Palladium Nanoparticles Immobilized on Individual Calcium Carbonate Plates Derived from Mussel Shell Waste: An Ecofriendly Catalyst for the Copper-Free Sonogashira Coupling Reaction

Article abstract of DOI:10.1002/asia.201700537

The conversion of waste into high-value materials is considered an important sustainability strategy in modern chemical industries. A large volume of shell waste is generated globally from mussel cultivation. In this work, mussel shell waste (Perna viridis) is transformed into individual calcium carbonate plates (ICCPs) and is applied as a support for a heterogeneous catalyst. Palladium nanoparticles (3–6 nm) are deposited with an even dispersion on the ICCP surface, as demonstrated by X-ray diffraction and scanning electron microscopy. Using this system, Sonogashira cross-coupling reactions between aryl iodides and terminal acetylenes were accomplished in high yields with the use of 1 % Pd/ICCP in the presence of potassium carbonate without the use of any copper metal or external ligand. The Pd/ICCP catalyst could also be reused up to three times and activity over 90 % was maintained with negligible Pd-metal leaching. This work demonstrates that mussel shell waste can be used as an inexpensive and effective support for metal catalysts in coupling reactions, as demonstrated by the successful performance of the Pd-catalyzed, copper-free Sonogashira cross-coupling process.

Full text of DOI:10.1002/asia.201700537

CHEMISTRY
AN ASIAN JOURNAL
www.chemasianj.org
Accepted Article
Title: Pd Nanoparticles immobilized on individual calcium carbonate
plate derived from mussel shell waste: An eco-friendly catalyst for
copper-free Sonogashira coupling reaction
Authors: Trin Saetan, Chutiparn Lertvachirapaiboon, Ekgasit Sanong,
Mongkol Sukwattanasinitt, and Sumrit Wacharasindhu
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Chem. Asian J. 10.1002/asia.201700537
Link to VoR: http://dx.doi.org/10.1002/asia.201700537
A Journal of
A sister journal of Angewandte Chemie
and Chemistry – A European Journal

10.1002/asia.201700537
Chemistry - An Asian Journal
FULL PAPER
Pd Nanoparticles immobilized on individual calcium carbonate
plate derived from mussel shell waste: An eco-friendly
catalyst for copper-free Sonogashira coupling reaction
Trin Saetan,[a] Chutiparn Lertvachirapaiboon,[b] Sanong Ekgasit,[b] Mongkol Sukwattanasinitt[a] and
Sumrit Wacharasindhu*[a]
Abstract: Conversion of waste into high value materials has been
considered an important sustainability strategy in modern chemical
industries. Large volume of shell waste is generated globally from
mussel cultivation. In this work, mussel shell wastes (Perna viridis)
are transformed into individual calcium carbonate plate (ICCP) and
Despite the use of homogeneous catalyst, heterogeneous version
gains more popularity in recent year due to the ease of
recyclability after use and compatibility with continuous flow
systems.[15] Therefore, a number of research have been focused
on the development of the solid support for palladium to catalyze
Sonogashira reaction including carbon sources (e.g. graphene,
charcoal[16-18] and carbon nanotube),[19] metal oxides,[20] modified
apply as
a
support for heterogeneous catalyst. Palladium
nanoparticles (3-6 nm) are deposited with even dispersion on ICCP
surface as demonstrated by X-ray diffraction and scanning electron
microscopy. Using the system, Sonogashira cross coupling reactions
between aryl iodides and terminal acetylenes are accomplished in
high yields with the use of 1% Pd/ICCP in the presence of potassium
carbonate without any use of copper metal or external ligand. The
Pd/ICCP can also be reused up to three times with remaining activity
over 90% and negligible Pd metal leaching. This work demonstrates
that mussel shell waste can be used as an inexpensive and effective
support for metal catalysts in coupling reactions as demonstrated by
our successful performance of Pd catalyzed, copper-free
Sonogashira cross coupling process.
[25-26]
silica,[21] chitosan,[22] dendrimer,[23] MOF[24] and polymers.
However, those catalysts in some cases require multi-step
preparation in hash condition; suffer from high metal leaching and
low reactivity requiring the use of external ligand and copper.
Among supported material, calcium carbonate, an inexpensive
and safe material, is widely used to embed palladium for
hydrogenation so called “Lindlar catalyst” but rarely use for the
Pd catalyzed C-C bond formation[27-28] especially in Sonogashira
cross coupling reaction. This may be due to low reusability
caused by low binding between calcium carbonate and palladium
species.
Nowadays, sustainability concept has become one of the
important criteria for the design of chemical process[29] bringing
waste-derived materials come to attention. One of the popular
example is the use of a nature-made composite materials so
Introduction
called biominerals as an alternative raw material for chemical
Since the discovery of Sonogashira reaction in the late 1970,[1] it
became a powerful tool for construction of C(sp)-C(sp2) bond
allowing the preparation of various acetylene derivatives for many
research fields such as pharmaceuticals, petrochemicals and
material science.[2-4] Classically, the Sonogashira reaction is
catalyzed by palladium/copper catalytic complexes in the
presence of phosphine ligands.[5-8] In recent years, however,
copper-free Sonogashira coupling reaction has been developed
[30-31]
industry.
Among them, calcium carbonate is the one of the
most abundant in nature found in numerous marine organisms. In
Asia pacific, green mussel is a common food which is harvested
in aquaculture facilities. Over 100,000 tons of waste shells are
produced each year. Most of shell wastes were disposed as a
[32]
landfill creating environmental problem. Therefore, transformation
of waste shell into more high-value material would benefit not only
economic but also environmental aspect. There were several
reports on the use of wasted mussel shells as raw material for
high value application.[33-35] Unlike precipitate calcium carbonate
which is a calcite polymorphism, the calcium carbonate derived
from natural shells is an aragonite polymorph which has higher
biocompatibility, density and hardness which make it a suitable
material in plastic, paper, glass, fiber and other industry. As for
the catalytic support, a simple grounded shell particle (SP) were
used in C-C bond formation to support Cu and Pd in Heck,[36]
Ulman[37] and click reaction[38] with good recycling ability. Such
property is attributed to the chelation of surface chitin and protein
molecules to metal species. Although there are much economic
and environmental benefits, an inconsistent and large size of
shell particle might affect the reproducibility and performance of
catalyst resulting in unequal effectiveness among each batch.17
Therefore, in this work we will prepare a new Pd supported
material based on Asian green mussel shell wastes (Scheme 1)
that is unlike any of the existing commercial Pd/CaCO3 or Pd
loaded on simple grounded shell particle Pd/SP. The virgin shell
[9-13]
in order to suppress the formation side product, diacetylenes.
[14]Even though those reaction conditions demonstrated high
reactivity and specificity, the use of homogeneous catalyst system
frequently causes a loss of palladium metal catalyst. Moreover,
trace metal contamination in the final product and environment is
very difficult to remove raising safety concern.
[a]
[b]
T. Saetan, Prof. M. Sukwattanasinitt, Prof. S. Wacharasindhu
Nanotec-CU Center of Excellence on Food and Agriculture,
Department of Chemistry, Faculty of Science, Chulalongkorn
University, Bangkok 10330, Thailand
E-mail: Sumrit.w@chula.ac.th
Dr. C. Lertvachirapaiboon, Prof. S. Ekgasit
Department Department of Chemistry, Faculty of Science,
Chulalongkorn University, Bangkok 10330, Thailand
Supporting information for this article is given via a link at the end of the
document.
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.

