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sample current of 6 nA; with a 20Ne beam energy of 5 keV and a Colleges and Universities in Jiangxi Province (KJLD14046) for finan-
+
sample current of 1.6 nA.
cial supports.
X-ray absorption spectra at the Ni K- and Ru K-edges were
recorded at beamlines 17C1 and 01C1, respectively, at the National
Synchrotron Radiation Research Center (NSRRC), Taiwan. Each of
these two beamlines employs an Si(111) double crystal mono-
chromator for energy selection with a resolution ΔE/E = 2 × 10 .
Double mirror systems were utilized for collimating and focusing
as well as harmonic rejection. All data at Ni K-edge were collected
in transmission mode using gas ionization chambers to measure
the intensities of the incidence and transmitted X-ray beams. On
the other hand, a fluorescence mode using a Lytle detector was
applied for data collection at Ru K-edge. The energies of Ni K- and
Ru K-edges were calibrated by defining the first inflection point on
the rising part of the XANES spectra for Ni and Ru reference foils as
[1] M. Valden, X. Lai, D. W. Goodman, Science 1998, 281, 1647.
[2] P. Paalanen, B. M. Weckhuysen, M. Sankar, Catal. Sci. Technol.
−4
2
013, 3, 2869.
3] J. Chen, W. Fang, Q. Zhang, W. Deng, Y. Wang, Chem. Asian J.
014, 9, 2187.
4] a) K. H. Park, K. Jang, H. J. Kim, S. U. Son, Angew. Chem. 2007,
19, 1170; b) K. H. Park, K. Jang, H. J. Kim, S. U. Son, Angew.
Chem Int. Ed. 2007, 46, 1152.
[
[
2
1
[5] H. J. Kim, S. M. Choi, S. H. Nam, M. H. Seo, W. B. Kim, Appl. Catal.
A 2009, 352, 145.
[
[
6] L. Hu, Q. Peng, Y. Li, J. Am. Chem. Soc. 2008, 130, 16136.
7] A. Khodakov, B. Olthof, A. T. Bell, E. Iglesia, J. Catal. 1999, 181,
8333 and 22117 eV, respectively. The background of the spectrum
2
05.
8] V. Petkov, Y. Ren, S. Shan, J. Luo, C.-J. Zhong, Nanoscale 2014, 6,
32.
[9] Z. Cui, M. Yang, F. J. DiSalvo, ACS Nano 2014, 8, 6106.
was subtracted using the AUTOBK algorithm, and data reduction
and fitting were performed using Athena and Artemis programs
from the IFEFFIT software suite.
[
5
Catalytic Performance Testing: The catalytic activity of the cata- [10] S. Shan, J. Luo, L. Yang, C.-J. Zhong, Catal. Sci. Technol. 2014, 4,
3
570.
lysts for benzene hydrogenation was evaluated in a stainless steel
high pressure reactor (Parr 4848). Ten milliliter of benzene and
[
11] S. Shan, V. Petkov, L. Yang, J. Luo, P. Joseph, D. Mayzel, B. Prasai,
L. Wang, M. Engelhard, C.-J. Zhong, J. Am. Chem. Soc. 2014, 136,
7
12] D. Sun, V. Mazumder, O. Metin, S. Sun, ACS Nano 2011, 5, 6458.
13] J. Yang, J. Yang, J. Y. Ying, ACS Nano 2012, 6, 9373.
50 mg of catalyst were added into the reactor and then it was quickly
140.
assembled. The reaction cell was firstly flushed with nitrogen
for 1 min to replace the air and then flushed with hydrogen for
[
[
1
min to remove the nitrogen. The outlet valve was then closed [14] L. Zhang, R. Iyyamperumal, D. F. Yancey, R. M. Crooks,
and hydrogen pressure was added to 4.8 MPa with a stirring rate of
about 500 rpm. The reactants were heated to 60 °C, and the pres-
sure reached 5.3 MPa, starting to record the reaction time. After
the reaction finishing, the temperature was quickly cooled down to
about 5 °C in an ice-water bath and then the autoclave was evacu-
ated. The products were quantified by gas chromatography (GC) on
G. Henkelman, ACS Nano 2013, 7, 9168.
[
[
15] J. Yin, S. Shan, L. Yang, D. Mott, O. Malis, V. Petkov, F. Cai,
M. Shan Ng, J. Luo, B. H. Chen, M. Engelhard, C.-J. Zhong, Chem.
Mater. 2012, 24, 4662.
