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Applied Catalysis A: General 338 (2008) 52–57

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Recoverable rhodium nanoparticles: Synthesis, characterization

and catalytic performance in hydrogenation reactions
Marcos J. Jacinto a,b, Pedro K. Kiyohara c, Sueli H. Masunaga c,
Renato F. Jardim c, Liane M. Rossi a,b,*
a
Instituto de Quı́mica, Universidade de São Paulo, 05508-000 São Paulo, SP, Brazil
b
CEPEMA-USP, Cubatão, SP, Brazil
c
Instituto de Fı́sica, Universidade de São Paulo, CP 66318, 05315-970 São Paulo, SP, Brazil
Received 18 October 2007; received in revised form 14 December 2007; accepted 17 December 2007
Available online 27 December 2007

Abstract
We here report the first magnetically recoverable Rh(0) nanoparticle-supported catalyst with extraordinary recovery and recycling properties.
Magnetic separation has been suggested as a very promising technique to improve recovery of metal-based catalysts in liquid-phase batch
reactions. The separation method is significantly simple, as it does not require filtration, decantation, centrifugation, or any other separation
technique thereby, overcoming traditional time- and solvent-consuming procedures. Our new magnetically separable catalytic system, comprised
of Rh nanoparticles immobilized on silica-coated magnetite nanoparticles, is highly active and could be reused for up to 20 times for hydrogenation
of cyclohexene (180,000 mol/molRh) and benzene (11,550 mol/molRh) under mild conditions.
# 2007 Elsevier B.V. All rights reserved.
Keywords: Rhodium nanoparticle; Catalyst recovery; Benzene hydrogenation

1. Introduction include the use of biphasic aqueous/organic systems [5–7], ionic-

liquid biphasic conditions [8–11] and MNPs supported on large
The development of new strategies for recovery and recycling surface area solids [1,12–14]. From a practical point of view,
of catalysts to enhance their lifetime and minimize the catalysts that are not soluble in the same phase as organic
consumption of auxiliary substances used in achieving separa- reactants have the inherent advantage of easy separation.
tions can result in significant economical and environmental However, supported catalysts may also exhibit severe problems
benefits. Ongoing research activities in this area include the use with respect to catalyst recovery in liquid-phase batch reactions.
of metal nanoparticles (MNPs) in catalysis [1–3]. It is widely In this scenario, immobilization of catalysts on magnetically
accepted that MNPs are very active catalysts because of their separable solid supports appears as an attractive way to give
large surface area and a great ratio of atoms remaining at the better handling properties to homogeneous [15–20] and MNP
surface, and so available to the chemical transformation of catalysts [21,22]. Solid supports containing magnetic nanopar-
substrates. However, the MNPs must be stabilized by protective ticles can be easily separated from the product of interest due to
agents to prevent agglomeration to the thermodynamically the magnetic interaction between the magnetic nanoparticles and
favored bulk metal. Although it results in very active soluble an external applied magnetic field. Furthermore, magnetic
MNP catalysts, the separation of the catalyst from the reaction separation constitutes an alternative approach to traditional time-
products can be problematic [4]. Attempts to improve separation and solvent-consuming steps during the purification process
since it is fast, it can be easily scaled-up, and it does not make use
of other chemical reagents and solvents that present considerable
environmental hazards.
* Corresponding author at: Instituto de Quı́mica, Universidade de São Paulo,
Here we report a general methodology for the preparation of a
05508-000 São Paulo, SP, Brazil. Tel.: +55 11 3091 2181;
fax: +55 11 3815 5579. magnetically recoverable rhodium metal nanocatalyst. The
E-mail address: lrossi@iq.usp.br (L.M. Rossi). approach is based on the uptake of Rh3+ by amino-functionalized