10.1002/asia.201700537
Chemistry - An Asian Journal
FULL PAPER
waste will be converted into the individual calcium carbonate plate
(ICCP) under convenient and benign process, offering a single
layer calcium carbonate plates with a uniform size, smooth
surface and high surface area as supported material for palladium
nanoparticle. Such heterogeneous catalyst will be first used in
ligand free, amine and copper free condition in Sonogashira
coupling reaction to prepare diarylacetylene derivatives. The new
catalyst is not only highlighted by comparisons of physical data
(e.g., TEM, SEM, TGA, DLS and XRD) with Pd/SP derived simple
shell particle and commercial Pd/CaCO3, but also by direct side-
by-side experiments in catalyzed Sonogashira couplings. This
new waste-derived heterogeneous catalyst could improve the
overall energy and atom-efficiency of existing Sonogashira
coupling reaction.
Scheme 1. Schematic illustration of the preparation of conventional Pd/shell particles (SP) and our Pd/ individual calcium carbonate plate (ICCP)
process could effectively break the nacreous structure into
individual calcium carbonate plate (ICCP). On the other hand, the
Results and Discussion
simple grounded shell particle (SP) displays the connection
among aragonite plates (figure 1a (top)). Assuming that, such
process lead to the partially cracking of the nacre structure
providing multiple size of shell particle which can be seen up to 9
diameter micrometer size. Moreover, palladium mapping
information from energy-dispersive X-ray reveals that Pd is well
dispersed onto the ICCP and SP as shown in figures 1b bottom
and top, respectively. The resemble images of SEM/EDX from
Pd/SP and Pd/ICCP are perhaps caused by its nanosize nature
that is hardly seen in the SEM technique. To verify thickness and
roughness of ICCP and SP, surface topologies of their stacked
aragonite layers were attempted (figure 1c). The enlarged SEM
images in figure 1d show the thickness of nacreous layer as ca.
0.4 micrometers. It clearly showed that the several nacreous
layers remain intact in Pd/SP (figure 1d (top). However, the
Pd/ICCP demonstrated a single particle of aragonite building
block (figure 1d (bottom). It suggested that our protocol is
undoubtedly selective removing the protein binder to create the
highly uniform “individual calcium carbonate plates” (ICCP) which
still maintain its original aragonite form. Moreover, in the edge
area of Pd/ICCP, bright field transmission electron microscopy
(TEM imaging shows a uniform morphology of Pd nanoparticles.
The palladium nanoparticles were predominantly 5 to 8 nm in
diameter with round-shape, as deduced from TEM image.
The X-ray diffraction (XRD) Studies.
Preparation of individual calcium carbonate plates and shell
particles supported palladium (Pd/ICCP and Pd/SP) catalysts. An
Asian green mussel shell is composed of thin aragonite calcium
[39-42]
carbonate layers bound by thin organic binding layers.
To
gain the advantage from this natural nanostructure, we therefore
hypothesized that the wasted shell can be fragmented into a
single aragonite plate so called “individual calcium carbonate
plate” (ICCP) without destroying the aragonite structure. To
selectively removing the organic protein binder between nacreous
layers, a dry shell was sonicated in aqueous 30% H2O2 for 24
hour followed by filtration with 200 mesh filter affording the ICCP.
For comparison, simple grounded shell particles (SP) were
prepared based on the procedure reported by Zeng[37] via
physical grounding of dry shell powder which is subsequently
filtered. Both Pd/ICCP and Pd/SP catalysts were prepared by
deposition-reduction of disodium tetrachloropalladate (Na2PdCl4)
on ICCP and SP, respectively, followed by reduction with NaBH4
in aqueous solution.
Characterization of Pd/ICCP and Pd/SP
To gain more information on the structure of Pd/ICCP and Pd/SP
catalyst, the SEM and EDX were measured. The SEM image
shows the catalyst received from treatment of dry shell with H2O2
under sonication yield mostly individual polygonal shaped particle
with 3 micrometer size (figure 2 (bottom)). It suggests that our
In order to characterize the crystallinity patterns of prepared
Pd catalysts (Pd/ICCP and Pd/SP) and commercial Pd/CaCO3,
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.

10.1002/asia.201700537
Chemistry - An Asian Journal
FULL PAPER
a
b
c
d
Pd/SP
Pd/ICCP
Figure 1. (a, b, c, d) SEM and EDX image of and shell particles (top, Pd/SP) and individual calcium carbonate plates supported palladium (bottom, Pd/ICCP)
catalysts.
Figure 3. X-ray diffraction patterns of the Pd/CaCO3, Pd/ICCP and Pd/SP
catalysts.
Thermogravimetric analysis
Figure 4 shows TG curves of Pd/ICCP (red line), Pd/SP (green
line) and Pd/CaCO3 (blue line). The TG curve obtained from
industrial calcium carbonate (Figure 4, blue line) showed a
thermal stability up to 600 °C with a single weight loss. This is
caused by the release of carbon dioxide, given rise to the
Figure 2. TEM image of individual calcium carbonate plates supported
palladium (Pd/ICCP) catalysts. Arrow indicate Pd nanoparticles.
formation of calcium oxide which is in good agreement with the
[44]
known literature.
The TG curve of Pd catalysts derived from
XRD analysis was performed for all samples. The diffractograms
in Figure 3 indicates different patterns among commercial CaCO3
vs. ICCP and SP suggesting the calcite and aragonite
polymorphs, respectively.[43] The resemble patterns are found in
before and after palladium loading of all supported materials
(commercial CaCO3, ICCP and SP, Figure S23) suggesting that
the Pd species is well dispersed on the surface and their particle
sizes are below the XRD detection limit.
shell calcium carbonate (Pd/ICCP, Pd/SP) on the other hands,
displays two major weight losses. The new decomposition is
o
founded at 200-300 C while the second one which is similar to
Pd/CaCO3 is at 600-800 oC. The new mass lost are corresponded
to volatile organic content such as protein and chitin from shell.
Interestingly, mass lost in the cast of Pd/ICCP, Pd/SP are
detected at 2.5 and 5.5 % respectively. These results confirmed
that our preparation method for ICCP partially remove organic
binder that was holding nacreous layers together but the organic
matrices on the surface which binds more strongly to the
aragonite plate were still preserved. This organic matrix has to be
maintained in order to stabilize Pd nanoparticle and increase the
reusability of catalyst in contrast to bare commercial Pd/CaCO3.
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.

10.1002/asia.201700537
Chemistry - An Asian Journal
FULL PAPER
the same method as above mentioned (Table 1, entry 3 and 4).
The slightly loss of Pd amount in those catalysts were observed
which is probably due to the decomposition under bench storage.
The palladium level measured here will be used for the entire
experiments in this investigation.
Table 1 Determination of Palladium content in the catalysts from ICP-OES
analysisa
Entry
Catalyst
Expected
Pd Contenta
Pd Content
1
2
3
4
Pd/ICCP
Pd/SP
7.0
6.1 ± 0.1%
5.7 ± 0.1%
4.3 ± 0.1%
6.9 ± 0.3%
7.0
Pd/CaCO3
Pd/C
5.0
10.0
Figure 4. Thermal gravimetric (TG) thermogram of Pd/ICCP, Pd/SP and
Pd/CaCO3
a Palladium weight percentage was determined from ICP-OES analysis.
Reaction condition screening
IR spectroscopic studies
With the catalysts in hand, we began our optimization of
Sonogasira coupling reaction between 4-iodotoluene (1b) and
phenyleneethynylene (2a) without copper and ligand (Table 2).
