ACS Catalysis
Letter
4. EXPERIMENTAL SECTION
REFERENCES
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(1) Qian, H.; Eckenhoff, W. T.; Zhu, Y.; Pintauer, T.; Jin, R. J. Am.
Chem. Soc. 2010, 132, 8280−8281.
Synthesis of HDPA-Fe3O4 Nanoparticles. The HDPA-
Fe3O4 nanoparticles are prepared using a modified reverse
coprecipitation procedure followed by hydrothermal treatment.
Typically, 0.40 mmol n-hexadecylphosphonic acid (HDPA,
Sigma-Aldrich) was dissolved in a mixture of 20 mL of
deionized water and 3.0 mLof ethanol at 353 K. Five milliliters
of 1.6 M FeCl2·4H2O and 5.0 mL of 1.6 M FeCl3·6H2O
aqueous solution were added into the HDPA solution slowly.
The resulting solution was stirred for 1.5 h. Then, the above
solution was added into 80 mL of 1.5 M NH3·H2O solution in a
fixed rate of 1.0 mL·min−1 at 353 K and then stirred for another
3 h. The resulting suspension was transferred into a Teflon-
lined autoclave and put into an oven at 453 K for hydrothermal
treatment of 24 h. The deposit was centrifuged and washed
with ethanol and dried in vacuum at 313 K overnight.
Characterization. Powder XRD measurements were
performed using a Philips X’Pert MPD Pro X-ray diffractometer
with graphite-monochromated high-intensity Cu Kα radiation
(0.15418 nm) at 40 kV and 40 mA. TEM images were recorded
with a JEM-110 Electron Microscope (JEOL) at an accelerating
voltage of 120 kV. HRTEM was performed with a JEOL JEM-
2100 instrument at an acceleration voltage of 200 kV. FT-IR
spectra were recorded under vacuum condition in a Bruker
VERTEX FT-IR spectrometer. TG-DTA analysis was carried
on a STA 449C-Thermal Star 300 (Netzsch) in N2 or air
atmosphere to 1073 K.
(2) Lee, H.; Habas, S. E.; Kweskin, S.; Butcher, D.; Somorjai, G. A.;
Yang, P. Angew. Chem., Int. Ed. 2006, 45, 7824−7828.
(3) Zhou, K.; Li, Y. Angew. Chem., Int. Ed. 2012, 51, 602−613.
(4) Xie, X.; Li, Y.; Liu, Z.-Q.; Haruta, M.; Shen, W. Nature 2009, 458,
746−749.
(5) Oliver-Meseguer, J.; Cabrero-Antonino, J. R.; Domínguez, I.;
́
Leyva-Perez, A.; Corma, A. Science 2012, 338, 1452−1455.
(6) Grirrane, A.; Corma, A.; García, H. Science 2008, 322, 1661−
1664.
(7) Chin, Y. H.; Buda, C.; Neurock, M.; Iglesia, E. J. Am. Chem. Soc.
2011, 133, 15958−15978.
(8) Zhao, D.; Xu, B.-Q. Angew. Chem., Int. Ed. 2006, 45, 4955−4959.
(9) Kesavan, L.; Tiruvalam, R.; Ab Rahim, M. H.; bin Saiman, M. I.;
Enache, D. I.; Jenkins, R. L.; Dimitratos, N.; Lopez-Sanchez, J. A.;
Taylor, S. H.; Knight, D. W.; Kiely, C. J.; Hutchings, G. J. Science 2011,
331, 195−199.
(10) Enache, D. I.; Edwards, J. K.; Landon, P.; Solsona-Espriu, B.;
Carley, A. F.; Herzing, A. A.; Watanabe, M.; Kiely, C. J.; Knight, D. W.;
Hutchings, G. J. Science 2006, 311, 362−365.
(11) Yamada, Y.; Tsung, C.-K.; Huang, W.; Huo, Z.; Habas, S. E.;
Soejima, T.; Aliaga, C. E.; Somorjai, G. A.; Yang, P. Nat. Chem. 2011,
3, 372−376.
(12) Schafer, S.; Wyrzgol, S. A.; Caterino, R.; Jentys, A.; Schoell, S. J.;
Havecker, M.; Knop-Gericke, A.; Lercher, J. A.; Sharp, I. D.;
Stutzmann, M. J. Am. Chem. Soc. 2012, 134, 12528−12535.
(13) Goel, S.; Wu, Z.; Zones, S. I.; Iglesia, E. J. Am. Chem. Soc. 2012,
134, 17688−17695.
