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Yang, M., Soroka, I. & Jonsson, M. (2017). Exploring the limitations of the Hantzsch method used for quantification of hydroxyl radicals in systems of relevance for interfacial radiation chemistry. Radiation Physics and Chemistry, 130, 1-4.
Open this publication in new window or tab >>Exploring the limitations of the Hantzsch method used for quantification of hydroxyl radicals in systems of relevance for interfacial radiation chemistry
2017 (English)In: Radiation Physics and Chemistry, ISSN 0969-806X, E-ISSN 1879-0895, Vol. 130, 1-4 p.Article in journal (Refereed) Published
Abstract [en]

In the presence of Tris or methanol, hydroxyl radicals in systems of relevance for interfacial radiation chemistry can be quantified indirectly via the Hantzsch method by determining the amount of the scavenging product formaldehyde formed. In this work, the influence of the presence of H2O2 on the Hantzsch method using acetoacetanilide (AAA) as derivatization reagent is studied. The experiments show that the measured CH2O concentration deviates from the actual concentration in the presence of H2O2 and the deviation increases with increasing [H2O2]0/[CH2O]0. The deviation is negative, i.e., the measured formaldehyde concentration is lower than the actual concentration. This leads to an underestimation of the hydroxyl radical production in systems containing significant amount of H2O2. The main reason for the deviation is found to be three coupled equilibria involving H2O2, CH2O and the derivative produced in the Hantzsch method.

Place, publisher, year, edition, pages
Elsevier, 2017
Keyword
Acetoacetanilide, Formaldehyde, Hantzsch method, Hydrogen peroxide, Hydroxyl radical, Derivatization reagent, Formaldehyde concentrations, Hantzsch, Hydroxyl radicals, Radiation chemistry, acetanilide derivative, unclassified drug, Article, chemical analysis, chemical reaction kinetics, concentration (parameters), controlled study, interfacial radiation chemistry, quantitative analysis, radiochemistry
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-195129 (URN)10.1016/j.radphyschem.2016.07.021 (DOI)000388777200001 ()2-s2.0-84979622715 (Scopus ID)
Note

QC 20161121

Available from: 2016-11-21 Created: 2016-11-02 Last updated: 2017-11-29Bibliographically approved
Nilsson, K., Roth, O. & Jonsson, M. (2017). Oxidative dissolution of ADOPT compared to standard UO2 fuel. Journal of Nuclear Materials, 488, 123-128.
Open this publication in new window or tab >>Oxidative dissolution of ADOPT compared to standard UO2 fuel
2017 (English)In: Journal of Nuclear Materials, ISSN 0022-3115, E-ISSN 1873-4820, Vol. 488, 123-128 p.Article in journal (Refereed) Published
Abstract [en]

In this work we have studied oxidative dissolution of pure UO2 and ADOPT (UO2 doped with Al and Cr) pellets using H2O2 and gammaradiolysis to induce the process. There is a small but significant difference in the oxidative dissolution rate of UO2 and ADOPT pellets, respectively. However, the difference in oxidative dissolution yield is insignificant. Leaching experiments were also performed on in-reactor irradiated ADOPT and UO2 pellets under oxidizing conditions. The results indicate that the U(VI) release is slightly slower from the ADOPT pellet compared to the UO2. This could be attributed to differences in exposed surface area. However, fission products with low UO2 solubility display a higher relative release from ADOPT fuel compared to standard UO2-fuel. This is attributed to a lower matrix solubility imposed by the dopants in ADOPT fuel. The release of Cs is higher from UO2 which is attributed to the larger grain size of ADOPT. © 2017 Elsevier B.V.