Using the known procedure,[45] the use of 1 %of Pd/C with
ethanol as solvent and potassium carbonate gave a full
conversion of starting iodide and provide the product 3b in 86%
yield (table 2, entry 1). Switching from the Pd/C into commercial
Pd/CaCO3, the coupling product was obtained in excellent yield
with no remaining starting material detected by GC (table 2, entry
2). To the best of our knowledge, this is the first use of Pd/CaCO3
as heterogeneous catalyst for Sonogasira coupling reaction. Next,
the wasted shell derived catalyst Pd/SP and Pd/ICCP were
subjected to above condition. When Pd/SP was used as a catalyst,
an incomplete reaction was observed and produced only 75% of
coupling product 3b with the remaining starting material. On the
other hand, no starting remains in the reaction condition in case
of Pd/ICCP and 94% of target product 3b was received. The
efficiency of Pd/ICCP over Pd/SP is perhaps governed by the
high surface are of ICCP support. We would like to note here that
this reaction condition is environmentally friendly and cost
effective. Ethanol and K2CO3 are the safe and inexpensive
chemicals favoring to use in the industry according to EPA
guideline.[46] Importantly, there is no need to use copper and extra
ligand in the reaction condition. We also ensured that there is no
trace cooper in our reaction by repeating the reaction using the
new glassware and freshly distilled solvent. Moreover, trace
analysis of copper performed by ICP-OES in Pd/ICCP and all
reagents used in the reaction confirmed that no copper were
present within the detection limit. Even though, we are satisfied
with the reaction condition but the effect of solvent and base were
further investigated to see their generality. Switching base from
K2CO3 to DIPA and Cs2CO3 or solvent from EtOH to MeCN and
DMSO, resulted in dramatically poor yields. The perforation of this
reaction condition comes from basicity and solubility of base and
solvent used in the reaction condition.
In FTIR analysis, we found that the peak at 1443.7 and 1444.4
cm-1 of ICCP and SP support, confirming the characteristic
stretching vibrations of C-O in aragonite form (Figure S24). On
the other hands, the structure of commercial CaCO3 was
corresponded to calcite morphology as the observation of
characteristic absorption peak at lower wavenumber at 1389.2
-
cm 1. The deposition of palladium into commercial CaCO3
resulted in an insignificant shift by 1.5 cm-1. In case of waste shell
derived catalysts Pd/ICCP and Pd/SP, up to 5 cm-1 shift were
2-
observed suggesting stronger interaction between CO3 from
waste shell and Pd species in comparison with commercial
CaCO3. The reason for the stronger interaction between calcium
carbonate in aragonite form in comparison with calcite is still
unclear and need to be further clarified.
Determination of Palladium content by ICP-OES analysis
Before the examination of catalytic activity of prepared catalyst,
Pd/ICCP, Pd/SP, Pd/CaCO3 and Pd/C contents were first
determined using inductively coupled plasma optical emission
spectrometry analysis (ICP-OES analysis) (table 1). Pd content in
those heterogeneous catalysts derived from the waste shell,
Pd/ICCP, Pd/SP were found at 6.6 and 5.7%(wt./wt.) respectively
(Table 1, entry 1 and 2). The higher loading of Pd/ICCP over
Pd/SP is perhaps due the surface morphology of the support. To
gain more information on the suface area of the support, BET
analysis of both supports were performed. Specific surface ares
of ICCP (6.12 m2g-1) is slightly higher than SP (4.21 m2g-1) which
supports the result of Pd loading in ICCP and SP. Also, we
hypothesized that the stacked nacreous in SP gave roughness
surface causing the reduction of the binding efficiency of Pd
nanoparticle toward the SP support. On the other hands, the
smoothness of ICCP surface facilitates the embedding between
Pd nanoparticle and ICCP. For comparison reason, the
commercial 5%Pd/CaCO3 and 10%Pd/C were analyzed under
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.

10.1002/asia.201700537
Chemistry - An Asian Journal
FULL PAPER
Table
3
Substrate scope of aryl iodide in the reaction with phenyl
acetylenea,b
Table 2 Optimization studies on the Sonogashira coupling reactiona
Entry
1
Catalyst
Solvent
EtOH
Base
%Yieldb
Pd/C
K2CO3
86
2
3
4
5
6
7
8
9
Pd/CaCO3
Pd/SP
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
MeCN
DMSO
K2CO3
K2CO3
K2CO3
DIPA
83
75
94
2
Pd/ICCP
Pd/ICCP
Pd/ICCP
Pd/ICCP
Pd/ICCP
Pd/ICCP
Cs2CO3
KOAc
K2CO3
K2CO3
15
9
5
3
aReaction condition: 4-iodotoluene (0.5 mmol), phenyl acetylene (0.6 mmol)
catalysts (0.005 mmol), bases (1.0 mmol), in solvents (6.0 mL). bDetermined
from the GC measurement.
aReaction condition: aryl iodides (0.5 mmol), phenyl acetylene (0.6 mmol)
Pd/ICCP (0.005 mmol), potassium carbonate (1.0 mmol), in EtOH (6.0 mL),
solution at 100 oC. bIsolated yields.
Substrate Scope
To evaluate substrate scope of this method, variety functional
groups need to be tested. Therefore, a series of aryl iodides either
commercially available or prepared according to literature
procedures were subjected to the coupling reaction with phenyl
acetylene in the presence of 2 mol % of Pd/ICCP under the
optimized reaction conditions (Table 1, entry 12) and the results
were summarized in Table 3. Good to excellent yields were
generally obtained after the column chromatography. The aryl
iodides bearing an electron donating group, such as methyl,
naphthyl, biphenyl and, methoxy (1a-1g) yielded the desired
bisarylacetylenes in excellent yields (3a-3g). However, the
cross-coupling of aryl iodides (1e) gave a fair yield of the target
product 3e under the optimized condition suggesting the steric
effect of the reaction. Aryl iodide bearing electron-withdrawing
groups for example, nitro, keto, aldehyde, cyano and
trifluoromethyl moieties were smoothly reacted with
phenylacetylene to generate the the diarylacetylene in good
yields (3i-3m). Nitrogen containing substrate such as 4-iodo
aniline (1n), phenylazide (1o) and pyridine (1p) were also suitable
for this transformation as they afforded the target compounds
(3n-p) in good yields. Moreover, other leaving groups, such as
chloro (1q) and bromo (1r) groups were well tolerated under
reaction conditions and were reacted selectively, giving the
desired products in good to excellent yields(3q-r).
We also expand the scope of the reaction into various terminal
alkyne substrates. The representative phenyl acetylenes bearing
electron-withdrawing (2b) and electron-donating groups (2c)
were proceeded smoothly under optimized reaction condition with
iodobenzene (1b) providing the coupled products 3s and 3t in
excellent yields. Moreover, terminal alkyne having alkyl
substituent such as 2d, were reacted with 1b to generate the
desired product 3u in good yield.
Scheme
2 Substrate scope of terminal alkynes in the reaction with
iodobenzenes
Reusability and metal leaching studies
To determine the reusability of catalyst, the three
consecutive runs of each catalyst including Pd/ICCP, Pd/SP and
Pd/CaCO3 were performed and the %conversion were carefully
monitored by GC. Table 4, we would like to note here that the
catalyst reuse process involves only filtration of the reaction
solution, wash with EtOH/water and drying in vacuum without any
activation via chemical or high temperature treatment. Significant
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.

10.1002/asia.201700537
Chemistry - An Asian Journal
FULL PAPER
losses of activity were found in both Pd/SP and Pd/CaCO3 since
second cycle. However, the Sonogashira reaction using Pd/ICCP
for three cycles gave the excellent conversion between 100-90%.
Significant losses of catalyst activity were found in both Pd/SP
and Pd/CaCO3 which may result from the catalyst deactivation
and leaching. The roughness surface of stacked aragonite in SP
may cause metal leaching due to the poor interaction between Pd
species and support. On the other hands, unlike the flat aragonite
in ICCP, commercial CaCO3 are found in form of calcite, therefore
the pore in those supports might be clogged during byproduct
generation in the reaction which cannot be washed away before
the next cycle. Also, lack of protein biding on the surface of
commercial CaCO3 could result in the loss of Pd species in each
cycle. To prove the hypothesis, metal leaching of each catalyst
was quantified. The reaction mixtures after the first run were
filtered and the crude products were subjected to ICP analysis.
