Cellulose nanocrystals as non-innocent supports for the synthesis of ruthenium nanoparticles and their application to arene hydrogenation

Article abstract of DOI:10.1039/c5ra08675b

Ru nanoparticles were synthesized from RuCl₃ under mild H₂ pressure within a suspension of cellulose nanocrystals. X-ray photoelectron spectroscopy and transmission electron microscopy revealed that the small Ru(0) nanoparticles (3.3 ± 1 nm) were deposited onto their cellulosic support. This hybrid proved to be a highly efficient arene hydrogenation catalyst operational at 4 bars and room temperature.

Full text of DOI:10.1039/c5ra08675b

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DOI: 10.1039/C5RA08675B
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Cellulose nanocrystals as non-innocent support to the synthesis of
ruthenium nanoparticles and their application to arene
hydrogenation
Received 00th January 20xx,
Accepted 00th January 20xx
Madhu Kaushik, Hava Meira Friedman, Mary Bateman and Audrey Moores*
DOI: 10.1039/x0xx00000x
www.rsc.org/
Ru nanoparticles were synthesized from RuCl3 under mild H2 innocent supports for metal NPs, as they act as reducers and
pressure within a suspension of cellulose nanocrystals. X-ray control metal seeding. Additionally, they were recently shown to
photoelectron spectroscopy and transmission electron microscopy act as chiral inducers in the enantionselective Pd-catalyzed
revealed that the small Ru(0) nanoparticles (3.3 ± 1 nm) were hydrogenation reaction of ketones.6 With these ideas in mind, we
deposited onto their cellulosic support. This hybrid proved to be a envisaged to apply CNCs for the design of catalysts towards the
highliy efficient arene hydrogenation catalyst operational at 4 bars challenging arene hydrogenation reaction.29 Arene hydrogenation is
30
and room temperature.
of prime industrial importance.
For instance, benzene
hydrogenation to dipic acid is an intermediate step in the
The development of more sustainable synthetic methods to access production of nylon. Lately, the increased regulation31, 32 on the
nanoparticles is an active research field, stimulated by both the aromatic content of fossil fuels has also triggered interest in more
interest in the discovery of novel and functional nanomaterials and efficient catalytic hydrogenation of aromatics. Conventionally,
the ever growing impact of mankind on its environment.1-4 In this arene hydrogenations are carried out at high temperatures
34
context, biomass derived nanomaterials constitute an opportunity (~120oC) and high H2 pressures (~100 bars).33,
Supported
to reduce nanosynthesis footprint, but also to discover unexpected nanoparticles of Rh(0), Ir(0), Ru(0) and Pt(0) have opened avenues
6
properties and enhanced applications.5, Cellulose Nanocrystals to achieve heterogeneous arene hydrogenations under milder
(CNCs) are easily obtained by strong acid hydrolysis of cellulose conditions.30, 35-39 The more prohibitive price of Rh, Ir and Pt has
from plant or bacterial origin.7-9 An industrial process provide made Ru NPs a very appealing candidate for this reaction. Recently,
access of this material at the ton scale from wood pulp. This ionic liquid stabilised Ru NPs have demonstrated their ability to
10
material is renewable, biodegradable and non-toxic. CNCs from hydrogenate arenes under conditions as mild as 4 bars of H2
37, 40
wood pulp, used in this study, present themselves as high aspect pressure and 75°C.
