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Reactivity of metal oxide clusters with hydrogen peroxide and water: a DFT study evaluating the performance of different exchange-correlation functionals
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Applied Physical Chemistry.ORCID iD: 0000-0002-0086-5536
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Applied Physical Chemistry.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Applied Physical Chemistry.ORCID iD: 0000-0003-2673-075X
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Applied Physical Chemistry.ORCID iD: 0000-0003-0663-0751
2013 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 15, no 15, 5539-5552 p.Article in journal (Refereed) Published
Abstract [en]

We have performed a density functional theory (DFT) investigation of the interactions of H2O2, H2O and HO radicals with clusters of ZrO2, TiO2 and Y2O3. Different modes of H2O adsorption onto the clusters were studied. In almost all the cases the dissociative adsorption is more exothermic than molecular adsorption. At the surfaces where H2O has undergone dissociative adsorption, the adsorption of H2O2 and the transition state for its decomposition are mediated by hydrogen bonding with the surface HO groups. Using the functionals B3LYP, B3LYP-D and M06 with clusters of 26 and 8 units of ZrO2, the M06 functional performed better than B3LYP in describing the reaction of decomposition of H2O2 and the adsorption of H2O. Additionally, we investigated clusters of the type (ZrO2)2, (TiO2)2 and (Y2O3) and the performance of the functionals B3LYP, B3LYP-D, B3LYP*, M06, M06-L, PBE0, PBE and PWPW91 in describing H2O2, H2O and HO˙ adsorption and the energy barrier for decomposition of H2O2. The trends obtained for HO˙ adsorption onto the clusters are discussed in terms of the ionization energy of the metal cation present in the oxide. In order to correctly account for the existence of an energy barrier for the decomposition of H2O2, the functional used must include Hartree-Fock exchange. Using minimal cluster models, the best performance in describing the energy barrier for H2O2 decomposition was obtained with the M06 and PBE0 functionals - the average absolute deviations from experiments are 6 kJ mol(-1) and 5 kJ mol(-1) respectively. With the M06 functional and a larger monoclinic (ZrO2)8 cluster model, the performance is in excellent agreement with experimental data. For the different oxides, PBE0 was found to be the most effective functional in terms of performance and computational time cost.

Place, publisher, year, edition, pages
2013. Vol. 15, no 15, 5539-5552 p.
Keyword [en]
Generalized Gradient Approximation, Temperature-Programmed Desorption, Main-Group Thermochemistry, Self-Interaction Error, Periodic Ab-Initio, Noncovalent Interactions, Density Functionals, Hydroxyl Radicals, Transition-Metal, Monoclinic Zirconia
National Category
Physical Sciences
URN: urn:nbn:se:kth:diva-119801DOI: 10.1039/c3cp44559cISI: 000316467800030PubMedID: 23460024ScopusID: 2-s2.0-84875478707OAI: diva2:612579
Swedish Foundation for Strategic Research

QC 20130322

Available from: 2013-03-22 Created: 2013-03-22 Last updated: 2013-04-19Bibliographically approved
In thesis
1. Reactions of aqueous radiolysis products with oxide surfaces: An experimental and DFT study
Open this publication in new window or tab >>Reactions of aqueous radiolysis products with oxide surfaces: An experimental and DFT study
2013 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The reactions between aqueous radiolysis products and oxide surfaces are important in nuclear technology in many ways. In solid-liquid systems, they affect (and at the same time are dependent on) both the solution chemistry and the stability of materials under the influence of ionizing radiation. The stability of surface oxides is a factor that determines the longevity of the materials where such oxides are formed. Additionally, the aqueous radiolysis products are responsible for corrosion and erosion of the materials.

  In this study, the reactions between radiolysis products of water – mainly H2O2 and HO radicals – with metal, lanthanide and actinide oxides are investigated. For this, experimental and computational chemistry methods are employed. For the experimental study of these systems it was necessary to implement new methodologies especially for the study of the reactive species – the HO radicals. Similarly, the computational study also required the development of models and benchmarking of methods. The experiments combined with the computational chemistry studies produced valuable kinetic, energetic and mechanistic data.

  It is demonstrated here that the HO radicals are a primary product of the decomposition of H2O2. For all the materials, the catalytic decomposition of H2O2 consists first of molecular adsorption onto the surfaces of the oxides. This step is followed by the cleavage of the O-O bond in H2O2 to form HO radicals. The HO radicals are able to react further with the hydroxylated surfaces of the oxides to form water and a surface bound HO center. The dynamics of formation of HO vary widely for the different materials studied. These differences are also observed in the activation energies and kinetics for decomposition of H2O2. It is found further that the removal of HO from the system where H2O2 undergoes decomposition, by means of a scavenger, leads to the spontaneous formation of H2.

  The combined theoretical-experimental methodology led to mechanistic understanding of the reactivity of the oxide materials towards H2O2 and HO radicals. This reactivity can be expressed in terms of fundamental properties of the cations present in the oxides. Correlations were found between several properties of the metal cations present in the oxides and adsorption energies of H2O, adsorption energies of HO radicals and energy barriers for H2O2 decomposition. This knowledge can aid in improving materials and processes important for nuclear technological systems, catalysis, and energy storage, and also help to better understand geochemical processes.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2013. 121 p.
Trita-CHE-Report, ISSN 1654-1081 ; 2013:12
hydrogen peroxide, hydrogen production, metal, oxides, lanthanide, catalysis, density functional theory, surface, reactions, chemistry
National Category
Physical Chemistry Materials Chemistry Theoretical Chemistry
Research subject
SRA - Energy; SRA - Production
urn:nbn:se:kth:diva-119780 (URN)978-91-7501-683-2 (ISBN)
Public defence
2013-04-12, K2, Teknikringen 28, KTH, Stockholm, 10:00 (English)
StandUpXPRES - Initiative for excellence in production research

QC 20130322

Available from: 2013-03-22 Created: 2013-03-21 Last updated: 2013-03-22Bibliographically approved

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