Professional Documents
Culture Documents
pubs.acs.org/JPCC
bS Supporting Information
ABSTRACT: The dumbbell- and ower-like AuFe3O4 heterostructures by thermal decomposition of the ironoleate
complex in the presence of Au nanoparticles (NPs) have been
successfully fabricated using dierent sizes of Au NPs as the
seeds for magnetically recyclable catalysis of p-nitrophenol and
2,4-dinitrophenol reduction. The heterostructures exhibit bifunctional properties with high magnetization and excellent catalytic activity toward nitrophenol reduction. The epitaxial linkages
in dumbbell- and ower-like heterostructures are dierent, leading
to the change in magnetic and catalytic properties of the heterostructured nanocatalysts. The pseudo-rst-order rate constants for
nitrophenol reduction are 0.630.72 min1 and 0.380.46 min1
for dumbbell- and ower-like AuFe3O4 heterostructures, respectively. In addition, the heterostructured nanocatalysts show good
separation ability and reusability which can be repeatedly applied
for nearly complete reduction of nitrophenols for at least six successive cycles. The reaction mechanism for nitrophenol reduction by
AuFe3O4 nanocatalysts is also proposed and conrmed by XPS and FTIR analyses. These unique properties make AuFe3O4
heterostructures an ideal platform to study various heterogeneous catalytic processes which can be potentially applied in a wide variety of
elds in purication, catalysis, sensing devices, and green chemistry.
1. INTRODUCTION
Nobel metal nanostructures have recently received much
attention because of their unique optical, catalytic, and electrochemical properties which make them suitable materials for
potential applications in various elds.1,2 Gold nanoparticles
(Au NPs) have been found to play an important role in several
catalytic processes including low-temperature CO oxidation,3
reductive catalysis of chlorinated or nitrogenated hydrocarbons,46
and organic synthesis.7,8 Due to the high cost and limited supply,
however, the improvement of the catalytic eciency and the
reduction of the used amounts are the top priorities for practical
applications. The deposition of Au NPs onto porous supports
such as TiO2, SiO2, and carbon is regarded as a conventional way
to solve the problem by maximizing the loading of catalysts and
to enhance the catalytic activity by well-tuning the surface functionality.912 However, the entrapment or immobilization of the
nanocatalysts on solid supports normally results in a decrease in
the catalytically active surface area and the reactivity of catalytic
species.13 Recently, the doping of Au NPs into the interior of
spherical AgC composites containing Ag NPs has been
synthesized for reduction of 4-nitrophenol in the presence of
sodium borohydride.12 The catalytic activity of bimetallic composites is highly enhanced over the monometallically doped
carbon spheres. However, these catalysts are usually recycled by
tedious and time-consuming centrifugation/redispersion cycles,
r 2011 American Chemical Society
2. EXPERIMENTAL SECTION
2.1. Chemicals. Iron chloride (FeCl3 3 6H2O, 98%), oleylamine (>70%), oleic acid (90%), 1-octadecene (90%), and
tert-butylamineborane complex (97%) were purchased from
Sigma-Aldrich. Sodium oleate (95%) was purchased from TCI.
Trisodium citrate dehydrate (>99%) was purchased from Ferak.
Sodium borohydride (95%) and ethanol absolute (99.8%) were
purchased from Riedel-de Haen. p-Nitrophenol and 2,4-dinitrophenol were purchased from Fluka. Hydrogen tetrachloroaurate(III) trihydrate (HAuCl4 3 3H2O) was purchased from Alfa
Aesar. Cyclohexane (99.95%) was purchased from TEDIA. nHexane was purchased from J. T. Baker.
2.2. Synthesis of Gold NPs with Different Sizes. The Au
NPs with sizes of 45 nm were prepared by dissolving 40 mg of
HAuCl4 3 3H2O in a mixture containing 4 mL of oleylamine and
4 mL of cyclohexane in air followed by magnetic stirring at 10 C
under a gentle stream of nitrogen gas. An amount of 0.2 mmol
of tert-butylamineborane complex was dissolved in 0.4 mL of
ARTICLE
ARTICLE
Figure 1. TEM images of (a) 5 nm Au NPs, (b) dumbbell-like AuFe3O4 heterostructures, (d) 10 nm Au NPs, and (e) ower-like AuFe3O4
heterostructures. Figures (c) and (f) are HRTEM images of dumbbell- and ower-like AuFe3O4 heterostructures, repsectively.
Figure 2. Histogram analysis of particle sizes of (a) dumbbell-like and (b) ower-like AuFe3O4 heterostructures.
