Mechanochemical Synthesis of Active Magnetite Nanoparticles Supported on Charcoal for Facile Synthesis of Alkynyl Selenides by C?H Activation

Article abstract of DOI:10.1002/cctc.201600280

Magnetite (Fe₃O₄) nanoparticles supported on charcoal, graphene, or SBA-15 were prepared by a simple solid-state grinding technique and subsequent thermal treatment. The Fe₃O₄ nanoparticles supported on activated charcoal exhibited high catalytic activity and furnished good yields of the alkynyl selenide product in the cross-coupling reaction of diphenyl diselenide and alkynes through activation of C?H and Se?Se bonds under ecofriendly conditions, surpassing traditional copper-based catalysts to effect the same organic transformation.

Full text of DOI:10.1002/cctc.201600280

DOI: 10.1002/cctc.201600280
Communications
Mechanochemical Synthesis of Active Magnetite
Nanoparticles Supported on Charcoal for Facile Synthesis
of Alkynyl Selenides by CÀH Activation
Balaji Mohan,[a, c] Ji Chan Park,*[b] and Kang Hyun Park*[a]
Magnetite (Fe3O4) nanoparticles supported on charcoal, gra-
phene, or SBA-15 were prepared by a simple solid-state grind-
ing technique and subsequent thermal treatment. The Fe3O4
nanoparticles supported on activated charcoal exhibited high
catalytic activity and furnished good yields of the alkynyl sele-
nide product in the cross-coupling reaction of diphenyl disele-
nide and alkynes through activation of CÀH and SeÀSe bonds
under ecofriendly conditions, surpassing traditional copper-
based catalysts to effect the same organic transformation.
lysts that are able to achieve target products at low catalyst
loadings can be obtained.
Considerable efforts have been made to fabricate Fe3O4 NPs
on various supports. Traditionally, methods used to prepare
the catalysts involve multiple steps, including the preparation
of the nanoparticles and their isolation, drying, and immobili-
zation on suitable supports. However, in industry, the use of
a simple method with low-costing supports is still needed, be-
cause the cost of preparing supported catalysts is important,
as is the activity and reusability of the catalyst. Therefore,
a facile and economical technique without any pretreatment
of the solid support is desired for the synthesis of a catalyst.
Recently, solid-state grinding with subsequent infiltration of
metal salts (i.e., melt–infiltration process) was utilized as a con-
venient and fast route to prepare supported metal catalysts
owing to easy synthetic procedures, superior product crystal-
linity, and ease of scaling up.[5] Herein, we report an easy syn-
thesis of iron-oxide NPs supported on activated charcoal
(Fe3O4/C) by a facile and economic synthetic technique. To
check and compare the high activity and stability of the Fe3O4/
C catalyst in reactions for the synthesis of alkynyl selenides,
other well-known supports (e.g., graphene and SBA-15) were
Transition-metal nanoparticles (NPs) have recently gained sci-
entific and technological interest in various areas such as sen-
sors, fuel cells, homogeneous catalysts, and heterogeneous
catalysts for important organic transformations.[1] So far,
a number of solid-supported transition-metal nanoparticles,
such as Cu, Au, Ru, Rh, Ir, Ni, and Pd, have been widely used as
heterogeneous catalysts for important catalytic processes.[2]
In particular, iron-oxide NPs have been widely used as solid
supports for the purpose of stabilizing metal nanoparticles to
avoid leaching, for complete recovery by using an external
magnetic field for recycling, and also to circumvent contamina-
tion with target products.[3] Owing to their low cost of prepara-
tion and the natural abundance and environmentally friendly
nature of iron, the use of iron-oxide NPs themselves as cata-
lysts for important organic reactions, such as, nitrophenol re-
duction, benzyl alcohol oxidation, Sonogashira coupling, bory-
lation, and multicomponent reactions, has been reported.[4] By
tuning the surface design of the support along with the size
and shape of the nanoparticles, more suitable solid supports
for Fe3O4 NPs to provide highly efficient more recyclable cata-
[a] Dr. B. Mohan, Prof. K. H. Park
Department of Chemistry and Chemistry Institute for Functional Materials
Pusan National University
Busan 609-735 (Republic of Korea)
Figure 1. Pictorial representation of the Fe3O4 NPs on (from left to right)
E-mail: chemistry@pusan.ac.kr
charcoal, single-layer graphene, and SBA-15.