Place, publisher, year, edition, pages
Elsevier B.V., 2017
Keyword
Doping (additives), Fission products, Fuels, Pelletizing, Solubility, Exposed surfaces, Grain size, Leaching experiments, Matrix solubility, Oxidative dissolution, Oxidizing conditions, Dissolution
National Category
Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-207344 (URN)10.1016/j.jnucmat.2017.02.044 (DOI)000400218100012 ()2-s2.0-85015707126 (Scopus ID)
Note

QC 20170522

Available from: 2017-05-22 Created: 2017-05-22 Last updated: 2017-05-23Bibliographically approved
Lousada, C. M., Soroka, I. L., Yagodzinskyy, Y., Tarakina, N. V., Todoshchenko, O., Hänninen, H., . . . Jonsson, M. (2016). Gamma radiation induces hydrogen absorption by copper in water. Scientific Reports, 6, Article ID 24234.
Open this publication in new window or tab >>Gamma radiation induces hydrogen absorption by copper in water
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2016 (English)In: Scientific Reports, ISSN 2045-2322, E-ISSN 2045-2322, Vol. 6, 24234Article in journal (Refereed) Published
Abstract [en]

One of the most intricate issues of nuclear power is the long-term safety of repositories for radioactive waste. These repositories can have an impact on future generations for a period of time orders of magnitude longer than any known civilization. Several countries have considered copper as an outer corrosion barrier for canisters containing spent nuclear fuel. Among the many processes that must be considered in the safety assessments, radiation induced processes constitute a key-component. Here we show that copper metal immersed in water uptakes considerable amounts of hydrogen when exposed to γ-radiation. Additionally we show that the amount of hydrogen absorbed by copper depends on the total dose of radiation. At a dose of 69 kGy the uptake of hydrogen by metallic copper is 7 orders of magnitude higher than when the absorption is driven by H2(g) at a pressure of 1 atm in a non-irradiated dry system. Moreover, irradiation of copper in water causes corrosion of the metal and the formation of a variety of surface cavities, nanoparticle deposits, and islands of needle-shaped crystals. Hence, radiation enhanced uptake of hydrogen by spent nuclear fuel encapsulating materials should be taken into account in the safety assessments of nuclear waste repositories.

Place, publisher, year, edition, pages
Nature Publishing Group, 2016
National Category
Manufacturing, Surface and Joining Technology Physical Sciences
Identifiers
urn:nbn:se:kth:diva-187004 (URN)10.1038/srep24234 (DOI)000374226400001 ()2-s2.0-84964306889 (Scopus ID)
Note

QC 20160523

Available from: 2016-05-23 Created: 2016-05-16 Last updated: 2017-11-30Bibliographically approved
Dispenza, C., Sabatino, M. A., Grimaldi, N., Mangione, M. R., Walo, M., Murugan, E. & Jonsson, M. (2016). On the origin of functionalization in one-pot radiation synthesis of nanogels from aqueous polymer solutions. RSC Advances, 6(4), 2582-2591.
Open this publication in new window or tab >>On the origin of functionalization in one-pot radiation synthesis of nanogels from aqueous polymer solutions
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2016 (English)In: RSC Advances, ISSN 2046-2069, E-ISSN 2046-2069, Vol. 6, no 4, 2582-2591 p.Article in journal (Refereed) Published
Abstract [en]

Radiation-engineered poly(N-vinyl pyrrolidone) nanogels are very interesting biocompatible nanocarriers for i.v. administration of therapeutics and contrast agents for bioimaging. The manufacturing process is fast and effective, it grants excellent control of particle size and simultaneous sterilization of the formed nanogels. Interestingly, primary amino groups and carboxyl groups, useful for (bio) conjugation, are also formed in a dose-dependent fashion. In this paper, by means of both numerical simulations and experiments, the origin of nanogel size control and functionalization is investigated. This understanding offers a new dimension for the design and production of radiation-sculptured multifunctional nanocarriers from aqueous solutions of polymers.

