Supplementary Material (ESI) for Chemical Communications
This journal is (c) The Royal Society of Chemistry 2009
°C min-1 under N2 atmosphere. The palladium contents of the samples were
determined quantitatively by atomic absorption spectroscopy (AAS) on a HITACHI
Z-2300 instrument.
Acid-base properties were determined by NH3-, and CO2-TPD measured by the
pulse technique using a Micromeritics AutoChem II 2920 instrument using TCD
detection. Typically, a sample of 100 mg was pretreated under a flow of helium (50 ml
min-1) at 150 °C for 3 h. Then the temperature was lowered to 100 °C under a flow of
He. The analysis was performed by successive pulse of 1 ml of ammonia (or CO2)
into the He flow using a loop. The TPD data were collected from 100 °C to 400 °C at
a heating rate of 10 °C min-1 in a helium flow.
Pd dispersion in the catalysts was determined by CO chemisorption measured by
the pulse technique using a Micromeritics AutoChem II 2920 apparatus. Before
analysis, the sample was treated at 200 °C in H2 for 1 h. The dispersion, D, defined as
the fraction of palladium at the surface, D = Pds/Pdtotal, was calculated with the
assumption of one CO molecule per surface Pd.[2]
3. Catalytic measurements
The liquid-phase synthesis of MIBK was performed in a 60 ml Teflon-lined
stainless steel autoclave quipped with a pressure gauge and a magnetic stirrer.
Typically, 2.0 g of acetone, 0.2 g of catalyst, and 0.3 g of decane (internal GC
standard) were added to the autoclave and the mixture was stirred at a constant
stirring speed of 800 rpm. The reaction time was 1.5 h unless stated otherwise. The
autoclave was purged five times with H2, then pressurized with H2 and loaded in an
oil bath, which was preheated to the target temperature. Most of the acetone remained
liquid under such conditions during the reactions, as judging from the resulting
pressure at each reaction temperature. At the end of the reaction, the autoclave was
cooled to 0 °C by placing it to an ice bath. The gaseous products were collected with a
gas bag. The reaction products were identified with a GC-MS (Shimadzu QP5050A)
and analyzed by a GC (Agilent 6820) equipped with a flame ionization detector and a
0.25 mm × 30 m capillary column (DB-WAX).
For the recyclability test, the catalyst was isolated from the reaction solution at
the end of each catalytic reaction, washed with acetone, and then dried at 150 °C
under vacuum. The dried catalyst was then reused in the second run. The catalytic
activity and MIBK selectivity of the catalyst was also obtained in the second run,
showing that the framework of the catalyst may remain intact during the catalytic
cycles. The catalyst remained effective for up to 5 cycles for the reaction (Table S4).
Reference
[1] Y. K. Hwang, D. Y. Hong, J. S. Chang, S. H. Jhung, Y. K. Seo, J. Kim, A. Vimont,
M. Daturi, C. Serre, G. Ferey, Angew. Chem. Int. Ed. Engl. 2008, 47, 4144.
[2] G. Agostini, R. Pellegrini, G. Leofanti, L. Bertinetti, S. Bertarione, E. Groppo, A.
Zecchina, C. Lamberti, J. Phys. Chem. C 2009, 113, 10485.