0926-860X/$ – see front matter # 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2007.12.018
 M.J. Jacinto et al. / Applied Catalysis A: General 338 (2008) 52–57 53

silica-coated magnetic nanoparticles followed by metal reduc- hydrogenation apparatus. The reaction was conducted under
tion under controlled H2 conditions, leading to the MNPs magnetic stirring (700 rpm) at the desired pressure and
formation. We have presented the first example of a Rh(0) temperature. The temperature was maintained by a hot-stirring
magnetically separable catalyst with enhanced recovery and plate connected to a digital controller (ETS-D4 IKA). The fall
recycling properties in hydrogenation reactions. in the hydrogen pressure in the hydrogen tank was monitored
with a pressure transducer interfaced through a Novus Field
2. Experimental Logger converter to a computer. The pressure versus time data
were collected by the FieldChart Novus Software, stored as a
2.1. Synthesis of oleic acid-coated magnetic nanoparticles data file and exported to MicroCal Origin 7.0 for the calculation
of hydrogenation rates. The catalyst was recovered magneti-
Fe3O4 nanoparticles were prepared by the coprecipitation cally by placing a magnet in the reactor wall and the products
method and coated with oleic acid as reported elsewhere [23]. were collected and analyzed by gas chromatography (GC) and
GC–MS. The isolated catalyst could be reused when a new
2.2. Synthesis of the silica-coated magnetic nanoparticles amount of substrate was added.

In a typical experiment, 44.6 g of polyoxyethylene(5) 2.6. Catalyst characterization

isooctylphenyl ether was dispersed in 700 mL of cyclohexane.
Then, 200 mg of Fe3O4 dispersed in cyclohexane was added. The catalyst was analyzed by different techniques,
The mixture was stirred until it became transparent. After this which ensured a complete composition, morphology, and size
step, 9.44 mL of ammonium hydroxide (29% aqueous solution) characterization.
was added to form a reverse microemulsion. Finally, 7.70 mL Transmission electron microscopy (TEM) was performed at
of tetraethylorthosilicate (TEOS) was added. The solution was the Instituto de Fı́sica (IFUSP) on a Philips CM200 microscope
gently stirred for 16 h. The nanocomposite Fe3O4/SiO2 was operating at 200 kV. Samples for TEM observations were
precipitated with methanol and collected by centrifugation at prepared by placing a drop containing the nanoparticles in a
7000 rpm. After being washed with ethanol, the material was coated carbon grid.
dried in vacuum. High-resolution transmission electron microscopy
(HRTEM) and X-ray energy dispersive spectroscopy (EDS)
2.3. Synthesis of the amino-modified silica-coated were performed at the Laboratório Nacional de Luz Sincroton
magnetic nanoparticles (LNLS) using a Jeol-3010 ARP microscope.
Magnetization measurements M (T, H) were performed by
Amino-modified silica particles were prepared as follows: using a superconducting quantum interference device magnet-
900 mL of 3-(aminopropyl)-triethoxysilane (APTES), dis- ometer from Quantum Design. Applied magnetic fields H
solved in 100 mL of dried toluene, was added to 600 mg of between 70 and 70 kOe and temperatures ranging from 5 to
Fe3O4/SiO2. The solution was stirred for 2 h at room 300 K were used in these experiments. In the zero-field cooled
temperature. The amino-functionalized solid (Fe3O4/SiO2– (ZFC) experiments, the sample was first cooled down to 5 K
NH2) was washed with toluene, separated by centrifugation, under zero applied magnetic field, the magnetic field was set,
and dried at 100 8C for 20 h. and the magnetization data were collected upon warming up to
300 K. In the field cooled (FC) process, the data were collected
2.4. Synthesis of the catalyst precursor upon cooling the sample from 300 K down to 5 K under an
applied magnetic field. In the hysteresis loops M(H) measure-
The catalyst precursor was prepared as follows: 50 mg of ments, the sample was ZFC down to a desired temperature and
Fe3O4/SiO2–NH2 were added to 10 mL of an aqueous rhodium the magnetic field sweep ( 70 kOe  H  70 kOe) was
chloride solution (2.1 mg). The mixture was stirred for 2 h at performed. These steps were repeated for several different
25 8C. The solid was then magnetically collected from the measuring temperatures.
solution and washed twice with acetone followed by drying at
100 8C for 3 h. 3. Results and discussion

2.5. Hydrogenation experiments The magnetic nanoparticles cores (Fe3O4 10 nm) were
synthesized by the coprecipitation method and stabilized in
The catalytic reactions were carried out in a modified cyclohexane with oleic acid [23]. Then, the Fe3O4 nanoparticles
Fischer–Porter glass reactor connected to a pressurized were spherically coated with silica by means of a microemul-
hydrogen tank at 20–50 atm. The Fischer–Porter bottle was sion technique, resulting in 60 nm silica spheres (Fig. 1a).
set at a constant pressure for the entire course of the reaction by The silica spheres were functionalized with 3-aminopropyl-
leaving it open to the hydrogen supply. In a typical experiment, triethoxysilane to improve the uptake of Rh3+ ions from RhCl3
catalytic quantities of rhodium (50 mg of magnetic solid) and solution. The metal-loaded solid was then subjected to
the desired quantity of substrate were added to the reactor under reduction in 6 atm and 75 8C of H2, a process that resulted
inert atmosphere. The reactor was evacuated and attached to the in Rh(0) nanoparticles stabilized on the surface of the magnetic
54 M.J. Jacinto et al. / Applied Catalysis A: General 338 (2008) 52–57