[b] Dr. J. C. Park
Clean Fuel Laboratory
Korea Institute of Energy Research
Daejeon 305-343 (Republic of Korea)
E-mail: jcpark@kier.re.kr
[c] Dr. B. Mohan
Department of Chemistry
Madanapalle Institute of Technology & Science, Madanapalle, Chittoor
Andhra Pradesh, 305-343 (India)
Supporting Information for this article can be found under http://
dx.doi.org/10.1002/cctc.201600280.
Scheme 1. Facile synthesis of Fe3O4/C nanocatalysts by infiltration and
thermal treatment.
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also tested. Figure 1 depicts photographs of Fe3O4 NPs
supported on charcoal, graphene, and SBA-15.
(111) peak by the Debye–Scherrer equation. N2 sorption ex-
periments at À1968C for the Fe3O4/C catalyst exhibited type IV
adsorption/desorption hysteresis with delayed capillary evapo-
ration at a relative pressure of 0.5 (Figure 2 f). The Brunauer–
Emmett–Teller (BET) surface area and total pore volume of
Fe3O4/C were calculated to be 642 m2 gÀ1 and 0.48 cm3 gÀ1, re-
spectively. The size of the small pores of Fe3O4/C was found to
be 3.9 nm, obtained from the desorption branches.
Scheme 1 demonstrates the simple procedure for the syn-
thesis of the Fe3O4/C catalyst. First, Fe(NO3)3·9H2O was melt-in-
filtrated into the mesoporous charcoal powder by grinding at
room temperature with subsequent aging at 508C for 24 h in
a tumbling oven. Then, small magnetite nanoparticles approxi-
mately 13 nm in size were obtained by thermal decomposition
of the confined salt in the carbon pores at 4008C under nitro-
gen flow. The high-angle annular dark-field scanning transmis-
sion electron microscopy (HAADF-STEM) image shows bright
dots, which implies incorporation of the Fe3O4 nanoparticles in
the porous charcoal support (Figure 2a). Small Fe3O4 particles
To compare the Fe3O4/C catalyst with other supported FeO4
catalysts, Fe3O4/SBA-15 and Fe3O4/graphene were introduced
through the same procedures. SBA-15 was chosen as a repre-
sentative porous silica support with high surface area and reg-
ular pore structure. Fe3O4/SBA-15 showed very small nanoparti-
cles approximately 2 nm in size (Figure 3a). HRTEM analysis re-
vealed the lattice fringe image of the Fe3O4 phase, which was
measured to be d=0.21 nm of the (400) planes (Figure 3b). In
the Fe3O4/graphene catalyst, the particle size was less than
2 nm and, therefore, not easily detected, even by HRTEM (Fig-
ure 3c). The red circles marked in Figure 3a,c indicate extreme-
ly small nanoparticles. The lattice fringe image of the Fe3O4
particles was measured to be d=0.253 nm of the (311) planes
(Figure 3d). Comparing peak intensities, the particle sizes of
Fe3O4 in SBA-15 and graphene were much smaller than those
of the Fe3O4/C catalyst (Figure 3e). The BET surface areas of
Fe3O4/SBA-15 and Fe3O4/graphene were calculated to be 303
and 394 m2 gÀ1, respectively (Figure 3 f). The total pore vol-
umes of Fe3O4/SBA-15 and Fe3O4/graphene were 0.88 and
1.24 cm3 gÀ1, respectively. The Fe-loading contents of all cata-
lysts were calculated to be approximately 10 wt% on the basis
of Fe converted from the iron nitrate salt after thermal
treatment.
The catalytic activity of the synthesized Fe3O4 NPs was
tested in the cross-coupling reaction of diphenyl diselenide
with alkynes to obtain the corresponding alkynyl selenides
through CÀH and SeÀSe bond activation.
