skip to main content
Idioma:

Tight electrostatic regulation of the OH production rate from the photolysis of hydrogen peroxide adsorbed on surfaces

Ruiz-López, Manuel F ; Martins-Costa, Marilia T C ; Francisco, Joseph S ; Anglada, Josep M

Proceedings of the National Academy of Sciences - PNAS, 2021-07, Vol.118 (30) [Periódico revisado por pares]

United States: National Academy of Sciences

Texto completo disponível

Citações Citado por
  • Título:
    Tight electrostatic regulation of the OH production rate from the photolysis of hydrogen peroxide adsorbed on surfaces
  • Autor: Ruiz-López, Manuel F ; Martins-Costa, Marilia T C ; Francisco, Joseph S ; Anglada, Josep M
  • Assuntos: Absorption ; Absorption spectra ; Aqueous electrolytes ; Biomedical materials ; Chemical Sciences ; Free radicals ; Hydrogen ; Hydrogen peroxide ; Interfaces ; or physical chemistry ; Oxidants ; Oxidizing agents ; Photochemicals ; Photochemistry ; Photolysis ; Physical Sciences ; Surface chemistry ; Theoretical and ; Vapor phases
  • É parte de: Proceedings of the National Academy of Sciences - PNAS, 2021-07, Vol.118 (30)
  • Notas: ObjectType-Article-1
    SourceType-Scholarly Journals-1
    ObjectType-Feature-2
    content type line 23
    Reviewers: B.C.-C., University of Lisbon; and V.V., University of Colorado Boulder.
    Contributed by Joseph S. Francisco, June 21, 2021 (sent for review April 5, 2021); reviewed by Benedito Costa-Cabral and Veronica Vaida
    Author contributions: M.F.R.-L., M.T.C.M.-C., J.S.F., and J.M.A. designed research; M.F.R.-L., M.T.C.M.-C., J.S.F., and J.M.A. performed research; M.F.R.-L., M.T.C.M.-C., J.S.F., and J.M.A. analyzed data; and M.F.R.-L. wrote the paper.
  • Descrição: Recently, experimental and theoretical works have reported evidence indicating that photochemical processes may significantly be accelerated at heterogeneous interfaces, although a complete understanding of the phenomenon is still lacking. We have carried out a theoretical study of interface and surface effects on the photochemistry of hydrogen peroxide (H O ) using high-level ab initio methods and a variety of models. Hydrogen peroxide is an important oxidant that decomposes in the presence of light, forming two OH radicals. This elementary photochemical process has broad interest and is used in many practical applications. Our calculations show that it can drastically be affected by heterogeneous interfaces. Thus, compared to gas phase, the photochemistry of H O appears to be slowed on the surface of apolar or low-polar surfaces and, in contrast, hugely accelerated on ionic surfaces or the surface of aqueous electrolytes. We give particular attention to the case of the neat air-water interface. The calculated photolysis rate is similar to the gas phase, which stems from the compensation of two opposite effects, the blue shift of the n→σ* absorption band and the increase of the absorption intensity. Nevertheless, due to the high affinity of H O for the air-water interface, the predicted OH production rate is up to five to six orders of magnitude larger. Overall, our results show that the photochemistry of H O in heterogeneous environments is greatly modulated by the nature of the surface, and this finding opens interesting new perspectives for technological and biomedical applications, and possibly in various atmospheres.
  • Editor: United States: National Academy of Sciences
  • Idioma: Inglês
Links
Voltar para lista de resultados
Ir para página anteriorAnterior Resultado  7 AvançarIr para próxima página

  • Realização: ABCD-USP USP   Logos de Redes Sociais: Freepik

Buscando em bases de dados remotas. Favor aguardar.