Palladium contents in crude products from Pd/ICCP, Pd/SP and
Pd/CaCO3 were founded as followed 1.1, 1.4 and 8% wt./wt. The
result confirms the significant loss of Pd content in Pd/CaCO3
catalyst. On the other hands, negligible leaching of Pd contents
from the catalyst supported on waste shell in either SP or ICCP
are perhaps due to the strong chelation between Pd and protein
on the surface of the shell supports. Therefore, Pd/ICCP catalyst
is a promising option for low level leaching metal heterogeneous
catalyst with high reactivity and reusability.
Pd/ICCP should serve as a catalyst of choice for green
Sonogashira coupling reactions.
Experimental Section
Materials and methods
All reagents were purchased from Sigma-Aldrich, Fluka® (Switzerland) or
Merck® (Germany) and used without further purification. Analytical thin-
layer chromatography (TLC) was performed on Kieselgel F-254 pre-coated
plastic TLC plates from EM Science. Gel column chromatography was
carried out with silica gel (60, 230-400 mesh) from ICN Silitech. The 1H-
and 13C-NMR spectra were obtained on
a Varian Mercury NMR
spectrometer, which operated at 400 MHz for 1H and 100 MHz for 13C
nuclei (Varian Company, CA, USA) The morphological structure of ICCP
and SP was observed using a scanning electron microscope (SEM, JEOL
JSM-6510A) operating at 20 kV under a high vacuum mode with a
secondary electron image (SEI) detector. The elemental composition
analysis of the material was investigated using a built-in energy dispersive
X-ray spectrometer (EDS). The morphological structure of Pd
nanoparticles on individual calcium carbonate plate was observed using a
transmission electron microscopy (TEM, JEOL, JEM-2100) operating at
100-120 kV. The XRD patterns were recorded by an X-ray diffractometer
(DMAX 2200 Rigaku) under Cu Ka radiation. All ATR FT-IR spectra were
recorded using
a germanium micro-IRE with Nicolet 6700 FT-IR
spectrometer equipped with a mercury–cadmium–telluride (MCT) detector
at 4 cm-1 resolution and 128 co-addition scans. Surface area analyzer, N2
adsorption-desorption isotherms and BET specific surface area of the
catalysts were carried out using a BEL Japan, BELSORP-mini instrument.
Table 4 Comparing reusability of palladium catalysts
Preparation of tetrachloropalladic acid (H2PdCl4) solution
A mixture of palladium metal (1g) in aqua regia (5 mL, a mixture of
concentrated nitric acid and hydrochloric acid with a ratio of 3:1 v/v) was
stirred at 100 °C until palladium was completely dissolved. The solution
was then kept heating until almost dry and pouring into a 100-mL
volumetric flask. Water was added to adjust concentration of H2PdCl4 to
0.094 M.
Catalyst
% Conversionb
%Palladium
leachingc (wt./wt.)
1st
2nd
3rd
Pd/ICCP
Pd/SP
100
92
90
1.1
1.4
8.6
Preparation of the individual calcium carbonate plates and shell
particles supported palladium (Pd/ICCP and Pd/SP) catalysts
72
26
52
15
33
Pd/CaCO3
100
Asian green mussel (Perna viridis) shells were first cleaned to remove
residual tissues and other contaminants then drying under an ambient air.
The dried shells were baked at 200 °C for 2 h. The thermal-treated shells
were submerged in 30 % (wt./wt.) hydrogen peroxide solution under
ultrasonic sonication for 24 h to dissolve the degraded organic binder. The
treated-shells were filtered with 200 mesh filter size to obtain individual
calcium carbonate plates. After that, the individual calcium carbonate
plates were washed with water several times and air dried before keeping
in a desiccator for preparation of individual calcium carbonate plates
supported palladium (Pd/ICCP) catalyst. A solution of 0.094 M H2PdCl4 25
mL was rapidly added into 5 grams of the individual calcium carbonate
plates in 100 mL water. The mixture was stirred until color changed from
yellow to colorless. The powders washed with water until the color of
supernatant turned colorless. Finally, the catalyst was reduced with 1.2
equivalent of sodium borohydride for 1 h. Shell particles supported
palladium (Pd/SP) catalyst was prepared by the same procedure but
grounded shell particles, without hydrogen peroxide treatment, was used
instead.
aReaction condition: 4-iodotoluene (0.5 mmol), phenyl acetylene (0.6 mmol)
catalysts (0.005 mmol), bases (1.0 mmol), in solvents (6.0 mL). bDetermined
from the GC measurement. cDetermined by ICP-OES from crude after 1st
run.
Conclusions
In summary, we have developed a new heterogeneous palladium
catalyst supported on individual calcium carbonate plate (ICCP)
derived from waste Asian green mussel shell. The catalyst has
been shown to be highly active for copper and ligand free
Sonogashira coupling reaction. The reaction proceeds in
excellent yield with a variety of aryl iodides and terminal alkynes.
The Pd/ICCP also exhibits reusability while the simple Pd/SP and
Pd/CaCO3 cannot be reused. As it is convenient to be prepared
from shell waste and demonstrates high and stable activity;
General procedure for Sonogashira coupling reaction
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.

10.1002/asia.201700537
Chemistry - An Asian Journal
FULL PAPER
A sealed tube equipped with a magnetic stirring bar was charged with
K2CO3 (1.0 mmol) and Pd catalyst (1 mol%). Aryl iodide (0.5 mmol), terminal
alkyne (0.6 mmol), and ethanol (6 mL) were added. Stirring was continued
at 100 oC under nitrogen for 4 hour, and then cooled to room temperature.
The reaction mixture was filtered. The residue was purified by
chromatography, eluting with hexane and ethyl acetate.
Synthesized according to procedure A using 1-iodo-4-methoxybenzene
(117 mg, 0.5 mmol), ethynylbenzene (51 mg, 0.6 mmol), Pd/ICCP (9 mg,
0.005 mmol), potassium carbonate (138 mg, 1.0 mmol) in EtOH (6 mL) for
4 h to afford 3f (91.6 mg, 0.44 mmol, 88%) as a white solid. 1H NMR (400
MHz, CDCl3) δ 7.95 (d, J = 8.4 Hz, 2H), 7.61 (t, J = 7.2 Hz, 2H), 7.59 – 7.53
(m, 2H), 7.42 – 7.34 (m, 3H), 2.61 (d, J = 6.2 Hz, 3H). 13C NMR (101 MHz,
CDCl3) δ 197.22, 136.24, 131.76, 131.70, 128.82, 128.46, 128.27, 128.20,
122.70, 92.75, 88.66, 26.55; GC-MS: m/z: 207.9.
1,2-diphenylethyne (3a).[26] [CAS: 501-65-5]:)
4-(phenylethynyl)aniline[48] (3g). [CAS: 1849-25-8]:
According to the general procedure, the reaction was performed by using
4-iodobenzene (102 mg, 0.5 mmol), ethynylbenzene (51 mg, 0.6 mmol),
Pd/ICCP (9 mg, 0.005 mmol), potassium carbonate (138 mg, 1.0 mmol) in
EtOH (6 mL) for 4 h to afford 3a (78.4 mg, 0.44 mmol, 88%) as a white solid.
1H NMR (400 MHz, CDCl3): δ 7.61 (dd, J = 6.6, 1.8 Hz, 4H), 7.51 – 7.32 (m,
6H); 13C NMR (101 MHz, CDCl3): δ 131.67, 128.40, 128.30, 123.37, 89.47;
GC-MS: m/z: 178.1.
