Mesoporous carbon supported ultrasmall palladium particles as highly active catalyst for Suzuki-Miyaura reaction

Article abstract of DOI:10.1002/aoc.5104

A fast and efficient eco-friendly two-step preparation of a palladium-containing mesoporous carbon catalyst (C1) from green and readily available carbon precursors (phloroglucinol and glyoxal), a porogen template (pluronic F-127) and PdCl₂ is described. Catalyst C1 contains ultra-small Pd nanoparticles (1.2 nm) uniformly dispersed in the carbon network and shows an outstanding activity for Suzuki-Miyaura reactions in pure water: extremely low amounts of palladium (10 μequiv. in most cases) are sufficient to afford almost palladium-free products (containing <0.25 ppm of precious metal without further purification steps).

Full text of DOI:10.1002/aoc.5104

Received: 18 March 2019
DOI: 10.1002/aoc.5104
Revised: 12 June 2019
Accepted: 15 June 2019
C O M M U N I C A T I O N
Mesoporous carbon supported ultrasmall palladium
particles as highly active catalyst for Suzuki‐Miyaura
reaction
Mohamed Enneiymy1,2 | Claude Le Drian1,2 | Camelia Matei Ghimbeu1,2
|
Jean‐Michel Becht1,2
1 Université de Haute‐Alsace, CNRS, IS2M
UMR 7361, F‐68100 Mulhouse, France
2 Université de Strasbourg, France
A fast and efficient eco‐friendly two‐step preparation of a palladium‐containing
mesoporous carbon catalyst (C1) from green and readily available carbon pre-
cursors (phloroglucinol and glyoxal), a porogen template (pluronic F‐127) and
PdCl2 is described. Catalyst C1 contains ultra‐small Pd nanoparticles (1.2 nm)
uniformly dispersed in the carbon network and shows an outstanding activity
for Suzuki‐Miyaura reactions in pure water: extremely low amounts of palla-
dium (10 μequiv. in most cases) are sufficient to afford almost palladium‐free
products (containing <0.25 ppm of precious metal without further purification
steps).
Correspondence
Jean‐Michel Becht, Université de Haute‐
Alsace, CNRS, IS2M UMR 7361, F‐68100,
Mulhouse, France.
Email: jean‐michel.becht@uha.fr
Funding information
Fondation pour l'ENSCMu
KEYWORDS
C‐C coupling, chemistry in water, mesoporous carbon, palladium nanoparticles, heterogeneous
catalysis
1 | INTRODUCTION
but expensive HandaPhos ligand.[4] Some of us have also
developed a magnetic palladium catalyst supported on a
The palladium‐catalyzed Suzuki‐Miyaura coupling is a
widely used reaction both in academic and industrial lab-
oratories for the creation of new carbon–carbon
bonds.[1,2] However this coupling presents some draw-
backs: 1) palladium is a scarce precious metal; 2) its price
increases rapidly (> 28.000 €.kg−1 in October 2018
and > 45.000 €.kg−1 in January 2019); 3) residual
cobalt core covered by
a
carbon shell bearing
diphenylphosphino groups for Suzuki‐Miyaura couplings
in ethanol.[5] The group of Grison has also reported an
EcoPd catalyst obtained from a plant (Eichhornia
crassipes) able to bioconcentrate palladium and its appli-
cation for Suzuki‐Miyaura couplings in glycerol in the
presence of 0.1–1 mequiv. of palladium.[6] The same year,
Sarkar et al. have described the preparation of a
palladium‐containing graphitic carbon nitride (nano‐Pd/
gC3N4) nanocomposite and its use for Suzuki‐Miyaura
reactions in water under microwave irradiations using
0.94 mequiv. of supported palladium.[7] Other groups
have reported heterogeneous palladium catalysts sup-
ported on silica bearing dimethylamino groups or N‐
heterocyclic ligands[8] hydroxyapatite nanospheres,[9]
montmorillonite,[10] MgO carbon quantum dots,[11] γ‐iron
amounts of palladium contaminates the final products[3]
4) cross‐couplings are often performed in
;
environmentally‐questionable organic solvents. In the
two last decades enormous progress has been made in
the field of preserving the resources in scarce precious
metals with the development of heterogeneous reusable
catalysts.[2] Very recently, the development of palladium
catalysts for Suzuki‐Miyaura reactions in “green” solvents
has suscited huge interest. For example the group of
Lipshutz has developed a Suzuki‐Miyaura reaction in
aqueous nanomicelles using an commercially available
oxide,[12]
cyclodextrin,[13] urea‐based amphiphilic porous organic
an
imidazolium‐functionalized
β‐
Appl Organometal Chem. 2019;e5104.
