The interaction of hydrazine monohydrate with the surface of metal-containing catalysts

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Abstract

The interaction of hydrazine monohydrate with nickel on various carriers has been investigated using a range of physical and chemical methods. Hydrazine monohydrate adsorbs on catalysts, both active and inactive, in the infrared region of the spectrum. The location of the particles of adsorbed hydrazine monohydrate is on the carrier. There was no correlation found between the spectral features on several of the catalysts studied and their catalytic activity in hydrogen formation. The main transformation reactions occur in the metallic phase of the supported catalysts. It was found that, due to the reaction energy, the size and structure of the clusters were reduced and rearranged to create centers suitable for the effective course of intramolecular dehydrogenation of hydrazine. At the same time, this process was most effective on smaller clusters, possibly because a stronger Me-H bond was formed on them. Adsorption of hydrazine monohydrate through hydrogen atoms was possible on these clusters. These conditions ensured the predominant formation of hydrogen at low temperatures. An increase in temperature contributed to the course of a competing reaction of ammonia formation, associated with the breaking of the N-N bond in the adsorption complex. As result, the formation of NH2 complexes is taking place, and then ammonia.

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V. A. Matyshak

Semenov Federal Research Center for Chemical Physics RAS

Email: son1108@yandex.ru
Russian Federation, Kosygina str., 4, Moscow, 119991

O. N. Silchenkova

Semenov Federal Research Center for Chemical Physics RAS

Author for correspondence.
Email: son1108@yandex.ru
Russian Federation, Kosygina str., 4, Moscow, 119991

A. N. Ilichev

Semenov Federal Research Center for Chemical Physics RAS

Email: son1108@yandex.ru
Russian Federation, Kosygina str., 4, Moscow, 119991

M. Ya. Bykhovsky

Semenov Federal Research Center for Chemical Physics RAS

Email: son1108@yandex.ru
Russian Federation, Kosygina str., 4, Moscow, 119991

O. S. Morozova

Semenov Federal Research Center for Chemical Physics RAS

Email: son1108@yandex.ru
Russian Federation, Kosygina str., 4, Moscow, 119991

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2. Fig. 1. H2-TPR profiles of catalysts 5% Ni/Al2O3 (1), 5% Ni/ZrO2 (2), 5% Pd/Al2O3 (3), 5% Ni/MgO (4), and 5% Ni/TiO2 (5).

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3. Fig. 2. Dependence of hydrogen concentration on temperature in the presence of 5% Pd/Al2O3 (1), 5% Ni/MgO (2), and 5% Ni/TiO2 (3) samples.

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4. Fig. 3. Time dependences of H2 (1) and N2 (2) concentrations at 30°C in the presence of 5% Ni/Al2O3 during the establishment of the steady state and after switching off hydrazine monohydrate from the mixture flow.

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5. Fig. 4. IR spectra obtained under hydrazine monohydrate conversion conditions at 60°C on Al2O3 (1) and 5% Ni/Al2O3 (2) samples and at 35°C on TiO2 (3) and 5% Ni/TiO2 (4) samples.

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6. Fig. 5. Time dependences of intensities of bands at 1630 (1) and 3350 cm-1 (2) during the establishment of the steady state and after switching off hydrazine monohydrate from the mixture flow on 5% Ni/MgO sample at 30°C.

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7. Fig. 6. Hydrogen formation rate after treatment of 5% NiO/TiO2 catalyst in the reaction mixture at elevated temperatures.

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8. Fig. 7. TEM images of 5% Ni/Al2O3 before (a) and after reaction (b), and of 5% Ni/ZrO2 before reaction (c). Metal particles are indicated by arrows.

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