Formation of phenoxy-type Environmental Persistent Free Radicals (EPFRs) from dissociative adsorption of phenol on Cu/Fe and their partial oxides

Oday H. Ahmed, Mohammednoor Altarawneh, Mohammad Al-Harahsheh, Zhong Tao Jiang, Bogdan Z. Dlugogorski

    Research output: Contribution to journalArticle

    Abstract

    The interplay of phenolic molecules with 3d transition metals, such as Fe and Cu, and their oxide surfaces, provide important fingerprints for environmental burdens associated with thermal recycling of e-waste and subsequent generation of notorious dioxins compounds and phenoxy-type Environmental Persistent Free Radicals (EPFRs). DRIFTS and EPR measurements established a strong interaction of the phenol molecule with transition metal oxides via synthesis of phenolic- and catecholic-type EPFRs intermediates. In this contribution, we comparatively examined the dissociative adsorption of a phenol molecule, as the simplest model for phenolic-type compounds, on Cu and Fe surfaces and their partially oxidized configurations through accurate density functional theory (DFT) studies. The underlying aim is to elucidate the specific underpinning mechanism forming phenoxy- or phenolate-type EFPRs. Simulated results show that, the phenol molecule undergoes fission of its hydroxyl's O–H bond via accessible activation energies. These values are lower by 46.5–74.1% when compared with the analogous gas phase value. Physisorbed molecules of phenol incur very low binding energies in the range of −2.1 to −5.5 over clean Cu/Fe and their oxides surfaces. Molecular attributes based on charge transfer and geometrical features are in accord with the very weak interaction in physisorbed states. Thermo-kinetic parameters established over the temperature region of 300 and 1000 K, exhibit a lower activation energy for scission of phenolic's O–H bonds over the oxide surfaces in reference to their pure surfaces (24.7 and 43.0 kcal mol−1 vs 38.4 and 47.0 kcal mol−1).

    Original languageEnglish
    Article number124921
    Pages (from-to)1-12
    Number of pages12
    JournalChemosphere
    Volume240
    DOIs
    Publication statusPublished - Feb 2020

    Fingerprint

    free radical
    Phenol
    Free radicals
    Oxides
    Adsorption
    Phenols
    Free Radicals
    phenol
    oxide
    adsorption
    Molecules
    transition element
    activation energy
    Metals
    Transition metals
    Activation energy
    Dioxins
    Dermatoglyphics
    Recycling
    Hydroxyl Radical

    Cite this

    Ahmed, Oday H. ; Altarawneh, Mohammednoor ; Al-Harahsheh, Mohammad ; Jiang, Zhong Tao ; Dlugogorski, Bogdan Z. / Formation of phenoxy-type Environmental Persistent Free Radicals (EPFRs) from dissociative adsorption of phenol on Cu/Fe and their partial oxides. In: Chemosphere. 2020 ; Vol. 240. pp. 1-12.
    @article{65e41d5cb5eb4f528281c2217c81d3fe,
    title = "Formation of phenoxy-type Environmental Persistent Free Radicals (EPFRs) from dissociative adsorption of phenol on Cu/Fe and their partial oxides",
    abstract = "The interplay of phenolic molecules with 3d transition metals, such as Fe and Cu, and their oxide surfaces, provide important fingerprints for environmental burdens associated with thermal recycling of e-waste and subsequent generation of notorious dioxins compounds and phenoxy-type Environmental Persistent Free Radicals (EPFRs). DRIFTS and EPR measurements established a strong interaction of the phenol molecule with transition metal oxides via synthesis of phenolic- and catecholic-type EPFRs intermediates. In this contribution, we comparatively examined the dissociative adsorption of a phenol molecule, as the simplest model for phenolic-type compounds, on Cu and Fe surfaces and their partially oxidized configurations through accurate density functional theory (DFT) studies. The underlying aim is to elucidate the specific underpinning mechanism forming phenoxy- or phenolate-type EFPRs. Simulated results show that, the phenol molecule undergoes fission of its hydroxyl's O–H bond via accessible activation energies. These values are lower by 46.5–74.1{\%} when compared with the analogous gas phase value. Physisorbed molecules of phenol incur very low binding energies in the range of −2.1 to −5.5 over clean Cu/Fe and their oxides surfaces. Molecular attributes based on charge transfer and geometrical features are in accord with the very weak interaction in physisorbed states. Thermo-kinetic parameters established over the temperature region of 300 and 1000 K, exhibit a lower activation energy for scission of phenolic's O–H bonds over the oxide surfaces in reference to their pure surfaces (24.7 and 43.0 kcal mol−1 vs 38.4 and 47.0 kcal mol−1).",
    author = "Ahmed, {Oday H.} and Mohammednoor Altarawneh and Mohammad Al-Harahsheh and Jiang, {Zhong Tao} and Dlugogorski, {Bogdan Z.}",
    year = "2020",
    month = "2",
    doi = "10.1016/j.chemosphere.2019.124921",
    language = "English",
    volume = "240",
    pages = "1--12",
    journal = "Chemosphere",
    issn = "0045-6535",
    publisher = "Global Science Books",

    }

    Formation of phenoxy-type Environmental Persistent Free Radicals (EPFRs) from dissociative adsorption of phenol on Cu/Fe and their partial oxides. / Ahmed, Oday H.; Altarawneh, Mohammednoor; Al-Harahsheh, Mohammad; Jiang, Zhong Tao; Dlugogorski, Bogdan Z.