wileyonlinelibrary.com/journal/aoc
© 2019 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.5104

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ENNEIYMY ET AL.
polymers,[14] an ionic liquid copolymer,[15] eumelanin,[16]
oak gum.[17] These catalysts showed an interesting activ-
ity for Suzuki‐Miyaura reactions in water but most of
them are prepared via a multi‐step synthesis[8,9] involving
toxic and sensitive reagents.[18]
Mesoporous carbons present some key advantages
compared to traditional supports, like high availability
and low cost, high specific surface area, well‐ordered
and interconnected porous structure and good chemical,
thermal and mechanical stabilities. Therefore, they have
attracted tremendous attention in many fields such as
adsorption, catalysis and energy storage.[19] In addition,
the mesoporous carbon has been widely used as supports
for metal‐based nanoparticles, their unique uniform pore
structure and rich surface functionalities allowing to
obtain very small and well dispersed supported nanopar-
ticles exhibiting enhanced performances due to the syner-
getic effects between the two materials.[20]
In this respect we have recently described direct prep-
arations of mesoporous carbons containing palladium
nanoparticles[21] or palladium/iron nanoalloys[22] from
biosourced precursors for Suzuki‐Miyaura reactions in
propane‐1,2‐diol at 140 °C using respectively 0.03 mequiv.
and 0.15 mequiv. of supported palladium. More recently
we have described a magnetic biosourced mesoporous
carbon containing palladium/cobalt nanoalloys and its
use for Suzuki‐Miyaura reactions in refluxing water
requiring however 10 mequiv. of supported palladium.[2]
Despite the efforts undertaken in the last years, the devel-
opment of efficient and easily accessible palladium cata-
lysts from safe precursors and their use in water with a
leaching of only extremely low amounts of palladium is
a major but relatively unexplored domain in catalysis.
We are therefore pleased to describe herein a novel
palladium‐containing mesoporous carbon catalyst (C1)
fulfilling all these requirements. This catalyst has the par-
ticularity of containing ultra‐small Pd nanoparticles
(1.2 nm) which are very homogeneously distributed in
the carbon framework providing thus unique catalytic
performances for aryl‐aryl bond forming reactions in pure
water.
2 | EXPERIMENTAL
All chemicals were purchased from Sigma‐Aldrich and
used without any further purification.
2.1 | Preparation of catalyst C1
The catalyst C1 was prepared by a two‐step bottom‐up
approach involving firstly the synthesis of carbon support
and then the synthesis of Pd nanoparticles. The general
synthesis pathway is illustrated in Scheme 1. The meso-
porous carbon support was synthesized by the evapora-
tion induced self‐assembly (EISA) route starting from a
solution containing a surfactant (Pluronic F‐127) and a
phenolic resin based on phloroglucinol‐glyoxal.[31]
Briefly, Pluronic F‐127 (3.27 g) and phloroglucinol
(1.65 g) were dissolved in 81 mL of ethanol under stirring,
followed by the addition of 0.2 g of citric acid and 1.62 ml
of glyoxal solution (40% in water). The obtained solution
is disposed in several petri dishes and left to evaporate
under the fume hood in order to form a polymer film
which is removed by mechanical scratching, dried at
80 °C and then pyrolysed at 600 °C under Ar atmosphere.
In a second step, the carbon (1.74 g) is impregnated with
an anhydrous ethanol solution (10 ml) of
tetrachloropalladous acid (H2PdCl4), prepared by mixing
a proper amount of PdCl2 (0.066 g) with HCl (37% wt,
SCHEME 1 Preparation of catalyst C1

ENNEIYMY ET AL.