The chemistry of organochalcogens, especially selenium, has
expanded rapidly over the last decade. Enormous efforts have
been devoted to developing novel organochalcogen com-
pounds for potential applications in the field of modern organ-
ic synthesis and catalysis. Organoselenium compounds are par-
ticularly attractive and have gained considerable attention
among researchers, because of their ability to mimic natural
compounds with important biological properties, including an-
tiviral, antimicrobial, antitumor, and antioxidant activities.[6]
Moreover, chalcogen derivatives have been applied in the de-
velopment of organic materials, such as liquid crystals, organic
semiconductors, and electroconductive polymers.[7] In this con-
text, we recently developed various synthetic procedures in-
volving the use of nanocatalysts to obtain organochalcogen
derivatives. Taking into consideration our program devoted to-
wards the synthesis of organochalcogen compounds, we
turned our attention to alkynyl selenides.[8,2b]
Figure 2. a) HADDF STEM image, b) low-resolution TEM image, c) HRTEM
image with corresponding Fourier transform pattern (inset), d) particle-size
distribution histogram, e) XRD spectrum, and f) N2 adsorption/desorption
isotherms of the Fe3O4/C catalyst. More than 200 particles were counted for
the sample. The bars represent 100 nm (a), 50 nm (b), and 5 nm (c).
with an average diameter of 12.6 nm are observed (Fig-
ure 2b,d). High-resolution transmission electron microscopy
(HRTEM) analysis revealed the lattice fringe images of the
Fe3O4 particles, and they were measured to be d=0.253 nm of
the (311) planes (Figure 2c). The X-ray powder diffraction
(XRD) spectrum matched well with the Fe3O4 phase (Figure 2e,
JCPDS No. 19-0629). The average size of the Fe3O4 nanoparti-
cles was estimated to be 13.0 nm from the broadness of the
A literature survey showed that various types of catalysts, es-
pecially copper, have been used to make CspÀSe bonds
through cross-coupling of either terminal alkynes or alkynyl
halides with a convenient source of electron-deficient seleniu-
m[9,8a] to afford alkynyl selenides in high yields. Although
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Figure 3. a) TEM and b) HRTEM images of Fe3O4/SBA-15 with corresponding Fourier transform pattern (inset); c) TEM and d) HRTEM images of Fe3O4/graphene
with corresponding Fourier transform pattern (inset); e) XRD spectra and f) N2 adsorption/desorption isotherms of Fe3O4/SBA-15 and Fe3O4/graphene. The
bars represent 20 nm (a,c) and 2 nm (b,d). The red circles (a,c) indicate small nanoparticles.
rather effective, these approaches suffer from several draw-
backs: 1) the preparation of alkynyl halides; 2) the requirement
for phosphine- or nitrogen-based ligands; 3) the use of toxic
solvents; 4) the process is homogeneous; 5) harsh reaction
conditions are required; 6) environmental impact, all of which
may in some cases increase the cost and limit the scope of the
reaction.
We began our studies by examining the cross-coupling of
diphenyl diselenide (1) and 4-ethynyltoluene (2) as a model re-
action to optimize the experimental conditions with KOtBu as
the base in ethanol at 808C for 12 h in air. Without the aid of
an additional catalyst, only 19% of 3 was observed by GC–MS
analysis even after 24 h (Table 1, entry 1). We found that the
addition of 0.5 mol% Fe3O4/C offered the product in 81% yield
after 12 h (Table 1, entry 2). Decreasing the basicity resulted in
an increase in the recovery of the starting materials (Table 1,
entries 3–7) under identical conditions. It was also found that
lowering the amount of base reduced the yield (71%; Table 1,
entry 8). Surprisingly, the catalysts prepared with different sup-
ports such as SBA-15 and graphene afforded the correspond-
ing cross-coupled products in yields of 61 and 70%, respec-
tively. The mesoporous silica support SBA-15 may not be
stable enough to completely stabilize the Fe3O4 NPs, especially
In addition, most of the reported synthetic techniques use
either DMSO or DMF as solvent and an oxidant to get higher
yields. To overcome the aforementioned drawbacks, new and
improved catalysts for this reaction are still being sought. In
designing such catalysts, special consideration should be given
to the cost and atom economy of the particular catalytic pro-
cesses. Additionally, the choice of solvent and catalyst should
be made with the consideration of environmental impact in
mind.