Synthesized according to procedure A using 4-iodoaniline (110 mg, 0.5
mmol), ethynylbenzene (51 mg, 0.6 mmol), Pd/ICCP (9 mg, 0.005 mmol) ,
potassium carbonate (138 mg, 1.0 mmol) in EtOH (6 mL) for 4 h to afford
3g (82.1 mg, 0.43 mmol, 85%) as a brown solid. 1H NMR (400 MHz, CDCl3)
δ 7.46 – 7.37 (m, 2H), 7.30 – 7.19 (m, 5H), 6.55 (d, J = 8.4 Hz, 2H), 3.72 (s,
2H). 13C NMR (101 MHz, CDCl3) δ 146.79, 133.09, 131.49, 128.39, 127.78,
114.89, 114.75, 112.79, 90.26, 87.47; GC-MS: m/z: 218.9.
1-methyl-4-(phenylethynyl)benzene[26] (3b). [CAS: 3287-02-3]:
1-chloro-4-(phenylethynyl)benzene[49] (3h). [CAS: 5172-02-1]:
Synthesized according to procedure A using 4-iodotoluene (109 mg, 0.5
mmol), ethynylbenzene (51 mg, 0.6 mmol), Pd/ICCP (9 mg, 0.005 mmol),
potassium carbonate (138 mg, 1.0 mmol) in EtOH (6 mL) for 4 h to afford
3b (80.7 mg, 0.42 mmol, 84%) as a colorless solid. 1H NMR (400 MHz,
CDCl3) δ 7.57 (d, J = 7.5 Hz, 2H), 7.48 (d, J = 7.1 Hz, 2H), 7.43 – 7.31 (m,
3H), 7.20 (d, J = 7.8 Hz, 2H), 2.41 (s, 3H); 13C NMR (101 MHz, CDCl3) δ
138.39, 131.57, 131.53, 129.13, 128.33, 128.08, 123.54, 120.26, 89.60,
88.76, 21.50; GC-MS: m/z: 192.0.
Synthesized according to procedure A using 1-chloro-4-iodobenzene (119
mg, 0.5 mmol), ethynylbenzene (51 mg, 0.6 mmol), Pd/ICCP (9 mg, 0.005
mmol), potassium carbonate (138 mg, 1.0 mmol) in EtOH (6 mL) for 4 h to
afford 3h (94.6 mg, 0.44 mmol, 89%) as a white solid. 1H NMR (400 MHz,
CDCl3) δ 7.62 – 7.54 (m, 2H), 7.50 (d, J = 8.4 Hz, 2H), 7.43 – 7.32 (m, 5H).
13C NMR (101 MHz, CDCl3) δ 134.39, 132.93, 131.73, 128.81, 128.59,
128.51, 123.10, 121.95, 90.49, 88.40; GC-MS: m/z: 211.8.
1-bromo-4-(phenylethynyl)benzene[50] (3i). [CAS: 13667-12-4]:
1-methyl-3-(phenylethynyl)benzene[26] (3c). [CAS: 14635-91-7]:
Synthesized according to procedure A using 1-bromo-4-iodobenzene (141
mg, 0.5 mmol), ethynylbenzene (51 mg, 0.6 mmol), Pd/ICCP (9 mg, 0.005
mmol), potassium carbonate (138 mg, 1.0 mmol) in EtOH (6 mL) for 4 h to
afford 3i (115.7 mg, 0.44 mmol, 90%) as a white solid. 1H NMR (400 MHz,
CDCl3) δ 7.57 – 7.45 (m, 4H), 7.43 – 7.31 (m, 5H). 13C NMR (101 MHz,
CDCl3) δ 133.17, 131.76, 131.74, 128.65, 128.54, 123.08, 122.62, 122.42,
90.66, 88.45; GC-MS: m/z: 255.8.
Synthesized according to procedure A using 3-iodotoluene (109 mg, 0.5
mmol), ethynylbenzene (51 mg, 0.6 mmol), Pd/ICCP (9 mg, 0.005 mmol),
potassium carbonate (138 mg, 1.0 mmol) in EtOH (6 mL) for 4 h to afford
3c (88.4 mg, 0.42 mmol, 92%) as a colorless oil. 1H NMR (400 MHz, CDCl3)
δ 7.64 – 7.53 (m, 2H), 7.40 (dd, J = 11.3, 5.2 Hz, 5H), 7.29 (t, J = 7.6 Hz,
1H), 7.20 (d, J = 7.6 Hz, 1H), 2.41 (s, 3H). 13C NMR (101 MHz, CDCl3) δ
138.46, 132.65, 132.06, 129.61, 129.15, 128.78, 128.69, 128.61, 123.88,
123.57, 90.05, 89.51, 21.66; GC-MS: m/z: 191.9.
1-nitro-4-(phenylethynyl)benzene[51] (3j). [CAS: 1942-30-9]:
1-methyl-2-(phenylethynyl)benzene[26] (3d). [CAS: 14309-60-5]:
Synthesized according to procedure A using 1-iodo-4-nitrobenzene (125
mg, 0.5 mmol), ethynylbenzene (51 mg, 0.6 mmol), Pd/ICCP (9 mg, 0.005
mmol), potassium carbonate (138 mg, 1.0 mmol) in EtOH (6 mL) for 4 h to
afford 3j (101.6 mg, 0.44 mmol, 91%) as a white solid. 1H NMR (400 MHz,
CDCl3) δ 8.21 (d, J = 8.7 Hz, 2H), 7.66 (d, J = 8.8 Hz, 2H), 7.56 (dd, J = 5.9,
2.6 Hz, 2H), 7.46 – 7.32 (m, 3H). 13C NMR (101 MHz, CDCl3) δ 147.11,
132.37, 131.96, 130.37, 129.40, 128.66, 123.74, 122.23, 94.83, 87.68; GC-
MS: m/z: 222.9.
Synthesized according to procedure A using 2-iodotoluene (109 mg, 0.5
mmol), ethynylbenzene (51 mg, 0.6 mmol), Pd/ICCP (9 mg, 0.005 mmol),
potassium carbonate (138 mg, 1.0 mmol) in EtOH (6 mL) for 4 h to afford
3d (86.5 mg, 0.45 mmol, 90%) as a colorless oil. 1H NMR (400 MHz, CDCl3)
1H NMR (400 MHz, CDCl3) δ 7.64 – 7.53 (m, 2H), 7.40 (dd, J = 11.3, 5.2 Hz,
5H), 7.29 (t, J = 7.6 Hz, 1H), 7.20 (d, J = 7.6 Hz, 1H), 2.41 (s, 3H). 13C NMR
(101 MHz, CDCl3) δ 138.46, 132.65, 132.06, 129.61, 129.15, 128.78,
128.69, 128.61, 123.88, 123.57, 90.05, 89.51, 21.66; GC-MS: m/z: 191.9.
1-(4-(phenylethynyl)phenyl)ethanone[26] (3k). [CAS: 1942-31-0]:
2-iodo-1,3-dimethylbenzene (3e)[47]. [CAS: 180783-48-6]:
Synthesized according to procedure A using 1-(4-iodophenyl)ethanone
(123 mg, 0.5 mmol), ethynylbenzene (51 mg, 0.6 mmol), Pd/ICCP (9 mg,
0.005 mmol) , potassium carbonate (138 mg, 1.0 mmol) in EtOH (6 mL) for
4 h to afford 3k (112.2 mg, 0.51 mmol, 102%(quantitative yield)) as a white
solid. 1H NMR (400 MHz, CDCl3) δ 7.95 (d, J = 8.4 Hz, 2H), 7.61 (t, J = 7.2
Hz, 2H), 7.59 – 7.53 (m, 2H), 7.42 – 7.34 (m, 3H), 2.61 (d, J = 6.2 Hz, 3H).
