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Mechanistic insights into methane total oxidation over Cu/Hydroxyapatite catalyst synthesized with β-Cyclodextrin assistance

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Abstract
The total oxidation of methane (CH4), a highly stable alkane volatile organic compound (VOC), using low-cost Cu-based catalysts, has garnered considerable attention. Nonetheless, challenges such as Cu particle agglomeration and the lack of consensus on mechanism of CH4 total oxidation over Cu-based catalysts remain. In this work, β-cyclodextrin (βCD) was introduced during Cu/hydroxyapatite catalyst (βCD-Cu/HAP) preparation, and its catalytic performance in CH4 total oxidation was compared with the Cu/HAP catalyst. Both materials were prepared using the wet impregnation method and thoroughly characterized. It was found that utilization of βCD, which decomposed during calcination, led to smaller Cu particle size (from 61 to 34 nm) and better Cu dispersion (from 1.9 to 3.5 %), resulting in an enhancement of the catalyst reduction properties. Additionally, the βCD-Cu/HAP catalyst possessed a higher oxygen storage capacity, demonstrating its superior ability to replenish the oxygen vacancies. The βCD-Cu/HAP catalyst activity was double that of the original Cu/HAP catalyst with a 20 lower activation energy, as determined by fitting the initial reaction rate to a power-law model. Further, Langmuir–Hinshelwood (LH), Eley–Rideal (ER), and Mars–van Krevelen (MVK) type rate expressions were regressed to the experimental data. After statistical and physico-chemical assessments, the MVK mechanism involving two oxidized sites and one reduced site with H2O adsorption on oxidized sites was identified as the most appropriate model for describing the experimental data. These findings offer an enhanced understanding of CH4 total oxidation, guiding the development of efficient, low-cost catalysts for this reaction.
Keywords
Catalytic oxidation, Volatile organic compounds, beta-cyclodextrin, Copper, Mars-van Krevelen, Roman symbols, OXIDE CATALYSTS, COPPER-OXIDE, COMBUSTION, KINETICS, CO, REDUCTION

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Citation

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MLA
Monjezi, Reza, et al. “Mechanistic Insights into Methane Total Oxidation over Cu/Hydroxyapatite Catalyst Synthesized with β-Cyclodextrin Assistance.” CHEMICAL ENGINEERING JOURNAL, vol. 489, 2024, doi:10.1016/j.cej.2024.151324.
APA
Monjezi, R., Bouriakova, A., Bjelić, A., Heynderickx, P., Heynderickx, G., Poelman, D., … Thybaut, J. (2024). Mechanistic insights into methane total oxidation over Cu/Hydroxyapatite catalyst synthesized with β-Cyclodextrin assistance. CHEMICAL ENGINEERING JOURNAL, 489. https://doi.org/10.1016/j.cej.2024.151324
Chicago author-date
Monjezi, Reza, Alexandra Bouriakova, Ana Bjelić, Philippe Heynderickx, Geraldine Heynderickx, Dirk Poelman, Jean-Marc Giraudon, Jean-François Lamonier, Rino Morent, and Joris Thybaut. 2024. “Mechanistic Insights into Methane Total Oxidation over Cu/Hydroxyapatite Catalyst Synthesized with β-Cyclodextrin Assistance.” CHEMICAL ENGINEERING JOURNAL 489. https://doi.org/10.1016/j.cej.2024.151324.
Chicago author-date (all authors)
Monjezi, Reza, Alexandra Bouriakova, Ana Bjelić, Philippe Heynderickx, Geraldine Heynderickx, Dirk Poelman, Jean-Marc Giraudon, Jean-François Lamonier, Rino Morent, and Joris Thybaut. 2024. “Mechanistic Insights into Methane Total Oxidation over Cu/Hydroxyapatite Catalyst Synthesized with β-Cyclodextrin Assistance.” CHEMICAL ENGINEERING JOURNAL 489. doi:10.1016/j.cej.2024.151324.
Vancouver
1.
Monjezi R, Bouriakova A, Bjelić A, Heynderickx P, Heynderickx G, Poelman D, et al. Mechanistic insights into methane total oxidation over Cu/Hydroxyapatite catalyst synthesized with β-Cyclodextrin assistance. CHEMICAL ENGINEERING JOURNAL. 2024;489.
IEEE
[1]
R. Monjezi et al., “Mechanistic insights into methane total oxidation over Cu/Hydroxyapatite catalyst synthesized with β-Cyclodextrin assistance,” CHEMICAL ENGINEERING JOURNAL, vol. 489, 2024.
@article{01HWKF5F2DFGX52WW6XV85NFNC,
  abstract     = {{The total oxidation of methane (CH4), a highly stable alkane volatile organic compound (VOC), using low-cost Cu-based catalysts, has garnered considerable attention. Nonetheless, challenges such as Cu particle agglomeration and the lack of consensus on mechanism of CH4 total oxidation over Cu-based catalysts remain. In this work, β-cyclodextrin (βCD) was introduced during Cu/hydroxyapatite catalyst (βCD-Cu/HAP) preparation, and its catalytic performance in CH4 total oxidation was compared with the Cu/HAP catalyst. Both materials were prepared using the wet impregnation method and thoroughly characterized. It was found that utilization of βCD, which decomposed during calcination, led to smaller Cu particle size (from 61 to 34 nm) and better Cu dispersion (from 1.9 to 3.5 %), resulting in an enhancement of the catalyst reduction properties. Additionally, the βCD-Cu/HAP catalyst possessed a higher oxygen storage capacity, demonstrating its superior ability to replenish the oxygen vacancies. The βCD-Cu/HAP catalyst activity was double that of the original Cu/HAP catalyst with a 20 
 lower activation energy, as determined by fitting the initial reaction rate to a power-law model. Further, Langmuir–Hinshelwood (LH), Eley–Rideal (ER), and Mars–van Krevelen (MVK) type rate expressions were regressed to the experimental data. After statistical and physico-chemical assessments, the MVK mechanism involving two oxidized sites and one reduced site with H2O adsorption on oxidized sites was identified as the most appropriate model for describing the experimental data. These findings offer an enhanced understanding of CH4 total oxidation, guiding the development of efficient, low-cost catalysts for this reaction.}},
  articleno    = {{151324}},
  author       = {{Monjezi, Reza and Bouriakova, Alexandra and Bjelić, Ana and Heynderickx, Philippe and Heynderickx, Geraldine and Poelman, Dirk and Giraudon, Jean-Marc and Lamonier, Jean-François and Morent, Rino and Thybaut, Joris}},
  issn         = {{1385-8947}},
  journal      = {{CHEMICAL ENGINEERING JOURNAL}},
  keywords     = {{Catalytic oxidation,Volatile organic compounds,beta-cyclodextrin,Copper,Mars-van Krevelen,Roman symbols,OXIDE CATALYSTS,COPPER-OXIDE,COMBUSTION,KINETICS,CO,REDUCTION}},
  language     = {{eng}},
  pages        = {{12}},
  title        = {{Mechanistic insights into methane total oxidation over Cu/Hydroxyapatite catalyst synthesized with β-Cyclodextrin assistance}},
  url          = {{http://doi.org/10.1016/j.cej.2024.151324}},
  volume       = {{489}},
  year         = {{2024}},
}

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