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2016
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-182875 (URN)10.1039/c5ra23926e (DOI)000368193500008 ()2-s2.0-84954058310 (Scopus ID)
Note

QC 20160224

Available from: 2016-02-24 Created: 2016-02-23 Last updated: 2017-11-30Bibliographically approved
Fidalgo, A. B., Dahlgren, B., Brinck, T. & Jonsson, M. (2016). Surface Reactions of H2O2, H-2, and O-2 in Aqueous Systems Containing ZrO2. The Journal of Physical Chemistry C, 120(3), 1609-1614.
Open this publication in new window or tab >>Surface Reactions of H2O2, H-2, and O-2 in Aqueous Systems Containing ZrO2
2016 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 120, no 3, 1609-1614 p.Article in journal (Refereed) Published
Abstract [en]

In radiolysis of water, three molecular products are formed (H2O2, O-2, and H-2). It has previously been shown that aqueous hydrogen peroxide is catalytically decomposed on many oxide surfaces and that the decomposition proceeds via the formation of surface-bound hydroxyl radicals. In this work, we have investigated the behavior of aqueous H-2 and O-2 in contact with ZrO2. Experiments were carried out in an autoclave with high H2 pressure and low O-2 pressure (40 and 0.2 bar, respectively). In the experiments the concentration of H-abstracting radicals was monitored as a function of time using tris(hydroxymethyl)aminomethane (Tris) as scavenger and the subsequent formation of formaldehyde to probe radical formation. The plausible formation of H2O2 was also monitored in the experiments. In addition, density functional theory (employing the hybrid PBE0 functional) was used to search for reaction pathways. The results from the,experiments show that hydrogen-abstracting radicals: are formed in the aqueous H2O2-system in contact with solid ZrO2. Formation of H2O2 is also detected, and the time dependent production of hydrogen-abstracting radicals follows the time-dependent H2O2 concentration, strongly:indicating that the radicals are produced upon catalytic decomposition of H2O2. The DFT study implies that H2O2 formation proceeds via a pathway where HO2 is a key intermediate. It is interesting to note that all the stable molecular products from aqueous radiolysis are precursors of quite intriguing radical reactions at water/oxide interfaces.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2016
National Category
Engineering and Technology Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-182780 (URN)10.1021/acs.jpcc.5b10491 (DOI)000369116100026 ()2-s2.0-84956691050 (Scopus ID)
Note

QC 20160223

Available from: 2016-02-23 Created: 2016-02-23 Last updated: 2017-04-21Bibliographically approved
Lousada, C. M., Brinck, T. & Jonsson, M. (2015). Application of reactivity descriptors to the catalytic decomposition of hydrogen peroxide at oxide surfaces. Computational and Theoretical Chemistry, 1070, 108-116.
Open this publication in new window or tab >>Application of reactivity descriptors to the catalytic decomposition of hydrogen peroxide at oxide surfaces
2015 (English)In: Computational and Theoretical Chemistry, ISSN 2210-271X, E-ISSN 2210-2728, Vol. 1070, 108-116 p.Article in journal (Refereed) Published
Abstract [en]

We have employed density functional theory (DFT) calculations using the PBE0 functional to study the reaction of decomposition of H2O2 on clusters of: ZrO2, TiO2, Y2O3, Fe2O3, CeO2, CuO, Al2O3, NiO2, PdO2 and Gd2O3. The formation of the products of decomposition of H2O2 and their binding onto these oxides are discussed. The obtained energy barriers for H2O2 decomposition deviate from experimental data in absolute average by 4 kJ mol(-1). The only exceptions are CeO2 and Fe2O3 for which the deviations are very large. The adsorption of HO radicals onto the clusters was also studied. Reactivity descriptors obtained with DFT calculations are correlated with experimental data from literature. We found a direct correlation between the adsorption energy of HO radicals and the change in Mulliken charge of the cation present in the oxide, upon adsorption of these radicals. Other DFT and experimentally obtained reactivity descriptors based on properties of the cations present in the oxides, such as the ionization potential and electronegativity are plotted against experimental and DFT computed properties, respectively. Following the Bronsted-Evans Polanyi principle, there is a correlation between the adsorption energy of the product HO radical and the energy barrier for decomposition of H2O2. The good correlations between experimental data and the data obtained with DFF using minimalistic cluster models of the oxides surfaces indicates that on the real systems the processes that determine the reactivity of H2O2 are very dependent on localized properties of the surfaces.

