Density functional theory analysis of reaction mechanism of hypophosphite ions on metal surfaces

Masahiro Kunimoto, Takuya Shimada, Shuichi Odagiri, Hiromi Nakai, Takayuki Homma

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    18 Citations (Scopus)

    Abstract

    The elementary steps of the reactions of hypophosphite ions with Cu, Ni, and Pd were calculated theoretically using Density Functional Theory (DFT) to demonstrate the reaction mechanism and gain insight at the molecular level. The elementary steps of these reactions are adsorption, dehydrogenation, and oxidation (hydroxyl base attack). In the adsorption step, hypophosphite ions adsorb onto each surface spontaneously with stabilities in the order of Ni (111) > Pd (111) > Cu (111). In the dehydrogenation step, hypophosphite ions dehydrogenate on Ni (111) and Pd (111) with small reaction barriers, whereas they react on Cu (111) with a large reaction barrier. The large reaction barrier on Cu (111) is not compensated for by the adsorption energy on the surface. In the oxidation step, dehydrogenated anions on each metal surface react spontaneously with the hydroxyl base. The reaction barriers on each metal surface in this step are not so significant compared to the adsorption energies on each surface, suggesting that a reaction barrier of hypophosphite ion oxidation should exist in the dehydrogenation step and only be observed for Cu (111). This proposition elucidates the experimental catalytic behaviors of metal surfaces in the electroless deposition process using hypophosphite ions.

    Original languageEnglish
    JournalJournal of the Electrochemical Society
    Volume158
    Issue number9
    DOIs
    Publication statusPublished - 2011

    Fingerprint

    metal surfaces
    Density functional theory
    Metals
    Ions
    density functional theory
    Dehydrogenation
    Adsorption
    ions
    dehydrogenation
    Hydroxyl Radical
    Oxidation
    adsorption
    oxidation
    Electroless plating
    electroless deposition
    Anions
    Negative ions
    attack
    anions
    energy

    ASJC Scopus subject areas

    • Electrochemistry
    • Electronic, Optical and Magnetic Materials
    • Materials Chemistry
    • Surfaces, Coatings and Films
    • Renewable Energy, Sustainability and the Environment
    • Condensed Matter Physics

    Cite this

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    abstract = "The elementary steps of the reactions of hypophosphite ions with Cu, Ni, and Pd were calculated theoretically using Density Functional Theory (DFT) to demonstrate the reaction mechanism and gain insight at the molecular level. The elementary steps of these reactions are adsorption, dehydrogenation, and oxidation (hydroxyl base attack). In the adsorption step, hypophosphite ions adsorb onto each surface spontaneously with stabilities in the order of Ni (111) > Pd (111) > Cu (111). In the dehydrogenation step, hypophosphite ions dehydrogenate on Ni (111) and Pd (111) with small reaction barriers, whereas they react on Cu (111) with a large reaction barrier. The large reaction barrier on Cu (111) is not compensated for by the adsorption energy on the surface. In the oxidation step, dehydrogenated anions on each metal surface react spontaneously with the hydroxyl base. The reaction barriers on each metal surface in this step are not so significant compared to the adsorption energies on each surface, suggesting that a reaction barrier of hypophosphite ion oxidation should exist in the dehydrogenation step and only be observed for Cu (111). This proposition elucidates the experimental catalytic behaviors of metal surfaces in the electroless deposition process using hypophosphite ions.",
    author = "Masahiro Kunimoto and Takuya Shimada and Shuichi Odagiri and Hiromi Nakai and Takayuki Homma",
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    AU - Kunimoto, Masahiro

    AU - Shimada, Takuya

    AU - Odagiri, Shuichi

    AU - Nakai, Hiromi

    AU - Homma, Takayuki

    PY - 2011

    Y1 - 2011

    N2 - The elementary steps of the reactions of hypophosphite ions with Cu, Ni, and Pd were calculated theoretically using Density Functional Theory (DFT) to demonstrate the reaction mechanism and gain insight at the molecular level. The elementary steps of these reactions are adsorption, dehydrogenation, and oxidation (hydroxyl base attack). In the adsorption step, hypophosphite ions adsorb onto each surface spontaneously with stabilities in the order of Ni (111) > Pd (111) > Cu (111). In the dehydrogenation step, hypophosphite ions dehydrogenate on Ni (111) and Pd (111) with small reaction barriers, whereas they react on Cu (111) with a large reaction barrier. The large reaction barrier on Cu (111) is not compensated for by the adsorption energy on the surface. In the oxidation step, dehydrogenated anions on each metal surface react spontaneously with the hydroxyl base. The reaction barriers on each metal surface in this step are not so significant compared to the adsorption energies on each surface, suggesting that a reaction barrier of hypophosphite ion oxidation should exist in the dehydrogenation step and only be observed for Cu (111). This proposition elucidates the experimental catalytic behaviors of metal surfaces in the electroless deposition process using hypophosphite ions.

    AB - The elementary steps of the reactions of hypophosphite ions with Cu, Ni, and Pd were calculated theoretically using Density Functional Theory (DFT) to demonstrate the reaction mechanism and gain insight at the molecular level. The elementary steps of these reactions are adsorption, dehydrogenation, and oxidation (hydroxyl base attack). In the adsorption step, hypophosphite ions adsorb onto each surface spontaneously with stabilities in the order of Ni (111) > Pd (111) > Cu (111). In the dehydrogenation step, hypophosphite ions dehydrogenate on Ni (111) and Pd (111) with small reaction barriers, whereas they react on Cu (111) with a large reaction barrier. The large reaction barrier on Cu (111) is not compensated for by the adsorption energy on the surface. In the oxidation step, dehydrogenated anions on each metal surface react spontaneously with the hydroxyl base. The reaction barriers on each metal surface in this step are not so significant compared to the adsorption energies on each surface, suggesting that a reaction barrier of hypophosphite ion oxidation should exist in the dehydrogenation step and only be observed for Cu (111). This proposition elucidates the experimental catalytic behaviors of metal surfaces in the electroless deposition process using hypophosphite ions.

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