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0.5 ml) at 60 °C. The carbon/Pd‐based suspension is
stirred under a fume‐hood until complete evaporation of
the solvent and then is dried at 80 °C for 12 hrs in air
followed by thermal reduction under a mixture Ar/H2
(10% of H2) at 300 °C for 4 hr.
3 | RESULTS & DISCUSSION
3.1 | Preparation and characterizations of
catalyst C1
Catalyst C1 was prepared by a two‐step bottom‐up syn-
thesis approach (Scheme 1) involving first the synthesis
of the carbon porous support and then the formation of
Pd nanoparticles in the carbon network. The carbon
was obtained by self‐assembly of phenolic resin precur-
sors (phloroglucinol‐glyoxal) with a pore creating agent
(Pluronic F‐127) followed by thermal annealing which
led to the formation of a porous carbon.[23] In a second
step, the impregnation of this carbon with a Pd‐based salt
solution followed by thermal reduction (Scheme 1) led to
the formation of Pd/Carbon catalyst C1 possessing Pd
nanoparticles of a narrowly distributed size and a homo-
geneous repartition on the carbon surface, as revealed by
STEM images (Figure 1a, b). The particle size was surpris-
ingly very small (ca. 1.2 nm) as can be observed in
Figure 1c. In our previous reports, the smallest Pd particle
sizes obtained were in the range of 2.5–3.0 nm, but other
carbon supports and Pd amounts were used which may
affect this parameter.[24]
For instance, the increase in the amount of metal par-
ticles generally induces an increase in the particle size.[25]
Herein, the amount of Pd in the carbon network is low
(~2.3%) allowing to avoid the particle growth and agglom-
eration. Moreover, the carbon surface chemistry, i.e., the
nature and the amount of functional groups may impact
the size and the dispersion of the particles.[26] Such func-
tional groups improve the wetting behaviour of carbon
with the metal salt and may act as active sites to anchor
the metal nanoparticles favouring their dispersion. The
small size of the nanoparticles could also be observed on
XRD patterns (Figure 2a) which show a broad peak at
around 41°, which is an overlap of (111)/(200) diffraction
peaks of the cubic‐face centered structure of Pd and that
of (100) peak of graphitic structure (G) of carbon support.
It can be noted that in the case of carbon, this peak is
shifted towards higher values (43°) compared to catalyst
C1, confirming the Pd formation (vertical lines corre-
spond to the theoretical Pd positions extracted from Crys-
tallography Open Database, COD‐9013416). The broad
peak shape suggested very small nanoparticles and low
degree of crystallinility, in line with other work[27] and
in agreement with STEM (Figure 1a, b) and the diffuse
diffraction circles observed on the Selected Area Electron
Diffraction (SAED) images (in‐set Figure 1a). The pres-
ence of Pd could be confirmed also by energy dispersive
analyses (EDX) as illustrated in Figure S1 (Supporting
Information). More insights about the surface chemistry
of catalyst C1 were obtained by the XPS technique
2.2 | Characterisation of catalyst C1
The crystalline structure of the carbon support and of cat-
alyst C1 was determined by X‐ray powder diffraction
(XRD) technique with a D8 ADVANCE A25 powder dif-
fractometer (from Bruker) in Bragg–Brentano reflexion
geometry θ – θ. The Pd catalyst dispersion on the carbon
support was investigated with a JEOL ARM‐200F trans-
mission electron microscope working at 200 kV in STEM
(Scanning Transmission Electron Microscopy) mode. The
Pd particle size distribution was obtained by ImageJ soft-
ware by counting ca. 500 particles from several STEM
images. The TEM set‐up is equipped with an energy dis-
persive analyzer (EDX) which was used to determine
the chemical composition of the materials. The surface
chemistry was obtained by X‐ray photoelectron spectros-
copy (XPS) with a VG Scienta SES 200–2 spectrometer
equipped with a monochromatized Al Kα X‐ray source
(1486.6 eV) and a hemispherical analyzer. The pass
energy was 100 eV. The porous characteristics of the cat-
alyst were obtained by N2 sorption isotherms with a
Micromeritics ASAP 2020 set‐up. The materials were
outgassed at 150 °C under vacuum for 12 hr prior to the
analyses. The BET specific surface area (SSA) was calcu-
lated in the relative pressure range (P/P0) of 0.05–0.3.