Zahmakiran et al. and Favier et al. have
ratio whiskers with well-defined size and morphology – 5 nm in achieved these hydrogenations at room temperatures and 3 bars H2
width from 150 to 250 nm in length. They possess high specific pressure, where they use Ru nanoclusters stabilised by nanozeolite
surface area,11 high crystalline order and chirality, superior framework and 4-(3-phenylpropyl)pyridine respectively.41, 42 Beyond
mechanical strength, and controllable surface chemistry.7-9 CNCs the study of the catalytic properties of Ru NPs, novel and
have thus been applied to a variety of fields, including the sustainable synthetic methods to access them have also been an
production of iridescent and birefringent films,7 chiral templating of active research field. To replace ruthenium chloride (RuCl3),41, 43-45
13
46-48
silica12 and carbon
materials, reinforcing fillers in plastics and bis(methylallyl)(1,5-cyclooctadiene) ruthenium(II)
and Ru(1,5-
polymers,7,
flocculants,18 aerogels,
hydrogels,20 and cyclooctadiene)(cyclooctatriene) 45 have been used as precursors, as
14 15-17
19
supercapacitors. 21As CNCs form stable colloidal suspensions in they do not lead to the generation of salt by-products upon
49
water and feature a high specific surface area, they are attractive reduction, and also they can be reduced under mild H2 pressures.
supports for various catalytically active nanoparticles (NPs)22 They are however expensive, require synthetic skills to prepare and
including Pd,23-26 Au,27 and Ag.28 Importantly, CNCs are non- careful handling. RuO2 was also used as a precursor compatible with
37, 50
H as a reductant.
On the other end, typical RuCl3 reduction
relies on the use of NaBH4 to afford the desired nanomaterial.41, 43
NaBH4 is a hazardous substance implying regulated handling and
the boron species generated during this reaction may affect the Ru
catalytic surface.51 Recently our group showed that RuCl3 could be
Centre for Green Chemistry and Catalysis, Department of Chemistry, McGill
University, 801 Sherbrooke St West, Montreal, QC H3A 0B8, Canada.
E-mail: audrey.moores@mcgill.ca; Fax: +1 (514) 398 3797; Tel: +1 (514) 398 4654
† Footnotes relating to the title and/or authors should appear here.
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
effectively reduced and supported by Fe NPs to afford
a
magnetically recoverable transfer hydrogenation catalysts.52
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Interestingly, very few examples exist where RuCl3 is effectively stirred at room temperature for over 72 hours, without the use of
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reduced by mild H2 pressure. For instance, when cyclodextrins are any external reducing agent, the colour of tDhOeI:su10s.p10e3n9s/ioCn5RcAh0a8n6g7e5Bd
used as stabilizers, this reactivity is enabled.53, 54 We present herein to light brown. This confirmed that the CNCs have the ability to
a novel approach where CNCs promote the generation of Ru NPs reduce the Ru (III) partially to Ru (II) but no further.
from RuCl3 using mild H2 pressure as the reducing agens and Transmission electron microscopy (TEM) was performed to
effectively support the resulting NPs to afford RuNPs@CNCs characterize the material. The imaging of CNC/metal hybrid
composite. Subsequently, RuNPs@CNCs were shown to act as material is a challenge, requiring conditions where both the organic
powerful arene hydrogenations catalysts under 4 bars H2 pressure, CNCs and the denser metal are seen with good contrast.58, 59 With
at room temperature.
RuNPs@CNCs, good images were acquired. CNCs were observed as
low contrast whiskers, as reported before.7-9, 58 The Ru NPs were
present in conjunction with CNCs, revealing that they were
deposited onto the CNC surface (Figure 1, S4). The Ru NPs, seen as
darker spots onto the less dense CNCs, featured an average size of
3.3 ± 1 nm, a size where Ru is known to be catalytically active
(Figure S5).37 The TEM also concluded that the CNCs did not
aggregate in the catalyst suspension and retain their high surface
area and rod-like form. These results show that the CNCs are
capable of facilitating the reduction of Ru (III) to Ru (0) in presence
of H2, as a mild reducing agent, at 4 bars and room temperature in
water. Additionally this reaction affords a Ru NP-hybrid composite
of CNC useful to sustain the catalytically active Ru under a reactive
environment.
u
.
