Application of TOF-SIMS Method in the Study of Wetting the Iron (111) Surface with Promoter Oxides

In the present work, a simplified model of the Fe(111) surface’s promoter-oxide system was investigated in order to experimentally verify the previously proposed and known models concerning the structure and chemical composition of the surfaces of iron nanocrystallites in the ammonia-synthesis catal...

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Main Authors: Walerian Arabczyk, Jacek Rogowski, Rafał Pelka, Zofia Lendzion-Bieluń
Format: Article
Language:English
Published: MDPI AG 2022-01-01
Series:Molecules
Subjects:
Online Access:https://www.mdpi.com/1420-3049/27/3/648
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author Walerian Arabczyk
Jacek Rogowski
Rafał Pelka
Zofia Lendzion-Bieluń
author_facet Walerian Arabczyk
Jacek Rogowski
Rafał Pelka
Zofia Lendzion-Bieluń
author_sort Walerian Arabczyk
collection DOAJ
description In the present work, a simplified model of the Fe(111) surface’s promoter-oxide system was investigated in order to experimentally verify the previously proposed and known models concerning the structure and chemical composition of the surfaces of iron nanocrystallites in the ammonia-synthesis catalyst. It was shown that efficient oxygen diffusion from metal oxides to the clean Fe(111) iron surface took place even at temperatures lower than 100 °C. The effective wetting of the iron surface by potassium oxide is possible when the surface is covered with oxygen at temperatures above 250 °C. In the TOF-SIMS spectra of the surface of iron wetted with potassium, an emission of secondary FeOK<sup>+</sup> ions was observed that implies that potassium atoms are bound to the iron surface atoms through oxygen. As a result of further wetting the iron surface with potassium ions, a heterogeneous surface structure was formed consisting of a thin K<sub>2</sub>O layer, next to which there was an iron-oxide phase covered with potassium ions. Only a limited increase in calcium concentration was observed on the Fe(111) iron surface upon sample annealing at up to 350 °C. As a result of wetting the iron surface with calcium ions, an oxide solution of CaO-Fe<sub>x</sub>O<sub>y</sub> was formed. In the annealing process of the sample containing alumina, only traces of this promoter diffusing to the iron surface were observed. Alumina formed a solution with a passive layer on the iron surface and under the process conditions (350 °C) it did not wet the pure iron (111) surface. The decrease in Fe<sup>+</sup>-ion emission from the Fe-Ca and Fe-Al samples at 350 °C implies a reduction in the oxygen concentration on the sample surface at this temperature.
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spelling doaj.art-e2235f4619e74606b4144e8e83b490ce2023-11-23T17:10:08ZengMDPI AGMolecules1420-30492022-01-0127364810.3390/molecules27030648Application of TOF-SIMS Method in the Study of Wetting the Iron (111) Surface with Promoter OxidesWalerian Arabczyk0Jacek Rogowski1Rafał Pelka2Zofia Lendzion-Bieluń3Department of Inorganic Chemical Technology and Environment Engineering, Faculty of Chemical Technology and Engineering, West Pomeranian University of Technology in Szczecin, 42 Piastów Ave., 71065 Szczecin, PolandInstitute of General and Ecological Chemistry, Lodz University of Technology, ul. Zeromskiego 116, 90924 Lodz, PolandDepartment of Inorganic Chemical Technology and Environment Engineering, Faculty of Chemical Technology and Engineering, West Pomeranian University of Technology in Szczecin, 42 Piastów Ave., 71065 Szczecin, PolandDepartment of Inorganic Chemical Technology and Environment Engineering, Faculty of Chemical Technology and Engineering, West Pomeranian University of Technology in Szczecin, 42 Piastów Ave., 71065 Szczecin, PolandIn the present work, a simplified model of the Fe(111) surface’s promoter-oxide system was investigated in order to experimentally verify the previously proposed and known models concerning the structure and chemical composition of the surfaces of iron nanocrystallites in the ammonia-synthesis catalyst. It was shown that efficient oxygen diffusion from metal oxides to the clean Fe(111) iron surface took place even at temperatures lower than 100 °C. The effective wetting of the iron surface by potassium oxide is possible when the surface is covered with oxygen at temperatures above 250 °C. In the TOF-SIMS spectra of the surface of iron wetted with potassium, an emission of secondary FeOK<sup>+</sup> ions was observed that implies that potassium atoms are bound to the iron surface atoms through oxygen. As a result of further wetting the iron surface with potassium ions, a heterogeneous surface structure was formed consisting of a thin K<sub>2</sub>O layer, next to which there was an iron-oxide phase covered with potassium ions. Only a limited increase in calcium concentration was observed on the Fe(111) iron surface upon sample annealing at up to 350 °C. As a result of wetting the iron surface with calcium ions, an oxide solution of CaO-Fe<sub>x</sub>O<sub>y</sub> was formed. In the annealing process of the sample containing alumina, only traces of this promoter diffusing to the iron surface were observed. Alumina formed a solution with a passive layer on the iron surface and under the process conditions (350 °C) it did not wet the pure iron (111) surface. The decrease in Fe<sup>+</sup>-ion emission from the Fe-Ca and Fe-Al samples at 350 °C implies a reduction in the oxygen concentration on the sample surface at this temperature.https://www.mdpi.com/1420-3049/27/3/648TOF-SIMSmonocrystalline ironsurface (111)wettingdiffusion
spellingShingle Walerian Arabczyk
Jacek Rogowski
Rafał Pelka
Zofia Lendzion-Bieluń
Application of TOF-SIMS Method in the Study of Wetting the Iron (111) Surface with Promoter Oxides
Molecules
TOF-SIMS
monocrystalline iron
surface (111)
wetting
diffusion
title Application of TOF-SIMS Method in the Study of Wetting the Iron (111) Surface with Promoter Oxides
title_full Application of TOF-SIMS Method in the Study of Wetting the Iron (111) Surface with Promoter Oxides
title_fullStr Application of TOF-SIMS Method in the Study of Wetting the Iron (111) Surface with Promoter Oxides
title_full_unstemmed Application of TOF-SIMS Method in the Study of Wetting the Iron (111) Surface with Promoter Oxides
title_short Application of TOF-SIMS Method in the Study of Wetting the Iron (111) Surface with Promoter Oxides
title_sort application of tof sims method in the study of wetting the iron 111 surface with promoter oxides
topic TOF-SIMS
monocrystalline iron
surface (111)
wetting
diffusion
url https://www.mdpi.com/1420-3049/27/3/648
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AT rafałpelka applicationoftofsimsmethodinthestudyofwettingtheiron111surfacewithpromoteroxides
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