Interaction between CO and a Coke-Resistant NiIn/SiO2 Methane Dry Reforming Catalyst: A DRIFTS and CO Pulse Study

Miklós Németh, Ferenc Somodi, Anita Horváth

Research output: Contribution to journalArticle

Abstract

Recently a new In-promoted Ni catalyst has been elaborated and published in our laboratory, that has beneficial properties in dry reforming of methane, including inhibited coking. In order to get deeper insights into the coke-free behavior of this SiO2-supported 3 wt % Ni 2 wt % In catalyst, we wished to monitor the interaction between CO and the catalyst. For this purpose DRIFTS studies under CO, CO2, or CO2 + CH4 flow at different temperatures and CO pulse flow experiments at 600 °C followed by mass spectrometry were carried out. A linear carbonyl band at 2013 cm-1 in the DRIFT spectra of the In-promoted catalyst was attributed to CO bonded on Ni atoms surrounded by In neighbors. The lack of bridge and multicoordinated carbonyls also proved the dilution of Ni surface with In. In the presence of a CH4:CO2 = 70:30 dry reforming mixture, stable Ni bonded CO species were found on NiIn/SiO2 suggesting that the metallic sites remained clean during the reaction (unlike on the reference Ni/SiO2). At the end of the reforming reaction, little surface segregation of the original bimetallic particles and the formation of islands with adjacent Ni sites were presumed based on the DRIFTS results. The pulse CO experiments at 600 °C, tailored to detect the most sensitive surface sites for Boudouard reaction, proved that CO dissociation on the bimetallic catalyst was markedly hindered, while it caused carbon deposition on the unpromoted sample. Based on all these results, we postulate a picture of the working catalyst that is dispersed ensembles of NiIn-InOx entities stabilized by SiO2.

Original languageEnglish
JournalJournal of Physical Chemistry C
DOIs
Publication statusPublished - Jan 1 2019

Fingerprint

coke
Methane
Carbon Monoxide
Reforming reactions
Coke
methane
catalysts
Catalysts
pulses
interactions
inosine dialdehyde
Surface segregation
Coking
axioms
Dilution
Mass spectrometry
dilution
mass spectroscopy
Experiments
dissociation

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

Cite this

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title = "Interaction between CO and a Coke-Resistant NiIn/SiO2 Methane Dry Reforming Catalyst: A DRIFTS and CO Pulse Study",
abstract = "Recently a new In-promoted Ni catalyst has been elaborated and published in our laboratory, that has beneficial properties in dry reforming of methane, including inhibited coking. In order to get deeper insights into the coke-free behavior of this SiO2-supported 3 wt {\%} Ni 2 wt {\%} In catalyst, we wished to monitor the interaction between CO and the catalyst. For this purpose DRIFTS studies under CO, CO2, or CO2 + CH4 flow at different temperatures and CO pulse flow experiments at 600 °C followed by mass spectrometry were carried out. A linear carbonyl band at 2013 cm-1 in the DRIFT spectra of the In-promoted catalyst was attributed to CO bonded on Ni atoms surrounded by In neighbors. The lack of bridge and multicoordinated carbonyls also proved the dilution of Ni surface with In. In the presence of a CH4:CO2 = 70:30 dry reforming mixture, stable Ni bonded CO species were found on NiIn/SiO2 suggesting that the metallic sites remained clean during the reaction (unlike on the reference Ni/SiO2). At the end of the reforming reaction, little surface segregation of the original bimetallic particles and the formation of islands with adjacent Ni sites were presumed based on the DRIFTS results. The pulse CO experiments at 600 °C, tailored to detect the most sensitive surface sites for Boudouard reaction, proved that CO dissociation on the bimetallic catalyst was markedly hindered, while it caused carbon deposition on the unpromoted sample. Based on all these results, we postulate a picture of the working catalyst that is dispersed ensembles of NiIn-InOx entities stabilized by SiO2.",
author = "Mikl{\'o}s N{\'e}meth and Ferenc Somodi and Anita Horv{\'a}th",
year = "2019",
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doi = "10.1021/acs.jpcc.9b06839",
language = "English",
journal = "Journal of Physical Chemistry C",
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T1 - Interaction between CO and a Coke-Resistant NiIn/SiO2 Methane Dry Reforming Catalyst

T2 - A DRIFTS and CO Pulse Study

AU - Németh, Miklós

AU - Somodi, Ferenc

AU - Horváth, Anita

PY - 2019/1/1

Y1 - 2019/1/1

N2 - Recently a new In-promoted Ni catalyst has been elaborated and published in our laboratory, that has beneficial properties in dry reforming of methane, including inhibited coking. In order to get deeper insights into the coke-free behavior of this SiO2-supported 3 wt % Ni 2 wt % In catalyst, we wished to monitor the interaction between CO and the catalyst. For this purpose DRIFTS studies under CO, CO2, or CO2 + CH4 flow at different temperatures and CO pulse flow experiments at 600 °C followed by mass spectrometry were carried out. A linear carbonyl band at 2013 cm-1 in the DRIFT spectra of the In-promoted catalyst was attributed to CO bonded on Ni atoms surrounded by In neighbors. The lack of bridge and multicoordinated carbonyls also proved the dilution of Ni surface with In. In the presence of a CH4:CO2 = 70:30 dry reforming mixture, stable Ni bonded CO species were found on NiIn/SiO2 suggesting that the metallic sites remained clean during the reaction (unlike on the reference Ni/SiO2). At the end of the reforming reaction, little surface segregation of the original bimetallic particles and the formation of islands with adjacent Ni sites were presumed based on the DRIFTS results. The pulse CO experiments at 600 °C, tailored to detect the most sensitive surface sites for Boudouard reaction, proved that CO dissociation on the bimetallic catalyst was markedly hindered, while it caused carbon deposition on the unpromoted sample. Based on all these results, we postulate a picture of the working catalyst that is dispersed ensembles of NiIn-InOx entities stabilized by SiO2.

AB - Recently a new In-promoted Ni catalyst has been elaborated and published in our laboratory, that has beneficial properties in dry reforming of methane, including inhibited coking. In order to get deeper insights into the coke-free behavior of this SiO2-supported 3 wt % Ni 2 wt % In catalyst, we wished to monitor the interaction between CO and the catalyst. For this purpose DRIFTS studies under CO, CO2, or CO2 + CH4 flow at different temperatures and CO pulse flow experiments at 600 °C followed by mass spectrometry were carried out. A linear carbonyl band at 2013 cm-1 in the DRIFT spectra of the In-promoted catalyst was attributed to CO bonded on Ni atoms surrounded by In neighbors. The lack of bridge and multicoordinated carbonyls also proved the dilution of Ni surface with In. In the presence of a CH4:CO2 = 70:30 dry reforming mixture, stable Ni bonded CO species were found on NiIn/SiO2 suggesting that the metallic sites remained clean during the reaction (unlike on the reference Ni/SiO2). At the end of the reforming reaction, little surface segregation of the original bimetallic particles and the formation of islands with adjacent Ni sites were presumed based on the DRIFTS results. The pulse CO experiments at 600 °C, tailored to detect the most sensitive surface sites for Boudouard reaction, proved that CO dissociation on the bimetallic catalyst was markedly hindered, while it caused carbon deposition on the unpromoted sample. Based on all these results, we postulate a picture of the working catalyst that is dispersed ensembles of NiIn-InOx entities stabilized by SiO2.

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