Catalytic Testing. The toluene oxidation reactions were
carried out in an 80 mL Teflon-lined autoclave with 6.6 mmol
toluene and 0.1 g of catalyst in 40 mL of deionized water, which
performed as dual media for dispersion of and transfer of
reactants and products. After purging the reactor three times
with oxygen, the temperature of the autoclave was heated up to
the reaction temperature, and then 3.0 MPa oxygen was fed to
the autoclave, and the oxidation reaction was started.
Qualitative determination was carried out using GC-TOF
(Micromass, column DB-5) and compared with the authentic
samples. Quantitative analysis was performed using Shimadzu
GC-2014 gas chromatography equipped with a HP-5 column
and FID detector. Ethylbenzene was added after reaction as
internal GC standard to calibrate the conversions of reactants.
(14) Niu, Z.; Li, Y. Chem. Mater. 2013, 26, 72−83.
(15) Gross, E.; Liu, J. H.; Alayoglu, S.; Marcus, M. A.; Fakra, S. C.;
Toste, F. D.; Somorjai, G. A. J. Am. Chem. Soc. 2013, 135, 3881−3886.
(16) Marshall, S. T.; O’Brien, M.; Oetter, B.; Corpuz, A.; Richards, R.
M.; Schwartz, D. K.; Medlin, J. W. Nat. Mater. 2010, 9, 853−858.
(17) Marshall, S. T.; Schwartz, D. K.; Medlin, J. W. Langmuir 2011,
27, 6731−6737.
(18) Taguchi, T.; Isozaki, K.; Miki, K. Adv. Mater. 2012, 24, 6462−
6467.
(19) Kwon, S. G.; Krylova, G.; Sumer, A.; Schwartz, M. M.; Bunel, E.
E.; Marshall, C. L.; Chattopadhyay, S.; Lee, B.; Jellinek, J.; Shevchenko,
E. V. Nano Lett. 2012, 12, 5382−5388.
(20) Jiang, Y.; Yin, P.; Li, Y.; Sun, Z.; Liu, Q.; Yao, T.; Cheng, H.; Hu,
F.; Xie, Z.; He, B.; Pan, G.; Wei, S. J. Phys. Chem. C 2012, 116, 24999−
25003.
(21) Tsunoyama, H.; Ichikuni, N.; Sakurai, H.; Tsukuda, T. J. Am.
Chem. Soc. 2009, 131, 7086−7093.
ASSOCIATED CONTENT
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(22) Long, W.; Brunelli, N. A.; Didas, S. A.; Ping, E. W.; Jones, C. W.
ACS Catal. 2013, 3, 1700−1708.
S
* Supporting Information
The preparation methods, some characterizations, and related
data are shown in Supporting Information. This material is
(23) Zhong, R.-Y.; Yan, X.-H.; Gao, Z.-K.; Zhang, R.-J.; Xu, B.-Q.
Catal. Sci. Technol. 2013, 3, 3013−3019.
(24) Gelalcha, F. G. Chem. Rev. 2007, 107, 3338−3361.
(25) Crabtree, R. H. Chem. Rev. 2010, 110, 575−575.
(26) Thomas, J. M.; Raja, R.; Gai, P. L.; Gronbeck, H.; Hernan
́
dez-
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AUTHOR INFORMATION
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Garrido, J. C. ChemCatChem 2010, 2, 402−406.
Corresponding Author
(27) Satrio, J. A. B.; Doraiswamy, L. K. Chem. Eng. J. 2001, 82, 43−
56.
25 83595077.
(28) Raja, R.; Thomas, J.; Dreyer, V. Catal. Lett. 2006, 110, 179−183.
(29) Brutchey, R. L.; Drake, I. J.; Bell, A. T.; Tilley, T. D. Chem.
Commun. 2005, 3736−3738.
(30) Lv, J.; Shen, Y.; Peng, L.; Guo, X.; Ding, W. Chem. Commun.
2010, 46, 5909−5911.
(31) Service, R. F. Science 2012, 335, 1167.
(32) Sun, S. H.; Zeng, H. J. Am. Chem. Soc. 2002, 124, 8204−8205.
(33) Sahoo, Y.; Pizem, H.; Fried, T.; Golodnitsky, D.; Burstein, L.;
Sukenik, C. N.; Markovich, G. Langmuir 2001, 17, 7907−7911.
(34) Yee, C.; Kataby, G.; Ulman, A.; Prozorov, T.; White, H.; King,
A.; Rafailovich, M.; Sokolov, J.; Gedanken, A. Langmuir 1999, 15,
7111−7115.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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The authors are grateful for the financial support from the
Ministry of Science and Technology of China
(2009CB623504), the National Science Foundation of China
(20673054, 21273107), and Sinopec Shanghai Research
Institute of Petrochemical Technology.
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dx.doi.org/10.1021/cs500643r | ACS Catal. 2014, 4, 2746−2752