    In: Chemosphere, Vol. 240, 124921, 02.2020, p. 1-12.

    Research output: Contribution to journalArticle

    TY - JOUR

    T1 - Formation of phenoxy-type Environmental Persistent Free Radicals (EPFRs) from dissociative adsorption of phenol on Cu/Fe and their partial oxides

    AU - Ahmed, Oday H.

    AU - Altarawneh, Mohammednoor

    AU - Al-Harahsheh, Mohammad

    AU - Jiang, Zhong Tao

    AU - Dlugogorski, Bogdan Z.

    PY - 2020/2

    Y1 - 2020/2

    N2 - The interplay of phenolic molecules with 3d transition metals, such as Fe and Cu, and their oxide surfaces, provide important fingerprints for environmental burdens associated with thermal recycling of e-waste and subsequent generation of notorious dioxins compounds and phenoxy-type Environmental Persistent Free Radicals (EPFRs). DRIFTS and EPR measurements established a strong interaction of the phenol molecule with transition metal oxides via synthesis of phenolic- and catecholic-type EPFRs intermediates. In this contribution, we comparatively examined the dissociative adsorption of a phenol molecule, as the simplest model for phenolic-type compounds, on Cu and Fe surfaces and their partially oxidized configurations through accurate density functional theory (DFT) studies. The underlying aim is to elucidate the specific underpinning mechanism forming phenoxy- or phenolate-type EFPRs. Simulated results show that, the phenol molecule undergoes fission of its hydroxyl's O–H bond via accessible activation energies. These values are lower by 46.5–74.1% when compared with the analogous gas phase value. Physisorbed molecules of phenol incur very low binding energies in the range of −2.1 to −5.5 over clean Cu/Fe and their oxides surfaces. Molecular attributes based on charge transfer and geometrical features are in accord with the very weak interaction in physisorbed states. Thermo-kinetic parameters established over the temperature region of 300 and 1000 K, exhibit a lower activation energy for scission of phenolic's O–H bonds over the oxide surfaces in reference to their pure surfaces (24.7 and 43.0 kcal mol−1 vs 38.4 and 47.0 kcal mol−1).

    AB - The interplay of phenolic molecules with 3d transition metals, such as Fe and Cu, and their oxide surfaces, provide important fingerprints for environmental burdens associated with thermal recycling of e-waste and subsequent generation of notorious dioxins compounds and phenoxy-type Environmental Persistent Free Radicals (EPFRs). DRIFTS and EPR measurements established a strong interaction of the phenol molecule with transition metal oxides via synthesis of phenolic- and catecholic-type EPFRs intermediates. In this contribution, we comparatively examined the dissociative adsorption of a phenol molecule, as the simplest model for phenolic-type compounds, on Cu and Fe surfaces and their partially oxidized configurations through accurate density functional theory (DFT) studies. The underlying aim is to elucidate the specific underpinning mechanism forming phenoxy- or phenolate-type EFPRs. Simulated results show that, the phenol molecule undergoes fission of its hydroxyl's O–H bond via accessible activation energies. These values are lower by 46.5–74.1% when compared with the analogous gas phase value. Physisorbed molecules of phenol incur very low binding energies in the range of −2.1 to −5.5 over clean Cu/Fe and their oxides surfaces. Molecular attributes based on charge transfer and geometrical features are in accord with the very weak interaction in physisorbed states. Thermo-kinetic parameters established over the temperature region of 300 and 1000 K, exhibit a lower activation energy for scission of phenolic's O–H bonds over the oxide surfaces in reference to their pure surfaces (24.7 and 43.0 kcal mol−1 vs 38.4 and 47.0 kcal mol−1).

    UR - http://www.scopus.com/inward/record.url?scp=85072772579&partnerID=8YFLogxK

    U2 - 10.1016/j.chemosphere.2019.124921

    DO - 10.1016/j.chemosphere.2019.124921

    M3 - Article

    C2 - 31726593

    AN - SCOPUS:85072772579

    VL - 240

    SP - 1

    EP - 12

    JO - Chemosphere

    JF - Chemosphere

    SN - 0045-6535

    M1 - 124921

    ER -