ARTICLE
Figure 3. (a) XRD patterns and (b) magnetic hysteresis loops of dumbbell- and ower-like AuFe3O4 heterostructures.
Figure 4. Time-dependent UVvis spectral changes in (a) p-nitrophenol (4-NP) and (b) 2,4-dinitrophenol (2,4-DNP) catalyzed by AuFe3O4
heterostructures and concentration change in nitrophenol compounds (Ct/C0) in the presence of (c) dumbbell-like and (d) ower-like AuFe3O4
nanocrystals. Insets in Figures (c) and (d) are linear relationship of ln(Ct/C0) as a function of time for 4-NP and 2,4-DNP, respectively.
ARTICLE
Figure 5. Catalytically recyclable reduction of (a) p-nitrophenol and (b) 2,4-nitrophenol by dumbbell-like AuFe3O4 NPs in the presence of NaBH4.
Conversion eciency of (c) p-nitrophenol in six successive cycles of reduction and (d) 2,4-nitrophenol in seven successive cycles of reduction by
AuFe3O4 and citrate-stabilized Au nanocatalysts.
constants for nitrophenol reduction by both dumbbell- and owerlike AuFe3O4 are higher than those previously reported values
obtained from the catalysis of p-nitrophenol by Au-based materials
(Supporting Information, Table S1).48,49 This result clearly indicates
that AuFe3O4 heterostructures are superior nanocatalysts
which can enhance the catalytic eciency and minimize the used
amounts of catalysts for reaction, especially only when trace
amounts of Au catalysts are used (0.380.96 mg Au) for reduction. It is noteworthy that the catalytic eciency of ower-like
AuFe3O4 is lower than that of dumbbell-like structures
(Supporting Information, Figure S5), presumably due to that
the Au surfaces in ower-like structures are mainly occupied
by the Fe3O4 leaves and thus suppress the reaction rate of
nitrophenols. Therefore, the dumbbell-like AuFe3O4 heterostructures are selected as the model nanocatalysts for further
experiments.
The as-prepared AuFe3O4 heterostructures show both
catalytic and magnetic properties which can be easily recycled
by an external magnet after the catalytic reduction. Figure 5 shows
the magnetically recyclable reduction of nitrophenols in the
presence of dumbbell-like AuFe3O4 nanocatalysts. The catalysts can be successfully recycled and reused for at least six
successive cycles of reaction with stable conversion eciency of
around 100%. The hydrodynamic size of AuFe3O4 nanoparticles remains unchanged after several cycles of catalytic reactions
(Supporting Information, Figure S6), indicating the stability of
the dumbbell-like nanoparticles in aqueous solutions. In addition, the citrate-stabilized Au NPs were used as the catalysts to
reduce nitrophenol compounds for comparison. The conversion
eciency of p-nitrophenol and 2,4-dinitrophenol by citratestabilized Au NPs drops dramatically after the second cycle,
which is primarily attributed to the loss of Au NPs after periodic
centrifugation/redispersion cycles. The average particle sizes of
citrate-stabilized Au NPs before and after the centrifugation,
determined by TEM images, are 11.2 ( 0.8 and 11.7 ( 1.8 nm,
respectively, clearly indicating that the decrease in conversion
6595
ARTICLE
Scheme 1. Possible Mechanism for Magnetically Recyclable Catalysis of Nitrophenols by AuFe3O4 Heterostructures
ARTICLE
Figure 6. (a) XPS N1s spectra of of dumbbell-like AuFe3O4 NPs before and after catalytic reaction. (b) FT-IR spectra of dumbbell-like AuFe3O4
NPs capped with dierent ligands.
4. CONCLUSIONS
In this study, we have rst demonstrated that the heterostructured AuFe3O4 nanocatalysts synthesized via thermal
decomposition of the ironoleate complex in the presence of
Au seeds have excellent bifunctional characteristics for reusability
and catalytic reduction. The size and morphology of AuFe3O4
nanocatalysts are highly dependent on the size of Au seeds. The
catalytic performance of both dumbbell- and ower-like Au
Fe3O4 NPs is excellent for nitrophenol reduction in the presence
of NaBH4. In addition, the catalytic eciency of dumbbell-like
AuFe3O4 NPs is higher than that of ower-like heterostructures because of the high surface coverage of the Au surface by
Fe3O4 nanocrystals in ower-like heterostructures. The dumbbell-like nanoparticles also show good separability and reusability
in successive cycles of reduction. The reaction mechanism of
successive reduction of nitrophenols by AuFe3O4 heterostructures has been proposed and conrmed. Results obtained in this
study open an avenue to the fabrication of highly ecient heterodimer nanocatalysts for serving as an ideal platform to study the
various heterogeneous catalytic processes.