R
l 3H
C 3 2O
ar r
H2 4b
t 24h
, ,
,
u
s
s
N
C C
R NP
@
s
u
s
N
C C
R NP
Scheme 1: Synthesis of RuNPs@CNCs
The synthesis of RuNPs@CNCs proceeded very easily by the
addition of RuCl3 to 20 ml 0.5% CNC (w/w) suspension in water. The
resulting mixture, dark brown in colour, was subjected to 4 bars H2
at room temperature for 24 hours (Scheme 1).
u
s
s
N
C C
R NP
@
ar
r
,
a er
W t
4 b H2 t 24h
,
R
R
Scheme 2: Arene hydrogenation at 4 bars H2 pressure, rt, 24h, in
water, using RuNPs@CNCs as catalyst
Table 1: Optimisation of reaction conditions for toluene
hydrogenation with RuNPs@CNCs (3mol% in Ru)
RuNPs@CNCs, was thus tested for the catalytic hydrogenation of
arenes (Scheme 2, Table 1). At first, we started with hydrogenation
conditions used by Schwab et al at 20 bars H2 pressure and 100oC.40
After 2h, 100% conversion of toluene to methylcyclohexane was
achieved (entry 1). The reaction was carried out in the water
suspension of the catalyst, with no addition of any other solvent,
allowing biphasic extraction for workup. In an attempt for using
milder conditions, the same reaction was carried out at room
temperature, instead of 100oC and only afforded a mere 16%
conversion to methylcyclohexane (entry 2). At room temperature,
20 bars of H2 pressure, the time of reaction was increased from 2
hours to 24 hours. After reaction, the products could be easily
extracted out of the catalyst aqueous suspension. Aliquots of the
reaction mixture were taken out at times 2h, 4h and 8h and
analysed by GC-MS. Conversions ramped up to 91% at 8 hours and
Fig. 1: TEM of unstained sample of RuNPs@CNCs. The inset shows
the EDS confirming the presence of Ru.
In 24 hours, the complete reduction to Ru (0) was confirmed by
both the black colour of the suspension and the XPS 3p3/2 peak at
461.27 eV (Figure S1 and S3). This suspension has a Ru content of
63 ppm. If stopped after 2 hours, the reduction was not complete
and a light brown coloured solution was obtained, corresponding to
Ru(II) species55-57 (Figure S1). For comparison, this experiment was
performed using NaBH4 instead of H2 as reducer, which also
resulted in the reduction of Ru (III) to Ru (0) in 24 hours. The
suspension colour was monitored over time and the following
colours were observed in sequence: dark brown, light brown, light
green and finally black, corresponding respectively to Ru (III), Ru (II),
55-57
Ru (I) and Ru (0) (Figure S1).
When the reaction mixture was
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24h afforded 100% conversions (entries 2-5). Next, H2 pressure was
reduced, at 24h and room temperature, to 10 bars, 4 bars and 2
bars, giving conversions of 100%, 100% and 11% respectively
(entries 6-8). Therefore, the mildest reaction conditions providing
complete conversion are 4 bars H2, 24 h at room temperature in
water. These reaction conditions are milder than the ones usually
Acknowledgement
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We thank the Natural Science and EngineerDinOgI:R1e0s.1e0a3r9c/hC5CRoAu0n8c6i7l 5oBf
Canada (NSERC) Discovery Grant program, the Canada Foundation
for Innovation (CFI), the Canada Research Chairs (CRC), the Centre
for Green Chemistry and Catalysis (CGCC), NSERC-Collaborative
Research and Training Experience (CREATE) in Green Chemistry and
McGill University for their financial support. We thank
FPInnovations for providing the CNC starting material. We are
grateful to Mitra Masnadi for her help with XPS and Hojatollah Vali
and Kelly Sears for useful conversations on TEM analysis.
reported for the arene hydrogenations including ones based on Ru
47
NPs stabilised by ionic liquids.40,
Hence, CNCs are a powerful
catalyst support for Ru NPs to achieve both easy synthesis and
reactivity
Notes and references
1. J. A. Dahl, B. L. Maddux and J. E. Hutchison, Chem. Rev., 2007,
107, 2228-2269.
2. C. J. Murphy, J. Mater. Chem., 2008, 18, 2173-2176.
3. M. J. Eckelman, J. B. Zimmerman and P. T. Anastas, J. Ind. Ecol.,
2008, 12, 316-328.