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yields (ꢀ70–71%) for the synthesis of alkynyl sele-
nides through activation of the CÀH and SeÀSe
bonds by a cross-coupling process based on their
small particle sizes and high surface areas and the
robust framework of the support. Particularly, in
terms of the efficiency relative to the price of the
support, the Fe3O4/C catalyst among the various
carbon-supported catalysts would be one of the best
(commercial price: single layer graphene=360$ per
0.5 g, activated charcoal=107$ per 1000 g). Accord-
ing to our knowledge, this is the first report in which
alkynyl selenides are synthesized by using ethanol as
the solvent in the absence of copper, ligands, and
additives with a heterogeneous catalyst loading of
0.5 mol% of Fe3O4 NPs under environmentally
benign conditions.
Table 1. Optimization of the reaction conditions.[a]
Entry
Base
Catalyst
Yield [%][b]
1
2
3
4
5
6
7
8
9
10
KOtBu
KOtBu
K2CO3
KOH
K3PO4
Na2CO3
Cs2CO3
KOtBu
KOtBu
KOtBu
–
19[b]
81 (78)[d]
59
73
63
2
64
71[e]
61[f]
70[g]
Fe3O4/C
Fe3O4/C
Fe3O4/C
Fe3O4/C
Fe3O4/C
Fe3O4/C
Fe3O4/C
Fe3O4/SBA 15
Fe3O4/graphene
On the basis of the optimized reaction conditions,
we then studied the scope of this novel system for
a variety of substrates. As shown in Table 2, a wide
range of aryl alkynes bearing electron-donating and
electron-withdrawing groups were smoothly coupled
with diphenyl diselenide to give the corresponding
alkynyl selenides in good to excellent yields (Table 2,
entries 1–6). Aliphatic alkynes (1-ethynylcyclohexene
and 1-hexyne) were also successfully coupled with
diaryl diselenides with 0.5 mol% Fe3O4 NPs/C
(Table 2, entries 7 and 8). Similarly, diaryl diselenides
with methoxy and trifluoromethyl groups were toler-
ated by the Fe3O4 NPs catalyst (Table 2, entries 9 and
10).
[a] Reaction conditions: 1 (1 mmol), 2 (2 mmol), base (2 mmol), catalyst (0.5 mol%
with respect to 1). [b] Determined by GC–MS. [c] In the absence of a catalyst, 24 h.
[d] Yield of isolated product. [e] Reaction with base (1 equiv.). [f] 0.5 mol% Fe3O4/SBA-
15 catalyst. [g] 0.5 mol% Fe3O4/graphene catalyst, 808C, 12 h.
Table 2. Evaluation of substrate scope.
Entry
1
Alkyne
Product
Yield[a] [%]
91 (89)[b]
2
3
4
5
6
7
8
76
The catalyst could be recycled efficiently five times
without any significant loss of catalytic activity, as
clearly shown in Figure 4; this confirmed the high
stability and robustness of the heterogeneous cata-
lytic system. These finding are very important in
terms of expanding organic processes for compli-
ance with the principles of green chemistry and sus-
tainability.
79
86
73
68
Magnetite nanoparticles on different solid sup-
ports (e.g., activated charcoal, graphene, and SBA-
15) were synthesized by using an economically feasi-
ble solid-state grinding approach followed by ther-
mal treatment. The Fe3O4/C catalyst possesses re-
markable catalytic efficiency for the synthesis of al-
kynyl selenides through activation of CÀH and SeÀSe
bonds by a cross-coupling process. The porous-char-
coal-based Fe3O4 catalyst was reused more than five
times without prominent Fe leaching, which proved
the high stability of the catalyst. The yields of the
target products with challenging substituents were
higher than those obtained with traditional copper
catalysts, which highlights the importance of nano-
catalysts.
67 (61)[b]
81
9
100 (96)[b]
10
54
[a] Determined by GC–MS. [b] Yield of isolated product, 12 h.
under basic reaction conditions with high temperatures. On
the other hand, carbon supports such as charcoal and gra-
phene can be quite stable, even under strongly basic reactions.