16] L. Yang, S. Shan, R. Loukrakpam, V. Petkov, Y. Ren, B. N. Wanjala,
M. H. Engelhard, J. Luo, J. Yin, Y. Chen, C.-J. Zhong, J. Am. Chem.
Soc. 2012, 134, 15048.
a Shimadzu GC 2010 instrument equipped with a DB-35 60 m × [17] a) R. R. Deshmukh, J. W. Lee, U. S. Shin, J. Y. Lee, C. E. Song,
Angew. Chem. 2008, 120, 8743; b) R. R. Deshmukh, J. W. Lee,
U. S. Shin, J. Y. Lee, C. E. Song, Angew. Chem. Int. Ed. 2008, 47,
0
.32 mm capillary column and a flame ionization detector (FID)
and were identified by gas chromatography–mass spectrometry
GC–MS) on a Shimadzu GC–MS 2010. The TOF of the catalyst was
8
615.
(
[
[
[
18] S. D. Lin, M. A. Vannice, J. Catal. 1993, 143, 539.
19] S. Srinivas, P. K. Rao, J. Catal. 1994, 148, 470.
20] T. Harada, S. Ikeda, Y. H. Ng, T. Sakata, H. Mori, T. Torimoto,
M. Matsumura, Adv. Funct. Mater. 2008, 18, 2190.
calculated on the basis of the mols of total metal. The metal dis-
persion was not calculated for most of the supported catalysts of
the liquid benzene hydrogenation in the reported references (as
shown in Table S1 in the Supporting Information). For comparison, [21] B. Yoon, C. M. Wai, J. Am. Chem. Soc. 2005, 127, 17174.
[
22] A. Corma, P. Serna, Science 2006, 313, 332.
the metal dispersion of the as-prepared catalysts was not calcu-
lated in this work. In fact, the TOF of the catalyst will increase if
metal dispersion was considered.
[23] Y. Tonbul, M. Zahmakiran, S. Özkar, Appl. Catal. B 2014, 148,
4
66.
[
[
[
24] M. Takasaki, Y. Motoyama, K. Higashi, S. H. Yoon, I. Mochida,
H. Nagashima, Chem. Asian J. 2007, 2, 1524.
25] .A N wo icki , .Y Z ah ng , B. Lé eg r , J.- .P oR lland , H. Br ioc ut , E. Mon ifle r,
A. Roucoux, Chem. Commun. 2006, 296.
26] a) S. Miao, Z. Liu, B. Han, J. Huang, Z. Sun, J. Zhang, T. Jiang,
Angew. Chem. 2005, 118, 272; b) S. Miao, Z. Liu, B. Han,
J. Huang, Z. Sun, J. Zhang, T. Jiang, Angew. Chem. Int. Ed. 2006,
Supporting Information
4
5, 266.
Supporting Information is available from the Wiley Online Library
or from the author.
[
[
27] Y. Ma, Y. Huang, Y. Cheng, L. Wang, X. Li, Appl. Catal. A 2014, 484, 154.
28] M. Zahmakıran, Y. Tonbul, S. Özkar, J. Am. Chem. Soc. 2010, 132,
6
541.
[
[
[
[
29] B. Yoon, H.-B. Pan, C. M. Wai, J. Phys. Chem. C 2009, 113, 1520.
30] A. Louloudi, N. Papayannakos, Appl. Catal. A 1998, 175, 21.
31] H. Duan, D. Wang, Y. Kou, Y. Li, Chem. Commun. 2012, 49, 303.
32] B. Pawelec, V. La Parola, R. Navarro, S. Murcia-Mascarós, J. Fierro,
Carbon 2006, 44, 84.
Acknowledgements
The authors would like to thank the National Natural Science
Foundation of China (Grant Nos. 201106118, 21303140, and
[
33] A. Venezia, V. L. Parola, B. Pawelec, J. Fierro, Appl. Catal. A 2004,
21263005) and the Landing Project of Science and Technology of
264, 43.
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