Fig. 1. (a) TEM image of silica-coated magnetic particles (inset: enlarged image); (b) HRTEM image of the spent catalyst, (c) EDS analysis of the area shown in
image (b); (d) EDS analysis of the particle shown in box (i); (e) EDS analysis of the particle shown in box (ii).

support. The catalyst contains 1.55 wt% of Rh, as determined

by atomic absorption analysis (ICP-AES). We have also found
that when the support was not previously functionalized with
amino groups only 0.14% of Rh was immobilized.
The catalyst exhibits a morphology comprised of silica
spheres that contains magnetic cores and Rh(0) nanoparticles of
about 3–5 nm decorating the silica shell (Fig. 1b). EDS analysis
revealed the presence of Fe atoms in the core nanoparticles (box
i, Fig. 1b) and Rh atoms in the nanoparticles with more contrast
in the image (box ii, Fig. 1b), respectively, as displayed in
Fig. 1c–e. The HRTEM image shown in Fig. 2 corroborates the
presence of Rh(0) nanoparticles since an interplanar distance of
2.26 Å, corresponding to the (1 1 1) Bragg plane of cubic
Rh(0), was obtained.
The magnetic properties of the catalyst sustained that the
material is comprised of nanoparticles, with blocking
temperature TB 70 K, and negligible magnetic interaction
between them, as inferred from the ZFC and FC curves Fig. 2. HRTEM image of a Rh nanoparticle showing interplanar distances
displayed in Fig. 3a [24]. Indeed, the absence of magnetic indicated by the Fourier transform obtained using Gatan software (inset).
 M.J. Jacinto et al. / Applied Catalysis A: General 338 (2008) 52–57 55