2.3 | General procedure for the synthesis
of biaryls 1a‐j
Catalyst C1 (10–100 μequiv. of supported Pd) was added
to a suspension of aryl bromide (20 mmol, 1 equiv),
areneboronic acid (22 mmol, 1.1 equiv.), K2CO3 (24 mmol,
1.2 equiv) in H2O (120 ml). The reaction mixture was
refluxed for 10 hr. After cooling to 20 °C, C1 was filtered
off using a 0.2 μm PTFE membrane. Ethyl acetate
(200 ml) was then added. The organic phase was washed
twice with water (50 ml), dried with MgSO4, filtered and
concentrated under vacuum. When necessary the residue
was purified by flash‐chromatography on silica gel using
AcOEt/cyclohexane as eluant. After drying under vac-
uum (0.1 mbar) pure biaryls were obtained as shown by
1
their H‐NMR spectra (CDCl3, 300 MHz) which were in
accordance with the literature (see Supporting
information).

4 of 8
ENNEIYMY ET AL.
FIGURE 1 HRTEM images of C1 catalyst before (a, b) and after (c, d) 1st catalytic test along with their corresponding particle size
distributions: (e) before test and (f) after test. In‐set of the Figure 1a: SAED image of the C1 material
(Figure 2). The C 1s spectra of carbon support (Figure 2b)
shows the presence of a main important peak placed at
284.4 eV corresponding to the C sp2 contribution. In addi-
tion, oxygen‐based functional groups such as ether (C‐
OR), carbonyl (C=O) and carboxyl (‐COOR) are observed
as well between 284.9 and 286.0 eV. These functional
groups provide a hydrophilic character to carbon which
favors the good impregnation with the palladium based
solution. The Pd 3d high resolution spectra (Figure 2c)
show two main peaks, i.e., Pd 3d5/2 and Pd 3d3/2 placed
at 335 eV and 340 eV, respectively. Each peak was
deconvoluted into two components, namely metallic pal-
ladium, Pd0 and palladium oxide, Pd2+. The Pd0 contribu-
tion is predominant compared to that of Pd2+ as reflected
by the more intense peak of the former one. The presence
of a layer of palladium oxide in the surface of Pd nanopar-
ticles is well known to occur due to the small size of the
particles which exhibit high reactivity towards oxygen.[28]
The presence of oxygen bonded with Pd can be remarked
in the O 1s peak (Figure 2d) as well, however its amount
is significantly much lower than the amount of the oxy-
gen bonded with carbon in functional groups.

ENNEIYMY ET AL.
5 of 8
FIGURE 2 XRD patterns of the carbon support and carbon/Pd catalyst, C1 (a) and XPS high resolution deconvoluted spectra of the C1
catalyst: C 1s core spectra (b), Pd 3d spectra (c) and O 1s core spectra (d)
Catalyst C1 presented also a developed specific surface
area of 785 m2/g, a porous volume of 0.76 cm3/g and had
an open 3D porous structure (Figure 1b) formed by
micropores (size <2 nm) and mesopores (~5.5 nm) as
revealed by the type 4 nitrogen adsorption/desorption iso-
therm and the pore size distribution (Figure S2,
Supporting Information). The size of the whole catalyst
was ca. 1–2 μm as shown by TEM (Figure S3, Supporting
Information). Such a Pd/carbon hybrid material combin-
ing an open carbon porous structure and small Pd nano-
particles allows a good diffusion of the reagents and in
addition short diffusion pathways due to the reduced size.
The Pd surface to bulk ratio was also increased which
may induce significant changes in the performances com-
pared to bulk materials.[29]
as the solvent gave 1a in 99% yield (entry 4). Decreasing
the reaction time from 20 hr to 10 hr resulted in the
obtention of 1a in still an excellent 98% yield (entry 5).