13C NMR (101 MHz, CDCl3) δ 197.22, 136.24, 131.76, 131.70, 128.82,
128.46, 128.27, 128.20, 122.70, 92.75, 88.66, 26.55; GC-MS: m/z: 219.9.
Synthesized according to procedure A using 2-iodo-1,3-dimethylbenzene
(116 mg, 0.5 mmol), ethynylbenzene (51 mg, 0.6 mmol), Pd/ICCP (9 mg,
0.005 mmol), potassium carbonate (138 mg, 1.0 mmol) in EtOH (6 mL) for
4 h to afford 3e (56.7 mg, 0.28 mmol, 55%) as a colorless oil. 1H NMR (400
MHz, CDCl3) 1H NMR (400 MHz, CDCl3) δ 7.66 – 7.57 (m, 2H), 7.47 – 7.33
(m, 3H), 7.18 (dt, J = 19.5, 6.9 Hz, 3H), 2.60 (s, 6H). 13C NMR (101 MHz,
CDCl3) δ 140.38, 131.52, 128.48, 128.20, 127.90, 126.83, 124.01, 123.13,
98.00, 87.30, 21.22.; GC-MS: m/z: 205.9.
4-(phenylethynyl)benzaldehyde[52] (3l). [CAS: 57341-98-7]:
1-methoxy-4-(phenylethynyl)benzene[26] (3f). [CAS: 7380-78-1]:
Synthesized according to procedure A using 4-iodobenzaldehyde (116 mg,
0.5 mmol), ethynylbenzene (51 mg, 0.6 mmol), Pd/ICCP (9 mg, 0.005
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.

10.1002/asia.201700537
Chemistry - An Asian Journal
FULL PAPER
mmol), potassium carbonate (138 mg, 1.0 mmol) in EtOH (6 mL) for 4 h to
potassium carbonate (138 mg, 1.0 mmol) in EtOH (6 mL) for 4 h to afford
3r (179.2 mg, 0.43 mmol, 86%) as a yellow solid. 1H NMR (400 MHz, CDCl3)
δ 8.77 (d, J = 1.4 Hz, 1H), 8.55 (dd, J = 4.9, 1.6 Hz, 1H), 7.82 (dt, J = 7.9,
1.9 Hz, 1H), 7.60 – 7.49 (m, 2H), 7.42 – 7.33 (m, 3H), 7.29 (ddd, J = 7.8, 4.9,
0.7 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ 152.25, 148.52, 138.70, 131.85,
128.98, 128.60, 123.22, 122.66, 120.73, 92.91, 86.00; GC-MS: m/z: 178.9.
1
afford 3l (65.9 mg, 0.32 mmol, 64%) as a white solid. H NMR (400 MHz,
CDCl3) δ 10.02 (s, 1H), 7.86 (d, J = 8.0 Hz, 2H), 7.67 (d, J = 8.0 Hz, 2H),
7.56 (dd, J = 6.3, 2.8 Hz, 2H), 7.43 – 7.32 (m, 3H). 13C NMR (101 MHz,
CDCl3) δ 191.50, 135.57, 132.24, 131.93, 129.70, 129.10, 128.61, 122.65,
93.59, 88.66.; GC-MS: m/z: 205.9.
1-(phenylethynyl)-4-(trifluoromethyl)benzene[26] (3m). [CAS: 370-99-0]:
1-fluoro-4-(phenylethynyl)benzene[57] (3s). [CAS: 405-29-8]:
Synthesized
according
to
procedure
A
using
1-iodo-4-
Synthesized according to procedure A using 4-iodobenzene (102 mg, 0.5
mmol), 1-ethynyl-4-fluorobenzene (72 mg, 0.6 mmol), Pd/ICCP (9 mg,
0.005 mmol), potassium carbonate (138 mg, 1.0 mmol) in EtOH (6 mL) for
4 h to afford 3s (81.4 mg, 0.42 mmol, 83%) as a white solid. 1H NMR (400
MHz, CDCl3) δ 7.52 (dt, J = 9.1, 5.2 Hz, 4H), 7.35 (dd, J = 9.2, 4.8 Hz, 3H),
7.04 (t, J = 8.6 Hz, 2H). 13C NMR (101 MHz, CDCl3) δ 163.89, 161.41,
133.65, 133.57, 131.70, 128.50, 128.46, 123.27, 119.56, 119.53, 115.87,
115.65, 89.20, 88.45; GC-MS: m/z: 195.9.
(trifluoromethyl)benzene (136 mg, 0.5 mmol), ethynylbenzene (51 mg, 0.6
mmol), Pd/ICCP (9 mg, 0.005 mmol) , potassium carbonate (138 mg, 1.0
mmol) in EtOH (6 mL) for 4 h to afford 3m (91.1 mg, 0.37 mmol, 74%) as a
white solid. 1H NMR (400 MHz, CDCl3) δ 7.70 – 7.62 (m, 4H), 7.59 (dd, J =
6.3, 2.9 Hz, 2H), 7.45 – 7.36 (m, 3H). 13C NMR (101 MHz, CDCl3) δ 131.96,
131.91, 128.98, 128.60, 125.48, 125.44, 125.41, 125.37, 122.75, 91.93,
88.12; GC-MS: m/z: 245.9.
4-(phenylethynyl)benzonitrile[53] (3n). [CAS: 29822-79-5]:
1-methoxy-4-(phenylethynyl)benzene[26] (3t). [CAS: 7380-78-1]:
Synthesized according to procedure A using 4-iodobenzonitrile (114 mg,
0.5 mmol), ethynylbenzene (51 mg, 0.6 mmol), Pd/ICCP (9 mg, 0.005
mmol), potassium carbonate (138 mg, 1.0 mmol) in EtOH (6 mL) for 4 h to
afford 3n (72.2 mg, 0.35 mmol, 71%) as a white solid. 1H NMR (400 MHz,
CDCl3) δ 7.64 (q, J = 8.3 Hz, 4H), 7.60 – 7.53 (m, 2H), 7.47 – 7.34 (m, 3H).
13C NMR (101 MHz, CDCl3) δ 132.08, 132.04, 131.80, 129.14, 128.52,
128.26, 122.26, 118.50, 111.51, 93.81, 87.75; GC-MS: m/z: 202.9.
Synthesized according to procedure A using 4-iodobenzene (102 mg, 0.5
mmol), 1-ethynyl-4-methoxybenzene (79 mg, 0.6 mmol), Pd/ICCP (9 mg,
0.005 mmol), potassium carbonate (138 mg, 1.0 mmol) in EtOH (6 mL) for
4 h to afford 3t (84.3 mg, 0.41 mmol, 81%) as a white solid. 1H NMR (400
MHz, CDCl3) δ 7.43 (d, J = 7.0 Hz, 2H), 7.38 (d, J = 8.7 Hz, 2H), 7.30 – 7.16
(m, 3H), 6.78 (d, J = 8.7 Hz, 2H), 3.71 (s, 3H).13C NMR (101 MHz, CDCl3)
δ 159.77, 133.17, 131.57, 128.42, 128.04, 123.75, 115.53, 114.14, 89.53,
88.21, 55.37; GC-MS: m/z: 207.9.
1-azido-4-(phenylethynyl)benzene[54] (3o). [CAS: 669090-70-4]:
oct-1-yn-1-ylbenzene[58] (3u). [CAS: 16967-02-5]:
Synthesized according to procedure A using 1-azido-4-iodobenzene (122
mg, 0.5 mmol), ethynylbenzene (51 mg, 0.6 mmol), Pd/ICCP (9 mg, 0.005
mmol), potassium carbonate (138 mg, 1.0 mmol) in EtOH (6 mL) for 4 h to
afford 3o (71.2 mg, 0.32 mmol, 65%) as a brown solid. 1H NMR (400 MHz,
CDCl3) δ 7.64 (q, J = 8.3 Hz, 4H), 7.60 – 7.53 (m, 2H), 7.47 – 7.34 (m, 3H).
