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decrease in the rate of 2-ethyl-9,10-anthraquinone
hydrogenation with an increase in the P/Pd ratio
(Tables 1, 2). The yield of hydrogen peroxide in the
presence of Pd–P/С is lower than for unsupported
catalytic systems (Tables 1, 2), but this question
requires further studies. It is important to note that the
ratio of turnover frequencies on two parts of kinetic
curves (TOF1/TOF2), which are related to the rates of
formation and further conversion of 2-ethyl-9,10-
anthrahydroquinone, is 4 times higher on palladium
black than on Pd–P catalysts, although the latter are
characterized by a higher selectivity to hydrogen peroxide
(Table 1). The yield of hydrogen peroxide increased
from 69% (palladium black) to 96% (Pd–P catalyst,
P/Pd = 0.3, Table 1). The Pd–P catalyst (P/Pd = 0.3,
Table 1) showed analogous properties when the reac-
tion was carried out in the toluene–octanol-2
medium. According to and GC–MS data, the devia-
tion of selectivity from 100% in the case of Pd–P cat-
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of 2-ethyl-9,10-anthrahydroquinone. If the selectivity
of palladium catalysts were determined only by the
ratio of the rates of formation and consumption of
2-ethyl-9,10-anthrahydroquinone, the highest yield of
hydrogen peroxide would be on palladium black.
Therefore, both the kinetic and thermodynamic fac-
tors (the ratio between adsorption equilibrium con-
stants for eAQ and eAQН2) affect the selectivity of pal-
ladium catalysts.
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ACKNOWLEDGMENTS
This work was supported by the Russian Science
Foundation (project no. 17-73-10158). Microscopic
images of catalyst samples were obtained using elec-
tron microscope of the Center for Shared Use Bai-
kal’skii Tsentr Nanotekhnologii IRINITU.
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Translated by Andrey Zeigarnik
KINETICS AND CATALYSIS
Vol. 59
No. 5
2018