reaction was followed by the consumption of hydrogen in a tank

connected to the main reactor. Curves of hydrogen pressure
versus time were obtained for each experiment. An induction
period without a detectable consumption of hydrogen was
usually observed in the first use of the catalyst (first run), which
is attributed to the in situ nanoparticle formation. When
performing recycling studies we did not observe this induction
period for the second cycle on. At the desired time, the reactor
was cooled to room temperature and depressurized. The
catalyst was recovered magnetically by placing a magnet in the
reactor wall and the liquid contents were analyzed by GC. The
conversion was usually complete after less than 1 h under mild
conditions and gives the corresponding cyclohexane. Similar
experiments performed under the same conditions but with
Fe3O4/SiO2 particles not loaded with metal did not show
consumption of hydrogen even with an extended reaction time
of 24 h.
A series of experiments were performed to verify the
catalyst stability and recyclability. Turnover frequencies
(TOFs) as high as 40,000 and 1100 h 1 were obtained in the
hydrogenation of cyclohexene and benzene at 75 8C and 6 atm
H2 (Fig. 4a and b), respectively. Such values of TOF are
remarkable when compared to those found for Rh nanoparticle-
based catalysts [25,26]. For example, in solventless conditions
(without stabilizing agents) and in ionic-liquid biphasic
conditions, the TOF for hydrogenation of benzene, under
Fig. 3. (a)Temperature dependence of the magnetization (FC and ZFC curves) similar conditions, were 21 and 11 h 1, respectively, and none
under magnetic field (H = 30 Oe) and (b) hysteresis loops at 5 K (*) and 300 K of the recovered Rh nanoparticles could be recycled [25]. In
(*) for the spent catalyst.
aqueous biphasic conditions, Rh–PVP (polyvinylpyrrolidone)
stabilized nanoparticles could be reused at least once,
hysteresis at 300 K (Fig. 3b) further suggests the super- corresponding to a total turnover number (TON) of 3600
paramagnetic behavior of the magnetic nanoparticles at room [26]. High turnovers and reusability were achieved in biphasic
temperature. In spite of the 10 times lower magnetization ionic liquid only under forced conditions (40 bar H2), reaching
when compared with the bare magnetite particles (62 emu/g a total TON of 20,000 in five recycles [27]. We also mention
at T = 300 K and H = 2 kOe) [23], the solid has been readily that Rh nanoparticles supported on nanofibers were reused up to
separated from the liquid media by using a small permanent 10 times (TON of 10,000), although the separation was not
magnet. straightforward as for most solid supports [28]. The new Rh
The catalytic activity of the magnetically separable Rh magnetically separable catalyst could be reused for up to 20
catalyst was investigated in the hydrogenation of cyclohexene successive batches without significant loss in catalytic activity,
and benzene in solventless conditions as shown in Table 1. The which resulted in a total TON of 180,000 and 11,550 for
reactor loaded with the catalyst and the substrate was subjected cyclohexene and benzene hydrogenation, respectively. All
to the desired hydrogen pressure and temperature, and the reaction batches achieved >99% conversion in different time
intervals, which explained the variaton on TOF values observed
Table 1 in the series of experiments. The rates of the first and the last
Hydrogenation of cyclohexenea and benzeneb by the magnetically recoverable batches in cyclohexene hydrogenation were similar (close to
Rh(0) catalyst under different reaction conditions
20,000 h 1), which means that the active metal sites were
Entry Substrate P (atm) T (8C) Time (min)c TOF (h 1)d maintained. Moreover, the catalyst activity did not change
1 Cyclohexene 6 75 15 7600 significantly, but peaks with higher activities were observed for
2 Cyclohexene 6 25 19 5937 batches 2–5, 9, 10, 12 and 13 (Fig. 4a). Similar behavior was
3 Cyclohexene 1 75 40 2835 observed for catalyst recycling in hydrogenation of benzene.
4 Cyclohexene 1 25 43 2638 After each run the catalyst was easily separated magneti-
5 Benzene 6 75 40 825
6 Benzene 6 25 168 196
cally, the product could be removed with a syringe, and new
a
portions of the substrate were added to the reactor (Fig. 4c). The
Catalyst/substrate molar ratio: 1/1900. time interval for the catalyst separation and product removal
b
Catalyst/substrate molar ratio: 1/550.
c
Time required for conversion >99% measured by GC. (<1 min) was negligible when compared to the time consumed
d
Catalytic turnover frequency: mole of substrate transformed per mole of during the reaction (40 min for benzene 550 turnovers). This
catalyst per hour. is a consequence of the magnetic separation that spares
56 M.J. Jacinto et al. / Applied Catalysis A: General 338 (2008) 52–57

Fig. 4. Catalyst recycling in successive hydrogenation reactions: (a) cyclohexene (10,000 TON each batch), and (b) benzene (550 TON each batch). Data collected at
75 8C and under H2 pressure of 6 atm. (c) Illustration of magnetic separation of the catalyst between each reaction batch.