Noteworthily replacing water by usual organic solvents
(DMF, ACN, toluene) gave only traces of 1a (entries 6–
8). Finally performing the cross‐coupling with 4‐
chloroacetophenone was unsuccessful even in the pres-
ence of 1 mequiv. of supported palladium and only traces
of 1a were obtained.
A hot filtration test was then performed to determine
the nature of the catalysis. After 2 hr of reaction between
4‐bromoacetophenone and benzeneboronic acid under
the optimized conditions of entry 5 (yield at that point:
64%) the catalyst was filtered off and the filtrate was
refluxed for another 8 hr (yield at that point: 74%). Solu-
ble palladium entities seem therefore to play only a minor
role in this coupling. The amount of residual palladium
present in product 1a after coupling was then determined
after complete mineralization of the crude mixture. It was
found that only ca. < 0.9% of the initial amount of sup-
ported palladium used was present. Even if palladium
was entirely found in the final product after work‐up, it
represents less than 0.25 ppm (wt/wt) of palladium in
3.2 | Suzuki‐Miyaura reactions in the
presence of catalyst C.
Performing the Suzuki‐Miyaura coupling in EtOH or in
EtOH/H2O mixtures afforded 1a in almost quantitative
yields (Table 1, entries 1–3). Gratifyingly using only water

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ENNEIYMY ET AL.
TABLE 2 Syntheses of biaryls
the final product. Therefore almost palladium‐free prod-
ucts can be obtained without tedious purification steps.
In addition after one use no significant changes were
observed by TEM and the Pd nanoparticles conserve a
small 1.3 nm size (Figure 1c,d,f). It is noteworthy that cat-
alyst C1 can be stored for several months without partic-
ular precautions and no loss of efficiency was observed
(Table 1).
Entrya
R1
R2
Pd (μequiv.)
Yieldb
Various biaryls were then prepared (Table 2) under the
optimized reaction conditions (Table 1, entry 5). Coupling
4‐bromoacetophenone with different areneboronic acids
led the corresponding biaryls in good yields (entries 1–
5). Reacting benzeneboronic acid with aryl bromides
bearing electro‐attracting or electron‐donating groups
afforded also the desired biaryls (entries 6–10). However
it is noteworthy that some couplings, in particular those
involing more hindered substrates, required the use of a
larger amount of supported palladium to proceed satisfac-
torily (entries 4, 9, 10). Finally the cross‐couplings of 3‐
thiopheneboronic acid with 4‐bromoacetophenone and
of benzeneboronic acid with 3‐bromopyridine were
unsuccessful even in the presence of 50 μequiv. of sup-
ported palladium, the desired products being obtained
in <20% yields.
1
2
4‐Ac
H
10
10
97 (1a)
99 (1b)
96 (1c)
68c (1d)
97d (1e)
96 (1f)
4‐Ac
4‐Me
3‐Me
2‐Me
4‐OMe
H
3
4‐Ac
10
4
4‐Ac
50
5
4‐Ac
50
6
4‐CO2Et
4‐CN
4‐Me
3‐Me
2‐Me
10
7
H
10
68 (1 g)
92 (1 h)
80e (1i)
49e (1j)
8
H
10
9
H
100
100
10
H
aReactions performed in the presence of an aryl bromide (1.0 equiv.), an
areneboronic acid (1.1 equiv.), K2CO3 (1.2 equiv.) and catalyst C1.
bIsolated yield.
cYield using 10 μequiv. of supported Pd: < 10%.
dYield using 10 μequiv. of supported Pd: 27%.
eYield using 10 μequiv. of supported Pd: < 10%.