ASSOCIATED CONTENT
bS
AUTHOR INFORMATION
Corresponding Author
ACKNOWLEDGMENT
The authors thank the National Science Council, Taiwan, for
nancial support under Contract No. NSC 99-2113-M-007-007MY3. The authors thank Prof. Hong-Ping Lin at National ChengKung University, Tainan, for help with the HR-TEM analysis.
REFERENCES
(1) Sau, T. K.; Rogach, A. L.; Jackel, F.; Klar, T. A.; Feldmann, J. Adv.
Mater. 2010, 22, 1805.
(2) Jain, P. K.; Huang, X. H.; El-Sayed, I. H.; El-Sayed, M. A. Acc.
Chem. Res. 2008, 41, 1578.
(3) Haruta, M.; Yamada, N.; Kobayashi, T.; Iijima, S. J. Catal. 1989,
115, 301.
(4) Orlov, A.; Jeerson, D. A.; Macleod, N.; Lambert, R. M. Catal.
Lett. 2004, 92, 41.
(5) S. Praharaj, S.; Nath, S.; Ghosh, S. K.; Kundu, S.; Pal, T. Langmuir
2004, 20, 9889.
(6) Zeng, J.; Zhang, Q.; Chen, J.; Xia, Y. Nano Lett. 2010, 10, 30.
(7) Gong, J. L.; Mullins, C. B. Acc. Chem. Res. 2009, 42, 1063.
(8) Hutchings, G. J. Top. Catal. 2008, 48, 55.
(9) Xu, C.; Xie, J.; Ho, D.; Wang, C.; Kohler, N.; Walsh, E. G.;
Morgan, J. R.; Chin, Y. E.; Sun, S. Angew. Chem., Int. Ed. 2008, 47, 173.
(10) Chen, M. S.; Goodman, D. W. Science 2004, 306, 252.
(11) Comotti, M.; Li, W. C.; Splietho, B.; Schuth, F. J. Am. Chem.
Soc. 2006, 128, 917.
(12) Tang, S. C.; Vongehr, S.; Meng, X. K. J. Mater. Chem. 2010, 20, 5436.
(13) Lim, C. W.; Lee, I. S. Nano Today 2010, 5, 412.
(14) Shylesh, S.; Schunemann, V.; Thiel, W. R. Angew. Chem., Int. Ed.
2010, 49, 3428.
(15) Zhu, Y.; Stubbs, L. P.; Ho, F.; Liu, R.; Ship, C. P.; Maguire, J. A.;
Hosmane, N. S. ChemCatChem 2010, 2, 365.
(16) Polshettiwar, V.; Varma, R. S. Green Chem. 2010, 12, 743.
(17) Ge, J. P.; Huynh, T.; Hu, Y. P.; Yin, Y. D. Nano Lett. 2008,
8, 931.
(18) Deng, Y. H.; Cai, Y.; Sun, Z. K.; Zhao, D. Y. J. Am. Chem. Soc.
2010, 132, 8466.
(19) Wang, C.; Yin, H. F.; Dai, S.; Sun, S. H. Chem. Mater. 2010,
22, 3277.
(20) Lee, Y. M.; Garcia, M. A.; Huls, N. A. F.; Sun, S. H. Angew.
Chem., Int. Ed. 2010, 49, 1271.
(21) Lopes, G.; Vargas, J. M.; Sharma, S. K.; Beron, F.; Pirota, K. R.;
Knobel, M.; Rettori, C.; Zysler, R. D. J. Phys. Chem. C 2010, 114, 10148.
(22) Costi, R.; Saunders, A. E.; Banin, U. Angew. Chem., Int. Ed. 2010,
49, 4878.
6597
ARTICLE
(23) Frey, N. A.; Phan, M. H.; Srikanth, H.; Srinath, S.; Wang, C.;
Sun, S. J. Appl. Phys. 2009, 105, 07B502.
(24) Xu, C. J.; Wang, B. D.; Sun, S. H. J. Am. Chem. Soc. 2009,
131, 4216.
(25) Jiang, J.; Gu, H. W.; Shao, H. L.; Devlin, E.; Papaefthymiou,
G. C.; Ying, J. Y. Adv. Mater. 2008, 20, 4403.
(26) Choi, J. S.; Jun, Y. W.; Yeon, S. I.; Kim, H. C.; Shin, J. S.; Cheon,
J. J. Am. Chem. Soc. 2006, 128, 15982.
(27) Sun, S. H.; Zeng, H. J. Am. Chem. Soc. 2002, 124, 8204.