Table 2: Arene hydrogenations of different substrates using
RuNPs@CNCs
4. J. M. Campelo, D. Luna, R. Luque, J. M. Marinas and A. A.
Romero, ChemSusChem, 2009, 2, 18-45.
5. S. Iravani, Green Chem., 2011, 13, 2638-2650.
6. M. Kaushik, K. Basu, C. Benoit, C. C. M., H. Vali and A. Moores, J.
Am. Chem. Soc., 2015, 137, 6124–6127.
7. D. Klemm, F. Kramer, S. Moritz, T. Lindström, M. Ankerfors, D.
Gray and A. Dorris, Angew. Chem. Int. Ed., 2011, 50, 5438-
5466.
8. S. J. Eichhorn, A. Dufresne, M. Aranguren, N. E. Marcovich, J. R.
Capadona, S. J. Rowan, C. Weder, W. Thielemans, M.
Roman, S. Renneckar, W. Gindl, S. Veigel, J. Keckes, H.
Yano, K. Abe, M. Nogi, A. N. Nakagaito, A. Mangalam, J.
Simonsen, A. S. Benight, A. Bismarck, L. A. Berglund and T.
Peijs, J. Mater. Sci., 2009, 45, 1-33.
In order to check the scope of the reaction, other aromatic
substrates with varied substitutions were also hydrogenated at the
optimised conditions (Table 2). Styrene (2) hydrogenation provided
a 96% yield for completely hydrogenated product, ethylcyclohexane
and 4% yield for partially hydrogenated product, ethylbenzene.
Acetophenone (3) gave 76% of ethylcyclohexane, and the rest were
a mixture of partially hydrogenated product (see ESI). Excellent
results for a heterocyclic aromatic (4) were also observed, giving
90% yield for the completely hydrogenated product. After reaction,
potential ruthenium leaching in the product was measured to be
negligible (0.6 ppb) by inductively coupled plasma
– mass
spectroscopy (ICP-MS). The catalyst was checked for recyclability,
and it was recyclable via biphasic separation for six cycles. After
that the conversion rates dropped significantly (Figure S2). In
addition, as a control experiment, when using just RuCl3.3H2O for
the reaction, no conversion was observed. To determine whether
the catalysis was truly heterogeneous, a poisoning experiment
using CS2 was also performed. The addition of 0.5 equivalents of CS2
to the reaction mixture made the catalyst totally ineffective under
the reaction conditions used.
9. Y. Habibi, L. A. Lucia and O. J. Rojas, Chem. Rev., 2010, 110, 3479-
3500.
10. T. Kovacs, V. Naish, B. O'Connor, C. Blaise, F. Gagné, L. Hall, V.
Trudeau and P. Martel, Nanotoxicology, 2010, 4, 255-270.
11. P. Lu and Y.-L. Hsieh, Carbohydr. Polym., 2010, 82, 329-336.
12. K. E. Shopsowitz, H. Qi, W. Y. Hamad and M. J. MacLachlan,
Nature, 2010, 468, 422-425.
13. K. E. Shopsowitz, W. Y. Hamad and M. J. MacLachlan, Angew.
Chem. Int. Ed., 2011, 50, 10991-10995.
14. K. M. Z. Hossain, R. M. Felfel, C. D. Rudd, W. Thielemans and I.
Ahmed, React. Funct. Polym., 2014, 85, 193-200.
15. K. M. Z. Hossain, I. Ahmed, A. J. Parsons, C. A. Scotchford, G. S.
Walker, W. Thielemans and C. D. Rudd, J. Mater. Chem.,
2012, 47, 2675-2686.
16. X. Cao, Y. Habibi and L. A. Lucia, J. Mater. Chem., 2009, 19,
7137-7145.
17. M. A. Hubbe, O. J. Rojas, L. A. Lucia and M. Sain, BioResources,
2008, 3, 929-980.