filtration, decantation, centrifugation, or any other workup Laboratório de Microscopia Eletrônica (Brazil) for HRTEM
procedure. ICP-AES analysis indicated that Rh leaching was images and EDS analysis.
negligible after 20 successive batches (Rh content <0.67 ppm
in the products). Changes in the size distribution of Rh
References
nanoparticles after catalyst reuses were not appreciable and
confirm the high stability of the system, also evidenced by high [1] D. Astruc, F. Lu, J.R. Aranzaes, Angew. Chem. Int. Ed. 44 (2005) 7852–
reusability and low metal leaching. 7872.
[2] A. Roucoux, J. Schulz, H. Patin, Chem. Rev. 102 (2002) 3757–3778.
[3] B.C. Gates, Chem. Rev. 95 (1995) 511–522.
4. Conclusions [4] J.A. Widegren, R.G. Finke, J. Mol. Catal. A: Chem. 191 (2003) 187–207.
[5] A. Roucoux, J. Schulz, H. Patin, Adv. Synth. Catal. 345 (2003) 222–229.
In summary, we have successfully prepared a magnetically [6] M.V. Vasylyev, G. Maayan, Y. Hovav, A. Haimov, R. Neumann, Org. Lett.
recoverable Rh nanocatalyst by a new method. The material is 8 (2006) 5445–5448.
[7] V. Mevellec, A. Roucoux, E. Ramirez, K. Philippot, B. Chaudret, Adv.
comprised of Rh nanoparticles immobilized on silica-coated Synth. Catal. 346 (2004) 72–76.
magnetite supports. The catalyst showed considerably repro- [8] J. Dupont, G.S. Fonseca, A.P. Umpierre, P.F.P. Fichtner, S.R. Teixeira, J.
ducible hydrogenation activity up to 20 cycles for the hydro- Am. Chem. Soc. 124 (2002) 4228–4229.
genation of benzene and cyclohexene, besides product separation [9] L.M. Rossi, G. Machado, P.F.P. Fichtner, S.R. Teixeira, J. Dupont, Catal.
Lett. 92 (2004) 149–153.
was immediate due to the magnetic property of the material.
[10] T.J. Geldbach, D. Zhao, N.C. Castillo, G. Laurenczy, B. Weyershausen,
These features provide a new appealing catalytic process. We P.J. Dyson, J. Am. Chem. Soc. 128 (2006) 9773–9780.
also argue that the method employed here seems to be suitable for [11] C.W. Scheeren, G. Machado, J. Dupont, P.F.P. Fichtner, S.R. Teixeira,
obtaining other transition-metal (Pt, Ru, Ir and Au) nanoparticle- Inorg. Chem. 42 (2003) 4738–4742.
based catalysts with increasing interest in liquid-phase reactions [12] H. Bönnemann, W. Brijoux, in: A. Fürstner (Ed.), Active Metals: Pre-
such as C–C couplings, hydrogenations, and oxidations. paration, Characterization, Applications, VCH, Weinheim, 1996, p. 339.
[13] J.P.M. Niederer, A.B.J. Arnold, W.F. Holderich, B. Spliethof, B. Tesche,
M. Reetz, H. Bonnemann, Top. Catal. 18 (2002) 265–269.
Acknowledgments [14] N. Zheng, G.D. Stucky, J. Am. Chem. Soc. 128 (2006) 14263–14278.
[15] T.-J. Yoon, W. Lee, T.-S. Oh, J.K. Lee, N. J. Chem. 27 (2003)
227–229.
The authors are grateful to the Brazilian agencies FAPESP [16] P.D. Stevens, G. Li, J. Fan, M. Yen, Y. Gao, Chem. Commun. (2005)
and CNPq for financial support and indebted to LNLS- 4435–4437.
 M.J. Jacinto et al. / Applied Catalysis A: General 338 (2008) 52–57 57

[17] P.D. Stevens, G. Li, J. Fan, H.M.R. Gardimalla, M. Yen, Y. Gao, Org. Lett. [24] F.C. Fonseca, G.F. Goya, R.F. Jardim, R. Muccillo, N.L.V. Carreno,
7 (2005) 2085–2087. E. Longo, E.R. Leite, Phys. Rev. B 66 (2002) 104406–104410.
[18] A. Hu, G.T. Yee, W. Lin, J. Am. Chem. Soc. 127 (2005) 12486–12487. [25] G.S. Fonseca, A.P. Umpierre, P.F.P. Fichtner, S.R. Teixeira, J. Dupont,
[19] M. Kotani, T. Koike, K. Yamaguchi, N. Mizuno, Green Chem. 8 (2006) Chem. Eur. J. 9 (2003) 3263–3266.
735–737. [26] J.L. Pellegatta, C. Blandy, V. Collie, R. Choukroun, B. Chaudret, P. Cheng,
[20] Y. Zheng, P.D. Stevens, Y. Gao, J. Org. Chem. 71 (2006) 537–542. K.J. Philippot, Mol. Catal. A: Chem. 178 (2002) 55–58.
[21] L.M. Rossi, F.P. Silva, L.L.R. Vono, P.K. Kiyohara, E.L. Duarte, R. Itri, R. [27] X. Mu, J. Meng, Z.-C. Li, Y. Kou, J. Am. Chem. Soc. 127 (2005)
Landers, G. Machado, Green Chem. 9 (2007) 379–381. 9694–9695.
[22] D.K. Yi, S.S. Lee, J.Y. Ying, Chem. Mater. 18 (2006) 2459–2461. [28] I.S. Park, M.S. Kwon, N. Kim, J.S. Lee, K.Y. Kang, J. Park, Chem.
[23] L.M. Rossi, L.L.R. Vono, F.P. Silva, P.K. Kiyohara, E.L. Duarte, J.R. Commun. (2005) 5667–5669.
Matos, Appl. Catal. A: Gen. 330 (2007) 139–144.