TABLE 1 Optimization of the reaction conditions
The activity of C1 was then compared to that of other
heterogeneous catalysts reported in the literature for
Suzuki‐Miyaura reactions in water (Table 3). Catalyst C1
is one of the most active in terms of amount of supported
palladium necessary and turn over frequency (TOF). It is
noteworthy that C1 exhibits also the smallest palladium
NPs sizes. 5. The author should give rational reason about
TABLE 3 Comparative study of reusable palladium‐catalysts for
Suzuki‐Miyaura reactions in water
Entrya
Solvent
Conditions
Yieldb
1
2
3
4
5
6
7
8
9
EtOH
Reflux, 20 hr
Reflux, 20 hr
Reflux, 20 hr
Reflux, 20 hr
Reflux, 10 hr
50 °C, 20 hr
100 °C, 20 hr
Reflux, 20 hr
100 °C, 20 hr
98%
Pd
PdNP TOF
h−1
EtOH/H2O 95: 5
EtOH/H2O 50: 50
H2O
99%
Entry Catalyst, additives
mequiv nm
97%
1
C1
0.01
0.94
0.7
1.2 10000
99%
2[7]
3[10]
nano‐Pd/gC3N4
15
11000
60
H2O
98%c,d
PdNPs@acid‐treated
<10
H2O
41%
montmorillonite
DMF
< 5%
< 5%
< 5%
48a
Pd@SiO2‐NMe2
5
2–7
2–5
‐
140
4950
400
5[15]
6[13]
7[17]
8[11]
9[16]
PdNPs@ionic copolymer, TBAB 0.1
ACN
Toluene
Pd@β‐cyclodextrine
PdNPs@oak gum
Pd@MgO‐CQDa
Pd NPs@Eumb
5
aReactions performed in the presence of 4‐bromoacetophenone (1.0 equiv.),
benzeneboronic acid (1.1 equiv.), K2CO3 (1.2 equiv.) and catalyst C1 (10
μequiv. of supported Pd).
bYields calculated by 1H‐NMR of the crude reaction mixture.
cIsolated yield: 97%.
3
5–7
2–6
2–3
60
3
150
0.5
1000
aCQD: carbon quantum dots.
bEum: eumelanin support.
dYield after refluxing the reaction mixture for 2 hr: 64%.

ENNEIYMY ET AL.
7 of 8
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In conclusion, a “green” and efficient preparation of a
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ous techniques (STEM, HRD, EDX and XPS) proving
the presence of ultra‐small Pd nanoparticles (1.2 nm)
homogeneously dispersed in a 3D open mesoporous
hydrophilic carbon framework. Catalyst C1 allows
Suzuki‐Miyaura reactions in water in the presence of
ppm amounts of supported palladium (10 μequiv. in most
cases). It is noteworthy that C1 is biosourced and repre-
sents so far one of the most active heterogeneous catalyst
for Suzuki‐Miyaura reactions in water leading to almost
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ACKNOWLEDGMENTS
We are grateful to the Fondation pour l'Ecole Nationale
Supérieure de Chimie de Mulhouse for a doctoral grant
and generous financial support to M. Enneiymy, to J.
Coulleray and B. Rety for helpful technical assistance, to
Dr. L. Vidal for TEM, to Dr. J.‐M. Le Meins for the XRD
and P. Fioux for the XPS analyses via IS2M technical
platform.
[19] a)A. Eftekhari, Z. Fan, Mater. Chem. Front. 2017, 1, 1001. b)W.
Libbrecht, A. Verberckmoes, J. Thybaut, P. Van der Voort, Car-
bon 2017, 116, 528. c)W. Xin, Y. Song, RSC Adv. 2015, 5, 83239.
[20] a)S. H. Joo, K. Kwon, D. JongYou, C. Pak, H. Chang, J. M. Kim,
Electrochim. Acta 2009, 54, 5746. b)X. Xu, Y. Li, Y. Gong, P.
Zhang, H. Li, Y. Wang, J. Am. Chem. Soc. 2012, 134, 16987. c)
M. J. Kim, T. W. Kim, H. J. Chae, C. U. Kim, S. Y. Jeong, J. R.
Kim, K. S. Ha, J. Nanosci. Nanotechnol. 2016, 16, 2004. d)Y.
Oumellal, K. Provost, C. Matei Ghimbeu, A. Martinez de Yuso,
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review about applications of Pd on charcoal in organic synthe-
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ORCID
Jean‐Michel Becht https://orcid.org/0000-0001-6489-3360
[21] C. Peter, A. Derible, J.‐M. Becht, J. Kiener, C. Le Drian, J.
Parmentier, V. Fierro, M. Girleanu, O. Ersen, J. Mater. Chem.
A 2015, 3, 12297.
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