 3f’ with high yields ranging from 82% to 99%. By expanding
Furthermore, in Table 2, a comparison is presented to evaluate
the range of aryl halides, the applicability can also be extended
the catalytic efficiency of PdCl2/ZnONWs in comparison to other pal-
to include aryl bromides (The range of aryl halides). For instance,

Scheme 3. Scope of substrates. Reaction conditions: Ar-X (X = I or Br, 0.25 mmol), Ar-B(OH)2 (0.375 mmol), PdCl2/ZnO NWs (1.0 mg, 76 mol ppm active metal), Na2CO3
(0.5 mmol), EtOH/H2O (1.0 mL/1.0 mL), 80 °C for 12 h. Isolated yields are reported.

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S. Pan, J. Guo, X. Chen et al. Arabian Journal of Chemistry 16 (2023) 105343

Scheme 4. Synthesis of biphenyl derivatives with 7.6 mol ppm palldium species.

Table 2
Efficiency comparison between PdCl2/ZnONWs and other catalysts in the Suzuki reaction.

Entry Catalyst Conditions Cycle Ref.

(mol% Pd) (times)
1 Pd-Ag/ZnO(13.3) EtOH, K3PO4, 78C 6 25
2 Pd/ZnO NPs(0.093) H2O, K2CO3, 100C 7 26
3 Pd/ZnO(0.08) EtOH/H2O, K3PO4, reflux 3 27
4 Pd NP/ZnO@Zn(0.01) DMF, K2CO3, 100C 3 28
5 Pd/ZnO(15) EtOH/H2O, K2CO3, 70C 5 29
6 Pd-PdO/ZnO(3.24) EtOH/H2O, K2CO3, 25C 5 30
7 PdCl2/ZnONWs (0.00076–0.0076) EtOH/H2O, Na2CO3, 80C 4 this work

ladium catalysts supported on ZnO for Suzuki coupling reactions reused up to three times with minimal loss in catalytic efficiency.
documented in the literature. The comparison results indicate that Additionally, the loading of palladium species has been success-
PdCl2/ZnONWs exhibited remarkable turnover number (TON) and fully reduced to 7.6 mol part per million, resulting in an impressive
turnover frequency (TOF) values. total turnover number of 130,000 and a turnover frequency of
0.75 s 1 for the PdCl2/ZnONWs catalyst. Furthermore, our laboratory
4. Conclusions is currently exploring the potential of expanding the applications
of this catalyst to other transformations.
In summary, we have developed a catalyst composed of palla-
dium chloride immobilized on ZnO nanowires and successfully Declaration of competing interest
applied it in the Suzuki reaction. This catalyst efficiently promoted
the reaction of aryl halides with arylboronic acids, resulting in the The authors declare that they have no known competing finan-
synthesis of biphenyl derivatives with high yields ranging from cial interests or personal relationships that could have appeared
82% to 99%. TEM analyses showed that palladium nanoparticles to influence the work reported in this paper.
were generated during the reaction and were the actual catalyti-
cally active species in this transformation. The impact of the sup- Acknowledgments
port on catalytic activity was thoroughly studied, and the results
revealed that the supported catalyst’s performance is predomi- This work was financially supported by the National Natural
nantly influenced by the crystalloid structure and morphology of Science Foundation of China (No. 21576211), Tianjin Science and
zinc oxide. The catalyst of palladium chloride immobilized on Technology Program (No. 22YDTPJC00920), Program for Tianjin
ZnO nanowires (PdCl2/ZnONWs) emonstrated remarkable catalytic Innovative Research Team in Universities (No. TD13-5031), and
activity. Furthermore, it exhibited the ability to be recovered and Tianjin 131 Research Team of Innovative Talents.
7
S. Pan, J. Guo, X. Chen et al. Arabian Journal of Chemistry 16 (2023) 105343

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