13C NMR (101 MHz, CDCl3) δ 132.08, 132.04, 131.80, 129.14, 128.52,
128.26, 122.26, 118.50, 111.51, 93.81, 87.75; GC-MS: m/z: 219.1.
Synthesized according to procedure A using 4-iodobenzene (102 mg, 0.5
mmol), oct-1-yne (66 mg, 0.6 mmol), Pd/ICCP (9 mg, 0.005 mmol),
potassium carbonate (138 mg, 1.0 mmol) in EtOH (6 mL) for 4 h to afford
3u (73.6 mg, 0.40 mmol, 79%) as a colorless oil. 1H NMR (400 MHz, CDCl3)
δ 7.43 (dd, J = 7.5, 2.0 Hz, 2H), 7.35 – 7.25 (m, 3H), 2.44 (t, J = 7.1 Hz, 2H),
1.67 – 1.62 (m, 2H), 1.55 – 1.32 (m, 10H), 0.94 (d, J = 6.8 Hz, 3H). 13C NMR
(101 MHz, CDCl3) δ 131.99, 128.60, 127.86, 90.91, 81.04, 31.83, 29.21,
29.06, 23.01, 19.87, 14.48.; GC-MS: m/z: 186.0.
1-(phenylethynyl)naphthalene[26] (3p). [CAS: 4044-57-9]:
General procedure for reuse of heterogeneous palladium catalysts
Synthesized according to procedure A using 1-iodonaphthalene (127 mg,
0.5 mmol), ethynylbenzene (51 mg, 0.6 mmol), Pd/ICCP (9 mg, 0.005
mmol), potassium carbonate (138 mg, 1.0 mmol) in EtOH (6 mL) for 4 h to
afford 3p (93.6 mg, 0.41 mmol, 82%) as a white solid. 1H NMR (400 MHz,
CDCl3) δ 8.56 (d, J = 8.3 Hz, 1H), 7.88 (dt, J = 21.1, 11.4 Hz, 3H), 7.80 –
7.65 (m, 3H), 7.60 (dd, J = 14.3, 7.2 Hz, 1H), 7.56 – 7.37 (m, 4H). 13C NMR
(101 MHz, CDCl3) δ 133.75, 133.69, 132.12, 130.82, 129.21, 128.88,
128.82, 128.76, 127.22, 126.87, 126.68, 125.72, 123.89, 121.38, 94.81,
88.03; GC-MS: m/z: 228.0.
The heterogeneous palladium catalyst was separated from the reaction
mixture by filtration. The reused palladium catalyst was washed with
ethanol, followed by removal of the solvent under a reduced pressure
before the next reaction.
General procedure for scanning electron microscopy and energy
dispersive X-ray (SEM and EDX) analysis
4-(phenylethynyl)-1,1'-biphenyl[55] (3q). [CAS: 15784-39-1]:
Scanning electron microscope (SEM, JEOL, JSM-6510A) was employed
for the structural investigation of morphology of the individual calcium
carbonate plates and shell particles supported palladium (Pd/ICCP and
Pd/SP) catalysts under a low acceleration voltage of 5 kV. To collect SEM
images, a specimen was wrapped with an aluminum foil before mounting
onto a modified stub with the cross-sectioned surface normal to the
electron beam. The elemental composition analysis of the materials was
investigated using a built-in energy dispersive X-ray spectrometer (EDS).
Synthesized according to procedure A using 4-iodo-1,1'-biphenyl (140 mg,
0.5 mmol), ethynylbenzene (51 mg, 0.6 mmol), Pd/ICCP (9 mg, 0.005
mmol), potassium carbonate (138 mg, 1.0 mmol) in EtOH (6 mL) for 4 h to
afford 3q (101.7 mg, 0.40 mmol, 80%) as a white solid. 1H NMR (400 MHz,
CDCl3) δ 7.64 (dt, J = 8.1, 5.9 Hz, 8H), 7.50 (t, J = 7.6 Hz, 2H), 7.46 – 7.35
(m, 4H). 13C NMR (101 MHz, CDCl3) δ 141.43, 140.82, 132.49, 132.08,
129.31, 128.82, 128.72, 128.08, 127.47, 123.78, 122.66, 90.55, 89.79; GC-
MS: m/z: 253.9.
Determination of organic content
3-(phenylethynyl)pyridine[56] (3r). [CAS: 13238-38-5]:
The organic contents in the Pd/ICCP and Pd/SP catalysts were
quantitatively determined by thermal gravimetric analysis (PerkinElmer,
Pyris 1). The catalyst was loaded into a ceramic crucible and heated up to
850 oC at a heating rate of 20 oC/min under nitrogen environment.
Synthesized according to procedure A using 3-iodopyridine (103 mg, 0.5
mmol), ethynylbenzene (51 mg, 0.6 mmol), Pd/ICCP (9 mg, 0.005 mmol),
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.

10.1002/asia.201700537
Chemistry - An Asian Journal
FULL PAPER
[26] T. Suzuka, Y. Okada, K. Ooshiro, Y. Uozumi, Tetrahedron 2010, 66,
.1069-1064
[27] L. Cerveny, P. Franzova, V. Ruzicka, Chem. Prum. 1986, 36, .596-592
[28] D. Wolf, PharmaChem 2012, 11,.19-18
General procedure for transmission electron microscopy (TEM)
analysis
[29] J. A. Bennett, K. Wilson, A. F. Lee, J. Mater. Chem. A 2016, 4, -3617
.3637
[30] A. Shafiu Kamba, M. Ismail, T. A. Tengku Ibrahim, Z. A. B. Zakaria, J
Nanomater. 2013, 2013, .9
[31] R. S. Varma, ACS Sustain. Chem. Eng. 2016, 4, .5878-5866
[32] Linnaeus, Food and Agriculture Organization of the United Nations,
http://www.fao.org/fishery/species/2691/en, 1758
Transmission electron microscopy (TEM, JEOL, JEM-2100) was employed
for the structural investigation of morphology of the individual calcium
carbonate plates supported palladium (Pd/ICCP), operated at 100−120 kV.
To collect TEM images, a particle was dropped onto grids for transmission
electron microscopy.
[33] P. Nair, B. Singh, S. N. Upadhyay, Y. C. Sharma, J. Cleaner Prod.
2012, 30-29, .90-82
General procedure for surface area analysis
[34] R. Rezaei, M. Mohadesi, G. R. Moradi, Fuel 2013, 109, .541-534
[35] N. Seco-Reigosa, S. Peña-Rodríguez, J. C. Nóvoa-Muñoz, M. Arias-
Estévez, M .J. Fernández-Sanjurjo, E. Álvarez-Rodríguez, A. Núñez-Delgado,
Environ Sci Pollut Res Int. 2013, 20, .2678-2670
[36] Y.-M. Shen, Y.-J. Du, M.-F. Zeng, D. Zhi, S.-X. Zhao, L.-M. Rong, S.-Q.
Lv, L. Du, C.-Z. Qi, Appl. Organomet. Chem. 2010, 24, .635-631
[37] M. Zeng, Y. Du, C. Qi, S. Zuo, X. Li, L. Shao, X.-M. Zhang, Green
Chem. 2011, 13, .356-350
The sample weights were nearly 40.0 mg and weighted exactly after
pretreatment at 200 0C for 2 hr. Glass rods were placed at sample cell and
blank cell positions after that the samples were analyzed with BEL-sorp-
mini instrument.