Place, publisher, year, edition, pages
Elsevier, 2015
National Category
Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-119809 (URN)10.1016/j.comptc.2015.08.001 (DOI)000361576000016 ()2-s2.0-84941272843 (Scopus ID)
Note

Updated from "In press" to "Published". QC 20151207. QC 20160304

Available from: 2013-03-22 Created: 2013-03-22 Last updated: 2017-12-06Bibliographically approved
Yang, M., Soroka, I. & Jonsson, M. (2015). Hydroxyl radical production in aerobic aqueous solution containing metallic tungsten. Catalysis communications, 71, 93-96.
Open this publication in new window or tab >>Hydroxyl radical production in aerobic aqueous solution containing metallic tungsten
2015 (English)In: Catalysis communications, ISSN 1566-7367, E-ISSN 1873-3905, Vol. 71, 93-96 p.Article in journal (Refereed) Published
Abstract [en]

Abstract In this work, we investigate the production of hydroxyl radicals from the W(s)/air aqueous system by quantifying the amount of scavenging product formaldehyde via the modified Hantzsch method. Tris(hydroxymethyl) aminomethane (Tris) and methanol are used as probe for HO. Meanwhile, the amount of dissolved tungsten is determined by ICP-OES. A turnover point ([W] ≈ 200 μM) is observed in the Tris case after which the production rate of CH2O overwhelms the constant rate in the methanol case. Based on the results, a mechanism is proposed for the studied system including both surface and solution reactions.

Keyword
Hydroxyl radical, Tungsten, H2O2, Oxidative dissolution, Haber–Weiss peroxide chain breakdown
National Category
Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-173119 (URN)10.1016/j.catcom.2015.08.026 (DOI)000362607000020 ()2-s2.0-84940653659 (Scopus ID)
Note

QC 20150922

Available from: 2015-09-07 Created: 2015-09-07 Last updated: 2017-12-04Bibliographically approved
Yang, M., Zhang, X., Grosjean, A., Soroka, I. & Jonsson, M. (2015). Kinetics and Mechanism of the Reaction between H2O2 and Tungsten Powder in Water. The Journal of Physical Chemistry C, 119(39), 22560-22569.
Open this publication in new window or tab >>Kinetics and Mechanism of the Reaction between H2O2 and Tungsten Powder in Water
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2015 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 119, no 39, 22560-22569 p.Article in journal (Refereed) Published
Abstract [en]

In this work, the reaction between H2O2 and tungsten powder in the presence of Tris(hydroxymethyl) aminomethane was studied experimentally. The production of hydroxyl radicals can be quantified indirectly by quantifying the scavenging product formaldehyde (CH2O). XRD, XPS, and SEM analysis shows that no significant structural or compositional changes occur after reaction. We compared H2O2 consumption and CH2O formation in both heterogeneous W(s)/H2O2/Tris system and homogeneous W(aq)/H2O2/Tris system. Increasing the amount of W powder leads to the increase in dissolution rate of W species, insignificant increase of H2O2 consumption rate and the decrease of final CH2O production. By contrast, the consumption rate of H2O2 increases as increasing the concentration of dissolved W species. Based on the experimental results, a mechanism of H2O2 reacting with W powder in the presence of Tris is proposed. The mechanism well explained the relationship between surface reactions and homogeneous Haber–Weiss peroxide chain breakdown.

National Category
Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-173748 (URN)10.1021/acs.jpcc.5b07012 (DOI)000362385700034 ()2-s2.0-84942761051 (Scopus ID)
Note

QC 20150922

Available from: 2015-09-17 Created: 2015-09-17 Last updated: 2017-05-30Bibliographically approved
Björkbacka, Å., Yang, M., Gasparrini, C., Leygraf, C. & Jonsson, M. (2015). Kinetics and mechanisms of reactions between H2O2 and copper and copper oxides. Dalton Transactions, 44(36), 16045-16051.
Open this publication in new window or tab >>Kinetics and mechanisms of reactions between H2O2 and copper and copper oxides
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2015 (English)In: Dalton Transactions, ISSN 1477-9226, E-ISSN 1477-9234, Vol. 44, no 36, 16045-16051 p.Article in journal (Refereed) Published
Abstract [en]

