Journal of the American Chemical Society
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UV−vis−NIR spectrophotometer (190−1600 nm) at room temper-
ature. MALDI-MS was performed with a PerSeptive Biosystems
Voyager DE super-STR time-of-flight (TOF) mass spectrometer.
trans-2-[3-(4-tert-Butylphenyl)-2-methyl-2-propenylidene]-
malononitrile (DCTB) was used as the matrix in MALDI analysis.23
Typically, 1 mg of matrix and 0.1 mL of analyte stock solution were
mixed in 100 μL of CH2Cl2, and 10 μL of this solution was applied to
the steel plate and then air-dried prior to MALDI analysis. ESI-MS was
performed using a Waters Q-TOF mass spectrometer equipped with a
Z-spray source. The sample was dissolved in toluene (1 mg/mL) and
then mixed 1:1 (v/v) with a dry methanol solution of CsOAc (50
mM). TGA was conducted on ∼2 mg samples under a N2 atmosphere
(flow rate ∼50 mL/min) on a TG/DAT 6300 analyzer (Seiko
Instruments, Inc.) at a heating rate of 10 °C/min.
Typical Procedure for Chemselective Hydrogenation of
Nitrobenzaldehyde. In a typical selective hydrogenation reaction, 4-
nitrobenzaldehyde (0.05 mmol), pyridine (0.1 mmol), and
Au99(SPh)42 nanoclusters (∼1 mg) or Au99(SPh)42/oxide (100 mg,
1 wt % loading) were added to a reactor (Parr Instrument Company,
series 4700, 22 mL capacity) under 20 bar H2. The reaction mixture
was kept at 80 °C as indicated in Table 1. After the reaction, the
mixture was extracted with ethyl acetate. The crude product was
obtained after removal of the solvent. The conversion of 4-
nitrobenzaldehyde and the selectivity for the 4-nitrobenzyl alcohol
product were determined by 1H NMR (300 MHz) spectroscopic
analysis (Figure S6 in the Supporting Information). In the recycling
tests, the Au99(SPh)42/CeO2 catalyst was collected after the reaction
by centrifugation at 1000 rpm for 5 min and then reused in a fresh
reaction. The reported conversion and selectivity values were averaged
over three measurements, and the error is ∼0.5%.
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ASSOCIATED CONTENT
■
S
* Supporting Information
UV−vis spectrum of the Aun(SPhCH3)m nanoclusters,
isothermal stability analysis at 150 °C and UV−vis spectra of
the nanoclusters before/after 150 °C thermal treatment, TEM
image of Au99(SPh)42 nanoclusters after the catalytic reaction,
UV−vis and MALDI-MS spectra of Au25(SPh)18 and
Au36(SPh)24 nanoclusters before and after hydrogenation
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Am. Chem. Soc. 2008, 130, 5883−5885.
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W. J. Am. Chem. Soc. 2008, 130, 3754−3755.
1
reaction, and H NMR data. This material is available free of
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AUTHOR INFORMATION
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(28) Li, Z.; Brouwer, C.; He, C. Chem. Rev. 2008, 108, 3239−3265.
(29) Li, G.; Liu, C.; Lei, Y.; Jin, R. Chem. Commun. 2012, 48, 12005−
12007.
Corresponding Author
(30) Li, G.; Jiang, D.; Liu, C.; Yu, C.; Jin, R. J. Catal. 2013, 306, 177−
Notes
183.
The authors declare no competing financial interest.
(31) Zhu, Y.; Qian, H.; Drake, B. A.; Jin, R. Angew. Chem., Int. Ed.
2010, 49, 1295−1298.
ACKNOWLEDGMENTS
(32) Yamamoto, H.; Yano, H.; Kouchi, H.; Obora, Y.; Arakawa, R.;
Kawasaki, H. Nanoscale 2012, 4, 4148−4154.
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This work was financially supported by the U.S. Department of
Energy, Office of Basic Energy Sciences (Grant DE-FG02-
12ER16354). We thank Joseph Suhan for assistance with TEM
imaging of nanoclusters.
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