In Table 1, both Fe3O4/C and Fe3O4/graphene showed high
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charcoal (0.5 g) in a mortar was physically ground until the color of
the powder was homogeneously black. The mixture was trans-
ferred into a polypropylene bottle and aged at 508C in a tumbling
oven for 24 h. After that, the product was cooled under an ambi-
ent atmosphere and transferred to an alumina boat in a tube-type
furnace. Finally, the Fe-incorporated charcoal powder was slowly
heated at a ramping rate of 2.78CminÀ1 up to 3508C under a nitro-
gen flow of 200 mLminÀ1. The sample was held at 3508C for 4 h
under a continuous nitrogen flow. For the preparation of the
Fe3O4/SBA-15 and Fe3O4/graphene catalysts, the procedures were
identical to that used for the synthesis of Fe3O4/C, except for the
use of 0.5 g of SBA-15 and single-layer graphene as supports, re-
spectively.
Typical procedure for the cross-coupling of alkynes and di-
phenyl diselenide
Diphenyl diselenide (100 mg, 0.32 mmol), phenyl acetylene (65 mg,
0.64 mmol), Fe3O4/C (3.7 mg, 0.5% with respect to diphenyl disele-
nide), base (72 mg, 0.64 mmol), and ethanol (2 mL) were added
into a 10 mL aluminum-capped vial, and the mixture was stirred in
a preheated oil bath maintained at 808C for 12 h. Then, the Fe3O4
NPS were filtered through a Celite bed, and the product was ex-
tracted into diethyl ether. The organic solvent was evaporated
under reduced pressure. The residue was purified by column chro-
matography (silica gel, hexane) to afford the pure cross-coupled
product. The cross-coupling reactions of other substrates were per-
formed in a similar way.
Figure 4. Recyclability of Fe3O4/C for the cross-coupling of diphenyl disele-
nide with 4-ethynyltoluene.
Experimental Section
Materials and methods
Iron nitrate nonahydrate [Fe(NO3)3·9H2O, ACS reagent, >98%], ac-
tivated charcoal (ꢀ100 mesh particle size, powder), Pluronic P123
(average Mn ꢀ5800), and tetraethoxysilane (TEOS, 98%) were pur-
chased from Sigma–Aldrich. A single-layer graphene powder was
obtained from ACS Material (USA). The chemicals were used as re-
1
ceived without further purification. H NMR spectra were recorded
Acknowledgements
with an Agilent 300 MHz spectrometer in the appropriate deuterat-
ed solvents. The chemical shift values were recorded as parts per
million [ppm] relative to tetramethylsilane as an internal standard
unless otherwise indicated. GC–MS spectra were recorded with
a Shimadzu GC-MS spectrometer. The nature of the magnetite
nanoparticles was determined by using a powder X-ray diffractom-
eter (Rigaku D/MAX-RB 12kW). The morphology of the catalysts
was measured by using a field-emission transmission electron mi-
croscope (Tecnai TF30 ST operated at 300 kV, KAIST). The surface
areas for the catalysts were measured (samples were degassed in
a vacuum at 3008C for 4 h) by the BET method with a Tristar II3020
at À1968C.
This research was supported by the Basic Science Research Pro-
gram through the National Research Foundation of Korea (NRF)
funded by the Ministry of Science, ICT & Future Planning (NRF-
2015R1D1A1A02060684 and NRF-2013R1A1A2012960).
Keywords: alkynes · CÀH activation · mechanochemistry ·
nanocatalysts · supported catalysts
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Received: March 9, 2016
Revised: April 12, 2016
Published online on && &&, 0000
&
ChemCatChem 2016, 8, 1 – 7
www.chemcatchem.org
6
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÝÝ These are not the final page numbers!

COMMUNICATIONS
B. Mohan, J. C. Park,* K. H. Park*
&& – &&
Mechanochemical Synthesis of Active
Magnetite Nanoparticles Supported
on Charcoal for Facile Synthesis of
Alkynyl Selenides by CÀH Activation
Alkynes of fun: Fe3O4 nanoparticles
separately supported on charcoal, gra-
phene, and SBA-15 are prepared by
solid-state grinding and subsequent
thermal treatment. The Fe3O4 nanoparti-
cles supported on activated charcoal ex-
hibit high catalytic activity and furnish
good yields of alkynyl selenide products
in the cross-coupling reactions of di-
phenyl diselenide with alkynes through
CÀH and SeÀSe bond activation under
ecofriendly conditions.
ChemCatChem 2016, 8, 1 – 7
www.chemcatchem.org
7
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
&
These are not the final page numbers! ÞÞ