Mendeleev Commun., 2018, 28, 603–605
Table 2 Kinetic parameters of liquid-phase alkyne hydrogenation and selectivity for DPE formation at PH = 5 bar and T = 25°C.a
2
S= (%)c
TOF1/s–1 TOF2/s–1 TOF1/TOF2 Scis (%)b Strans (%)b
–1
–1
Treatment
r1/mmol min–1 gcat
r2/mmol min–1 gcat
X5º0% (%) Xº95% (%)
H2, 500°C
0.25
0.62
2.38
0.26
0.007
0.015
0.121
0.007
0.018
0.044
0.169
0.019
0.0005
0.0011
0.0086
0.0005
36.0
40.7
19.6
38.0
95.4
94.7
93.5
95.6
4.6
4.3
4.5
4.4
97.0
96.8
96.7
97.1
96.0
95.3
94.3
95.9
O2/N2, 25°C, 30 min
O2/N2, 150°C, 30 min
H2, 250°C
a See ref. 25 for details of calculations. b Selectivity was determined at DPA conversions of 95% (Xº95%). c Selectivity was determined at DPA conversions of
50% (X5º0%) and 95% (Xº95%).
Remarkably, PdIn/Al2O3 retains high selectivity in alkene
formation after oxidation at 150°C (see Table 2) despite the
transformation of isolated Pd1 sites to multiatomic Pdn surface
centers upon oxidative treatment. This observation suggests that
the high selectivity of PdIn/Al2O3 is due to the hindering of sub-
surface hydride formation (since PdIn is not capable to adsorb
hydrogen18) rather than site isolation of Pd1 centers.
It is important that the subsequent reduction at 250°C completely
restores the catalytic characteristics of PdIn/Al2O3 (see Table 2),
which is in agreement with CO-FTIR and XPS data.
Thus, a comparison of the characterization data and the catalytic
results for PdIn/Al2O3 demonstrate that the mild oxidative treat-
ment makes it possible to tune the structure of active sites on the
surface of Pd nanoparticles. Partial oxidation of indium component
deteriorates the isolation of Pd sites and leads to the transforma-
tion of a part of isolated Pd sites to multiatomic Pdn centers
demonstrating high hydrogenation activity.
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This study was supported by the Russian Science Foundation
(grant no. 16-13-10530). The catalyst characterization by electron
microscopy was performed at the Department of Structural Studies
of the N. D. Zelinsky Institute of Organic Chemistry, Russian
Academy of Sciences. We are grateful to Professor M. N. Vargaftik
and Dr. I. A. Yakushev (N. S. Kurnakov Institute of General and
Inorganic Chemistry, Russian Academy of Sciences) for supplying
us with the Pd(m-O2CMe)4In(O2CMe) complex, which was used
as a precursor for the catalyst preparation.
Online Supplementary Materials
Supplementary data associated with this article can be found
in the online version at doi: 10.1016/j.mencom.2018.11.013.
22 I. A. Witon´ska, M. J. Walock, P. Dziugan, S. Karski andA. V. Stanishevsky,
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Received: 6th July 2018; Com. 18/5644
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