18. K. H. M. Kan, J. Li, K. Wijesekera and E. D. Cranston,
Biomacromol., 2013, 14, 3130-3139.
Conclusions
These results conclusively show that the role of CNCs as a non-
innocent support for catalytically active NPs. In the synthesis of Ru
NPs, the CNCs and H2 gas synergistically achieve the reduction of Ru
(III) to Ru (0) at just 4 bars and room temperature. Furthermore, the
catalyst, RuNPs@CNCs was successfully applied to arene
hydrogenations under mild conditions of
4 bars H2, room
temperature in water. The product is easily extracted in a biphasic
system, and the catalysts can be recycled up to 6 times with no loss
of activity. These reaction conditions are competitive with the best
results in the field.
19. X. Yang and E. D. Cranston, Chem. Mater., 2014, 26, 6016-6025.
20. J. Yang, C.-R. Han, J.-F. Duan, M.-G. Ma, X.-M. Zhang, F. Xu, R.-C.
Sun and X.-M. Xie, J. Mater. Chem., 2012, 22, 22467-
22480.
21. S. Y. Liew, D. A. Walsh and W. Thielemans, RSC Adv., 2013, 3,
9158-9162.
This journal is © The Royal Society of Chemistry 20xx
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Please do not adjust margins
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Page 4 of 4
COMMUNICATION
Journal Name
22. E. Lam, K. B. Male, J. H. Chong, A. C. W. Leung and J. H. T. Luong, 49. J. D. Scholten, M. H. G. Prechtl and J. Dupont, in Handbook of
View Article Online
Trends Biotechnol., 2012, 30, 283-290.
23. C. M. Cirtiu, A. F. Dunlop-Brière and A. Moores, Green Chem.,
2011, 13, 288-291.
24. X. Wu, C. Lu, W. Zhang, G. Yuan, R. Xiong and X. Zhang, J. Mater.
Chem. A, 2013, 1, 8645-8652.
Green Chemistry, Green Processes,DGOrIe:e1n0.1N0a3n9o/Cs5ciReAn0c8e6,75B
eds. A. Perosa and M. Selva, Wiley-VCH, Weinheim, 1
edn., September 2013, vol. 8, ch. Formation of
nanoparticles assisted by ionic liquids, pp. 1-31.
50. L. M. Rossi, J. Dupont, G. Machado, P. F. P. Fichtner, C. Radtke, I.
J. R. Baumvol and S. R. Teixeira, J. Braz. Chem. Soc., 2004,
15, 904-910.
25. P. Zhou, H. Wang, J. Yang, J. Tang, D. Sun and W. Tang, Ind. Eng.
Chem. Res., 2012, 51, 5743-5748.
26. M. Rezayat, R. K. Blundell, J. E. Camp, D. A. Walsh and W.
Thielemans, ACS Sustainable Chem. Eng., 2014, 2, 1241-
1250.
27. E. Lam, S. Hrapovic, E. Majid, J. H. Chong and J. H. T. Luong,
Nanoscale, 2012, 4, 997-1002.
28. R. Xiong, C. Lu, W. Zhang, Z. Zhou and X. Zhang, Carbohydr.
Polym., 2013, 95, 214-219.
51. X. Yan, H. Liu and K. Y. Liew, J. Mater. Chem., 2001, 11, 3387-
3391.
52. R. Hudson, V. Chazelle, M. Bateman, R. Roy, C. Li and A. Moores,
ACS Sustainable Chem. Eng., 2015, 3, 814-820.
53. N. T. T. Chau, S. Handjani, J.-P. Guegan, M. Guerrero, E.
Monflier, K. Philippot, A. Denicourt-Nowicki and A.
Roucoux, ChemCatChem, 2013, 5, 1497-1503.
29. R. C. Larock, Comprehensive organic transformations, A Guide to 54. A. Denicourt-Nowicki, A. Ponchel, E. Monflier and A. Roucoux,
Functional Group Preparations, Wiley-VCH, 2010.
30. J. A. Widegren and R. G. Finke, J. Mol. Catal. A: Chem., 2003,
191, 187-207.