One of the main challenges for the nuclear power industry today is the disposal of spent nuclear fuel. One of the most developed methods for its long term storage is the Swedish KBS-3 concept where the spent fuel is sealed inside copper canisters and placed 500 meters down in the bedrock. Gamma radiation will penetrate the canisters and be absorbed by groundwater thereby creating oxidative radiolysis products such as hydrogen peroxide (H2O2) and hydroxyl radicals (HO[radical dot]). Both H2O2 and HO[radical dot] are able to initiate corrosion of the copper canisters. In this work the kinetics and mechanism of reactions between the stable radiolysis product, H2O2, and copper and copper oxides were studied. Also the dissolution of copper into solution after reaction with H2O2 was monitored by ICP-OES. The experiments show that both H2O2 and HO[radical dot] are present in the systems with copper and copper oxides. Nevertheless, these species do not appear to influence the dissolution of copper to the same extent as observed in recent studies in irradiated systems. This strongly suggests that aqueous radiolysis can only account for a very minor part of the observed radiation induced corrosion of copper.

National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:kth:diva-172417 (URN)10.1039/C5DT02024G (DOI)000360471000033 ()2-s2.0-84940774487 (Scopus ID)
Note

QC 20150929. Updated from e-pub ahead of print to published.

Available from: 2015-08-21 Created: 2015-08-21 Last updated: 2017-12-04Bibliographically approved
Dispenza, C., Grimaldi, N., Sabatino, M. A., Soroka, I. L. & Jonsson, M. (2015). Radiation-Engineered Functional Nanoparticles in Aqueous Systems. Journal of Nanoscience and Nanotechnology, 15(5), 3445-3467.
Open this publication in new window or tab >>Radiation-Engineered Functional Nanoparticles in Aqueous Systems
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2015 (English)In: Journal of Nanoscience and Nanotechnology, ISSN 1533-4880, E-ISSN 1533-4899, Vol. 15, no 5, 3445-3467 p.Article, review/survey (Refereed) Published
Abstract [en]

Controlled synthesis of nanoscalar and nanostructured materials enables the development of novel functional materials with fine-tuned optical, mechanical, electronic, magnetic, conductive and catalytic properties that are of use in numerous applications. These materials have also found their potential use in medicine as vehicles for drug delivery, in diagnostics or in combinations thereof. In principle, nanoparticles can be divided into two broad categories, organic and inorganic nanoparticles. For both types of nanoparticles there are numerous possible synthetic routes. Considering the large difference in nature of these materials and the elementary reactions involved in the synthetic routes, most manufacturing techniques are complex and only suitable for one type of particle. Interestingly, radiation chemistry, i.e., the use of ionizing radiation from radioisotopes and accelerators to induce nanomaterials or chemical changes in materials, has proven to be a versatile tool for controlled manufacturing of both organic and inorganic nanoparticles. The advantages of using radiation chemistry for this purpose are many, such as low energy consumption, minimal use of potentially harmful chemicals and simple production schemes. For medical applications one more advantage is that the material can be sterile as manufactured. Radiation-induced synthesis can be carried out in aqueous systems, which minimizes the use of organic solvents and the need for separation and purification of the final product. The radiation chemistry of water is well known, as are the various ways of fine-tuning the reactivity of the system towards a desired target by adding different solutes. This, in combination with the controllable and adjustable irradiation process parameters, makes the technique superior to most other chemical methods. In this review, we discuss the fundamentals of radiation chemistry and radiation-induced synthesis of nanoparticles in aqueous solutions. The impact of dose and dose rate as well as of controlled addition of various solutes on the final particle composition, size and size distribution are described in detail and discussed in terms of reaction mechanism and kinetics.

Keyword
Ionizing Radiation, Water Radiolysis, Functional Nanoparticles
National Category
Nano Technology
Identifiers
urn:nbn:se:kth:diva-159605 (URN)10.1166/jnn.2015.9865 (DOI)000347435200019 ()2-s2.0-84920742455 (Scopus ID)
Note

QC 20150209

Available from: 2015-02-09 Created: 2015-02-05 Last updated: 2017-12-04Bibliographically approved
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ORCID iD: ORCID iD iconorcid.org/0000-0003-0663-0751

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