Paper
Catalysis Science & Technology
In a typical synthesis of Fe48Pd52 NPs, 0.25 mmol of Pd(acac)2
and 0.25 mmol of Fe(acac)3 were dissolved in 3 mL of OAm
in a glass vial. Separately, 0.2 g of MB was dissolved in OAm
(3 mL) and ODE (7 mL) in a four-necked round bottom flask.
Next, the metal precursor mixture was quickly injected into
the reactor at 100 °C under vigorous stirring. After injection,
the color of the solution turned dark brown indicating the
co-reduction of Pd(II) and Fe(III) ions and the formation of al-
loy NPs. The reaction solution was kept at this temperature
for 1 h before it was cooled down to room temperature. An
acetone/ethanol mixture (v/v = 7/3) was added to precipitate
out the product, and the NPs were separated by centrifuga-
tion at 9000 rpm for 12 min. The NP product was re-
dispersed in hexane and precipitated by ethanol. After centri-
fugation, the solvent was discarded and the NPs were dis-
persed in hexane and kept for further use.
by thin layered chromatography (TLC). Most of the reactions
were completed within 10–20 min. Upon reaction comple-
tion, the catalysts were separated by centrifugation and
cleaned several times using a water/methanol mixture. The
reaction products were purified by first evaporating the sol-
vents using a rotary evaporator and secondly passing through
the silica gel column using acetone/n-hexane (1 : 4) as an elu-
ent. The yields of anilines were determined by 1H-NMR and
13C-NMR, and the purified products were dissolved in D2O,
d6-DMSO, CD3OD or CDCl3 depending on the product solu-
bility. Please see the supporting information of our previous
paper for the 1H-NMR and 13C-NMR spectra of the purified
amine products.10
Acknowledgements
By changing the ratio of the metal precursors, two other
compositions of FePd NPs were synthesized using the same
protocol. To obtain Fe39Pd61 NPs, 0.2 mmol of Fe(acac)3 and
0.3 mmol of Pd(acac)2 were used, while to synthesize Fe62Pd38
NPs, 0.3 mmol of Fe(acac)3 and 0.2 mmol of Pd(acac)2 were
used.
This work was mostly conducted at the Department of Chem-
istry, Atatürk University and financially supported by the Sci-
entific and Technological Research Council of Turkey
(TUBITAK, Project No. 113Z276). The part conducted at Brown
University was supported by the U.S. Army Research Labora-
tory and the U.S. Army Research Office under the Multi Uni-
versity Research Initiative (MURI, grant number W911NF-11-
1-0353) on “Stress-Controlled Catalysis via Engineered
Nanostructures”.
The monodisperse Pd NPs were synthesized by using the
reported method.25
Synthesis of reduced graphene oxide (rGO)
rGO was prepared by using well-established procedures. First, Notes and references
graphene oxide (GO) was prepared via modified Hummer's
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and characterization of rGO can be found in our previous
report.36
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Supporting NPs on rGO
In a typical procedure, 40 mg of rGO was dispersed in 40 mL
of ethanol (1 mg ml−1) via sonication, and then 20 mg of the
hexane dispersion of FePd NPs was added. The final mixture
was sonicated for 2 h to assemble the FePd NPs on the rGO.
The rGO–FePd was separated by centrifugation at 7500 rpm
for 12 min and then purified by washing twice with ethanol
and dried under vacuum. The same procedure was applied to
support Pd NPs on rGO.
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General procedure for the transfer hydrogenation reactions
All catalytic transfer hydrogenation reactions were performed
in a 38 mL thermolysis tube under air atmosphere as de-
scribed in our previous reports.10,22 In a typical catalytic
transfer hydrogenation reaction, 1 mmol of substrate and 5
mg of rGO–FePd catalyst were mixed in 10 mL of water–meth-
anol solvent mixture (v/v = 3/7) inside the thermolysis tube
for 10 min at room temperature. Next, 3 mmol of H3NBH3
(AB) were added to the reaction mixture and the reaction was
started by closing the thermolysis tube tightly. Next, the reac-
tion was continued under vigorous stirring at room tempera-
ture and the progress of the catalytic reaction was monitored
Catal. Sci. Technol.
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