[38] X. Xiong, L. Cai, Y. Jiang, Q. Han, ACS Sustain. Chem. Eng. 2014, 2,
.771-765
[39] A. P. Jackson, J. F. V. Vincent, R. M. Turner, Proceedings of the Royal
Society B: Biological Sciences 1988, 234, .440-415
Acknowledgements
[40] I. M. Weiss, C. Renner, M. G. Strigl, M. Fritz, Chem. Mater. 2002, 14,
.3259-3252
[41] H. M. Leung, S. K. Sinha, TRIBOL. INT. 2009, 42, .49-40
[42] G. Zhang, J. Xu, J. Struct. Biol. 2013, 182, .43-36
[43] W. Siriprom, N. Chumnanvej, A. Choeysuppaket, P. Limsuwan,
Procedia Eng. 2012, 32, .1126-1123
[44] C. Lertvachirapaiboon, T. Jirapisitkul, P. Pienpinijtham, K. Wongravee,
C. Thammacharoen, S. Ekgasit, J. Mater. Sci. 2014, 49, .6289-6282
[45] N. Iranpoor, H. Firouzabadi, Y. Ahmadi, Eur. J. Org. Chem. 2012, 2012,
.311-305
[46] C. Capello, U. Fischer, K. Hungerbuhler, Green Chem. 2007, 9, -927
.934
This study is financially supported by Thailand Research Fund
(TRF-RSA6080018) and National Nanotechnology Center
(NANOTEC), NSTDA, Ministry of Science and Technology,
Thailand, through its program of the Center of Excellence Network.
This work is also partially supported by a Grant for International
Research Integration: Chula Research Scholar and the student
scholarship was received from 90th Anniversary of Chulalongkorn
University fund (Ratchadaphiseksomphot Endowment Fund).
[47] M. S. Maji, S. Murarka, A. Studer, Org. Lett. 2010, 12, .3881-3878
[48] G. Adjabeng, T. Brenstrum, C. S. Frampton, A. J. Robertson, J.
Hillhouse, J. McNulty, A. Capretta, J. Org. Chem. 2004, 69, .5086-5082
[49] L. Melzig, A. Metzger, P. Knochel, Chem. Eur. J. 2011, 17, .2956-2948
[50] P. Karastatiris, J. A. Mikroyannidis, I. K. Spiliopoulos, A. P. Kulkarni, S.
A. Jenekhe, Macromolecules 2004, 37, .7878-7867
[51] S. Bong Park, H. Alper, Chem. Commun. 2004, .1307-1306
[52] L. Salvi, S.-J. Jeon, E. L. Fisher, P. J. Carroll, P. J. Walsh, J. Am.
Chem. Soc. 2007, 129, .16125-16119
[53] H. Kim, P. H. Lee, Adv. Synth. Catal. 2009, 351, .2832-2827
[54] H. Tomioka, S. Sawai, Org. Biomol. Chem. 2003, 1, .4450-4441
55]] P. Li, L. Wang, H. Li, Tetrahedron 2005, 61, .8640-8633
[56] H.-J. Chen, Z.-Y. Lin, M.-Y. Li, R.-J. Lian, Q.-W. Xue, J.-L. Chung, S-.C.
Chen, Y.-J. Chen, Tetrahedron 2010, 66, .7761-7755
[57] N. Kakusawa, K. Yamaguchi, J. Kurita, J. Organomet. Chem. 2005,
690, .2966-2956
Keywords: heterogeneous catalyst • biomineral • sonogashira •
• shell waste • aragonite
[1]
K. Sonogashira, Y. Tohda, N. Hagihara, Tetrahedron Lett. 1975, 16,
.4470-4467
[2]
[3]
[4]
[5]
R. Chinchilla, C. Nájera, Chem. Rev. 2007, 107, .922-874
L. Chen, C.-J. Li, Adv. Synth. Catal. 2006, 348, .1484-1459
H. Doucet, J.-C. Hierso, Angew. Chem. Int. Ed. 2007, 46, .871-834
J. Cheng, Y. Sun, F. Wang, M. Guo, J.-H. Xu, Y. Pan, Z. Zhang, J. Org.
Chem. 2004, 69, .5432-5428
[6]
[7]
A. Elangovan, Y.-H. Wang, T.-I. Ho, Org. Lett. 2003, 5, .1844-1841
D. García, A. M. Cuadro, J. Alvarez-Builla, J. J. Vaquero, Org. Lett.
2004, 6, .4178-4175
[8]
A. Soheili, J. Albaneze-Walker, J. A. Murry, P. G. Dormer, D. L.
[58] L. Wang, P. Li, Synth. Commun. 2003, 33, .3685-3679
Hughes, Org. Lett. 2003, 5, .4194-4191
[9]
B. Liang, M. Dai, J. Chen, Z. Yang, J. Org. Chem. 2005, 70, .393-391
[10] T. Fukuyama, M. Shinmen, S. Nishitani, M. Sato, I. Ryu, Org. Lett.
2002, 4, .1694-1691
[11] S. Urgaonkar, J. G. Verkade, J. Org. Chem. 2004, 69, .5755-5752
[12] M. García-Melchor, M. C. Pacheco, C. Nájera, A. Lledós, G. Ujaque,
ACS Catal. 2012, 2, .144-135
[13] J.-H. Li, Y. Liang, Y.-X. Xie, J. Org. Chem. 2005, 70, .4396-4393
[14] For palladium free Sonogashira coupling reaction. J. Kou, A. Saha, C.
Bennett-Stamper, R. S. Varma, Chem. Commun. 2012, 48, .5864-5862
[15] Yin, J. Liebscher, Chem. Rev. 2007, 107, .173-133
[16] A. Komaromi, Z. Novak, Chem. Commun. 2008, .4970-4968
[17] S. Mori, T. Yanase, S. Aoyagi, Y. Monguchi, T. Maegawa, H. Sajiki,
Chem. Eur. J. 2008, 14, .6999-6994
[18] C. Duplais, A. J. Forman, B. A. Baker, B. H. Lipshutz, Chem. Eur. J.
2010, 16, .3371-3366
[19] R. G. Heidenreich, K. Köhler, J. G. E. Krauter, J. Pietsch, Synlett 2002,
2002, .1122-1118
[20] P. D. Stevens, G. Li, J. Fan, M. Yen, Y. Gao, Chem. Commun. 2005,
.4437-4435
[21] N. Kim, M. S. Kwon, C. M. Park, J. Park, Tetrahedron Lett. 2004, 45,
.7059-7057
[22] S. E. S. Leonhardt, A. Stolle, B. Ondruschka, G. Cravotto, C. D. Leo, K.
D. Jandt, T. F. Keller, Applied Catalysis A: General 2010, 379, .37-30
[23] M. Esmaeilpour, A. Sardarian, J. Javidi, Catal. Sci. Technol. 2016, 6,
.4019-4005
[24] S. Gao, N. Zhao, M. Shu, S. Che, Applied Catalysis A: General 2010,
388, .201-196
[25] Z.-W. Ye, W.-B. Yi, J. Fluorine Chem. 2008, 129, .1128-1124
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.

10.1002/asia.201700537
Chemistry - An Asian Journal
FULL PAPER
FULL PAPER
Text for Table of Contents
Trin Saetan, Chutiparn
Lertvachirapaiboon, Sanong Ekgasit,
Mongkol Sukwattanasinitt and Sumrit
Wacharasindhu*
Page No. – Page No.
Pd Nanoparticles immobilized on
individual calcium carbonate plate
derived from mussel shell waste: an
Eco-friendly catalyst for copper-free
Sonogashira coupling reaction
For internal use, please do not delete. Submitted_Manuscript
This article is protected by copyright. All rights reserved.