A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä
Metal–water interface formation : Thermodynamics from ab initio molecular dynamics simulations (2024)
Domínguez-Flores, F., Kiljunen, T., Groß, A., Sakong, S., & Melander, M. M. (2024). Metal–water interface formation : Thermodynamics from ab initio molecular dynamics simulations. Journal of Chemical Physics, 161(4), Article 044705. https://doi.org/10.1063/5.0220576
JYU-tekijät tai -toimittajat
Julkaisun tiedot
Julkaisun kaikki tekijät tai toimittajat: Domínguez-Flores, Fabiola; Kiljunen, Toni; Groß, Axel; Sakong, Sung; Melander, Marko M.
Lehti tai sarja: Journal of Chemical Physics
ISSN: 0021-9606
eISSN: 1089-7690
Julkaisuvuosi: 2024
Ilmestymispäivä: 26.07.2024
Volyymi: 161
Lehden numero: 4
Artikkelinumero: 044705
Kustantaja: AIP Publishing
Julkaisumaa: Yhdysvallat (USA)
Julkaisun kieli: englanti
DOI: https://doi.org/10.1063/5.0220576
Julkaisun avoin saatavuus: Ei avoin
Julkaisukanavan avoin saatavuus:
Julkaisu on rinnakkaistallennettu (JYX): https://jyx.jyu.fi/handle/123456789/97032
Tiivistelmä
Metal–water interfaces are central to many electrochemical, (electro)catalytic, and materials science processes and systems. However, our current understanding of their thermodynamic properties is limited by the scarcity of accurate experimental and computational data and procedures. In this work, thermodynamic quantities for metal–water interface formation are computed for a range of FCC(111) surfaces (Pd, Pt, Au, Ag, Rh, and PdAu) through extensive density functional theory based molecular dynamics and the two-phase entropy model. We show that metal–water interface formation is thermodynamically favorable and that most metal surfaces studied in this work are completely wettable, i.e., have contact angles of zero. Interfacial water has higher entropy than bulk water due to the increased population of low-frequency translational modes. The entropic contributions also correlate with the orientational water density, and the highest solvation entropies are observed for interfaces with a moderately ordered first water layer; the entropic contributions account for up to ∼25% of the formation free energy. Water adsorption energy correlates with the water orientation and structure and is found to be a good descriptor of the internal energy part of the interface formation free energy, but it alone cannot satisfactorily explain the interfacial thermodynamics; the interface formation is driven by the competition between energetic and entropic contributions. The obtained results and insight can be used to develop, parameterize, and benchmark theoretical and computational methods for studying metal–water interfaces. Overall, our study yields benchmark-quality data and fundamental insight into the thermodynamic forces driving metal–water interface formation.
YSO-asiasanat: pintakemia; rajapinnat (pinnat); rajapintailmiöt; termodynamiikka; simulointi; molekyylidynamiikka; tiheysfunktionaaliteoria
Vapaat asiasanat: density functional theory; molecular dynamics; quantum mechanical/molecular mechanical calculations; thermodynamics; computational methods; liquid solid interfaces; catalysts and catalysis; solvation
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OKM-raportointi: Kyllä
VIRTA-lähetysvuosi: 2024
Alustava JUFO-taso: 1