(28) Park, J.; Lee, E.; Hwang, N. M.; Kang, M.; Kim, S. C.; Hwang,
Y.; Park, J. G.; Noh, H. J.; Kim, J. Y.; Park, J. H.; Hyeon, T. H. Angew.
Chem., Int. Ed. 2005, 44, 2872.
(29) Kovalenko, M. V.; Bodnarchuk, M. I.; Lechner, R. T.; Hesser,
G.; Schaer, F.; Heiss, W. J. Am. Chem. Soc. 2007, 129, 6352.
(30) Shavel, A.; Rodruez-Gonzaez, B.; Pacico, J.; Spasova, M.;
Farle, M.; Liz-Marza, L. M. Chem. Mater. 2009, 21, 1326.
(31) Zeng, H.; Rice, P. M.; Wang, S. X.; Sun, S. J. Am. Chem. Soc.
2004, 126, 11458.
(32) Sun, S.; Zeng, H.; Robinson, D. B.; Raoux, S.; Rice, P. M.;
Wang, S. X.; Li, G. J. Am. Chem. Soc. 2004, 126, 273.
(33) Jana, N. R.; Chen, Y.; Peng, X. Chem. Mater. 2004, 16, 3931.
(34) Cheon, J.; Kang, N. J.; Lee, S. M.; Lee, J. H.; Yoon, J. H.; Oh, S. J.
J. Am. Chem. Soc. 2004, 126, 1950.
(35) Gu, H.; Yang, Z.; Gao, J.; Chang, C. K.; Xu, B. J. Am. Chem. Soc.
2005, 127, 34.
(36) Jiang, J.; Gu, H.; Shao, H.; Devlin, E.; Papaefthymiou, G. C.;
Ying, J. Y. Adv. Mater. 2008, 20, 4403.
(37) Wang, C.; Xu, C.; Zeng, H.; Sun, S. Adv. Mater. 2009, 21, 1.
(38) Yu, H.; Chen, M.; Rice, P. M.; Wang, S. X.; White, R. L.; Sun, S.
Nano Lett. 2005, 5, 379.
(39) Choi, S. H.; Na, H. B.; Park, Y. I.; An, K.; Kwon, S. G.; Jang, Y.;
Park, M.; Moon, J.; Son, J. S.; Song, I. C.; Moon, W. K.; Hyeon, T. J. Am.
Chem. Soc. 2008, 130, 15573.
(40) Wei, Y.; Klajn, R.; Pinchuk, A. O.; Grzybowski, B. A. Small
2008, 4, 1635.
(41) Cornell, M. R.; Schwertmann, U. The Iron Oxides; VCH: New
York, 1996; p 117.
(42) Zhen, G.; Muir, B. W.; Moat, B. A.; Harbour, P.; Murray, K. S.;
Moubaraki, B.; Suzuki, K.; Madsen, I.; Agron-Olshina, N.; Waddington,
L.; Mulvaney, P.; Hartley, P. G. J. Phys. Chem. C 2011, 115, 327.
(43) Wu, Y. P.; Zhang, T.; Zheng, Z. H.; Ding, X. B.; Peng, Y. X.
Mater. Res. Bull. 2010, 45, 513.
(44) Dotzauer, D. M.; Dai, J. H.; Sun, L.; Bruening, M. L. Nano Lett.
2006, 6, 2268.
(45) Huang, J. F.; Vongehr, S.; Tang, S. C.; Lu, H. M.; Shen, J. C.;
Meng, X. K. Langmuir 2009, 25, 11890.
(46) Pradhan, N.; Pal, A.; Pal, T. Langmuir 2001, 17, 1800.
(47) Wessels, J. S. C. Biochim. Biophys. Acta 1965, 109, 357.
(48) Hayakawa, K.; Yoshimura, T.; Esumi, K. Langmuir 2003, 19, 5517.
(49) Rashid, M. H.; Bhattacharjee, R. R.; Kotal, A. T.; Mandal, K.
Langmuir 2006, 22, 7141.
(50) Huang, J.; Vongehr, S.; Tang, S.; Lu, H.; Shen, J.; Meng, X.
Langmuir 2009, 25, 11890.
(51) DAmours, M.; Beanger, D. J. Phys. Chem. B 2003, 107
48114817.
6598