Dalton Trans., 2007, 5714-5719.
55. E. A. Seddon and K. R. Seddon, The Chemistry of Ruthenium,
Elsevier, Amsterdam, 2013.
31. G. Karavalakis, T. D. Durbin, M. Shrivastava, Z. Zheng, M. Villela
and H. Jung, Fuel, 2012, 93, 549-558.
32. M. Fang and R. A. Sanchez-Delgado, J. Catal., 2014, 311, 357-
368.
33. R. L. Augustine, Heterogeneous catalysis for the synthetic
chemist, CRC Press, New York, 1995.
34. J. G. Donkervoort and E. G. M. Kuijpers, in Fine Chemicals
through Heterogeneous Catalysis, eds. R. A. Sheldon and
H. v. Bekkum, Wiley-VCH Verlag GmbH, Weinheim, 2001,
ch. Catalytic hydrogenation and dehydrogenation, pp.
351-470.
56. A. Bossi, F. Garbassi, A. Orlandi, G. Petrini and L. Zanderighi, eds.
B. Delmon, P. Grange, P. Jacobs and G. Poncelet, Elsevier,
1979, vol. 3, ch. Preparation Aspects of Ru-Supported
Catalysts and their Influence on the Final Products, pp.
405-416.
57. G. Fownes, A manual of elementary chemistry, theoretical and
practical, Blanchard and Lea, Philadelphia, 1862.
58. M. Kaushik, W. C. Chen, T. G. van de Ven and A. Moores, Nordic
Pulp and Paper Res. J. , 2014, 29, 77-81.
59. M. Kaushik, J.-L. Putaux, C. Fraschini, G. Chauve and A. Moores,
in The Transmission Electron Microscope, Intech, 2015, ch.
Transmission Electron Microscopy for the
35. S.-C. Qi, X.-Y. Wei, Z.-M. Zong and Y.-K. Wang, RSC Adv., 2013, 3,
14219-14232.
36. A. Gual, C. Godard, S. Castillón and C. Claver, Dalton Trans.,
2010, 39, 11499-11512.
Characterization of Cellulose Nanocrystals, p. Accepted
May 25 2015.
37. L. M. Rossi and G. Machado, J. Mol. Catal. A: Chem., 2009, 298,
69-73.
38. S. A. Stratton, K. L. Luska and A. Moores, Catal. Today, 2012,
183, 96-100.
39. B. Leger, A. Denicourt-Nowicki, A. Roucoux and H. Olivier-
Bourbigou, Adv. Synth. Catal., 2008, 350, 153-159.
40. F. Schwab, M. Lucas and P. Claus, Angew. Chem. Int. Ed., 2011,
50, 10453-10456.
41. M. Zahmakıran, Y. Tonbul and S. Ozkar, J. Am. Chem. Soc., 2010,
132, 6541-6549.
42. I. Favier, P. Lavedan, S. Massou, E. Teuma, K. Philippot, B.
Chaudret and M. Gómez, Top. Catal., 2013, 56, 1253-
1261.
43. M. Fang, N. Machalaba and R. A. Sanchez-Delgado, Dalton
Trans., 2011, 40, 10621-10632.
44. S. Niembro, S. Donnici, A. Shafir, A. Vallribera, M. L. Buil, M. A.
Esteruelas and C. Larramona, New J. Chem., 2013, 37,
278-282.
45. J. Llop Castelbou, E. Breso-Femenia, P. Blondeau, B. Chaudret, S.
Castillon, C. Claver and C. Godard, ChemCatChem, 2014,
6, 3160-3168.
46. M. H. Prechtl, M. Scariot, J. D. Scholten, G. Machado, S. R.
Teixeira and J. Dupont, Inorg. Chem., 2008, 47, 8995-
9001.
47. J. Julis, M. Hölscher and W. Leitner, Green Chem., 2010, 12,
1634-1639.
48. K. L. Luska and A. Moores, Green Chem., 2012, 14, 1736-1742.
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