Alvaro Mayoral

University of Zaragoza, Caesaraugusta, Aragon, Spain

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Publications (77)306.81 Total impact

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    ABSTRACT: In this work we investigate the formation of PtAu monodisperse alloyed nanoparticles by ageing pure metallic Au and Pt small nanoparticles (sNPs), nanoparticle size <5 nm, under certain conditions. We demonstrate that those bimetallic entities can be obtained by controlling the size of the initial metallic sNPs separately prepared and by selecting their appropriate capping agents. The formation of this spontaneous phenomenon was studied using HR-STEM, EDS, ionic conductivity, UV-Vis spectroscopy and cyclic voltammetry. Depending on the type of capping agent used and the size of the initial Au sNPs, three different materials were obtained: (i) AuPt bimetallic sNPs showing a surface rich in Au atoms, (ii) segregated Au and Pt sNPs and (iii) a mixture of bimetallic nanoparticles as well as Pt sNPs and Au NPs. Surface segregation energies and the nature of the reaction environment are the driving forces to direct the distribution of atoms in the bimetallic sNPs. PtAu alloyed nanoparticles were obtained after 150 h of reaction at room temperature if a weak capping agent was used for the stabilization of the nanoparticles. It was also found that Au atoms diffuse towards Pt sNPs, producing a surface enriched in Au atoms. This study shows that even pure nanoparticles are prone to be modified by the surrounding nanoparticles to give rise to new nanomaterials if atomic diffusion is feasible.
    Nanoscale 06/2015; 7(22):10152-10161. DOI:10.1039/c5nr01819f · 6.74 Impact Factor
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    ABSTRACT: Nano-hydrotalcite (nano-HT), particles have been supported on silica and tested for chromium(VI) retention through anion exchange mechanism. Ultra high resolution has been achieved in the structural characterization of the nano-hydrotalcite particles allowing identification of the Cr within few layers of the nanoparticles. Compared to a reference hydrotalcite (HT), in which the Cr(VI) retention takes place via memory effect, nano-HT/SiO2 exhibits better adsorption capacity, for 4 mg/L Cr(VI) solutions, even when the adsorption mechanism of the later is anion exchange. This higher adsorption capacity can be attributed to the considerable smaller size of the crystals, which would favor adsorption kinetics and would minimize possible hindrances between the layers of hydrotalcite. The adsorption behavior of nano-HT/SiO2 can be described by a Freundlich isotherm suggesting a non-uniform surface, which is consistent to their arrangement in nanocrystallites observed by TEM.
    Journal of Environmental Chemical Engineering 05/2015; DOI:10.1016/j.jece.2015.05.009
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    ABSTRACT: Super-paramagnetic iron oxide-based nanoparticles (SPIONS) have attracted an enormous amount of attention for their potential use in biomedical applications, due to their good biocompatibility and low toxicity. The current study considers citric acid-conjugated manganese ferrite and its synergy to be used in MRI and in hyperthermia treatment, thus showing theragnostic applications. High colloidal stability was obtained with this functionalisation. SPIONS with super-paramagnetic behaviour of crystal sizes of approximately 20 nm were obtained via an electrochemical synthesis method. One of the highest specific absorption rate (SAR) values was achieved in this work (1661 W g-1), under a magnetic field of 30 mT at 717 kHz frequency, compared with other magnetic ferrites in the literature. These nanoparticles dissipate heat through Néel relaxation, and together with the high SAR value obtained indicate an excellent material for hyperthermia treatment of cancer. In addition, these nanoparticles exhibit transverse relaxivity behaviour, with an r2 value of 394 mM-1 s-1, i.e., at least two times higher than the value of a commercial magnetic contrast agent based on iron oxides. Finally, no toxicity effects of these nanoparticles are evidenced; as a result, these nanoparticles are appropriate for in vivo application.
    The Journal of Physical Chemistry C 03/2015; 119(12):6828-6834. DOI:10.1021/jp510937r · 4.84 Impact Factor
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    Alvaro Mayoral, Daniel Llamosa, Yves Huttel
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    ABSTRACT: Core@shell Co@Au nanoparticles of around 8 nm have been produced by inert gas condensation method, revealing for the first time that most of the nanoparticles present an icosahedral shape in agreement with the theoretical prediction. Additionally, we report the existence of a novel morphology which consists of a Co icosahedron surrounded by fcc Au facets, reported here for the first time.
    Chemical Communications 02/2015; 51(40):8442. DOI:10.1039/C5CC00774G · 6.72 Impact Factor
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    ABSTRACT: The synthesis of nano-sized ZIF-11 with an average size of 36±6 nm is reported. This material has been named nano zeolitic imidazolate framework-11 (nZIF-11). It has the same chemical composition and thermal stability properties and analogous H2 and CO2 adsorption properties as the conventional microcrystalline ZIF-11 (i.e. 1.9±0.9 µm). nZIF-11 has been obtained following the centrifugation route, typically used for solid separation, as a fast new technique (pioneering for MOFs) for obtaining nanomaterials where the temperature, time and rotation speed can easily be controlled. Compared with traditional synthesis consisting of stirring + separation, the reaction time was lowered from several hours to a few minutes when using this centrifugation synthesis technique. Employing the same reaction time (2, 5 or 10 min), micro-sized ZIF-11 was obtained in the traditional synthesis while nano-scale ZIF-11 was achieved only by using centrifugation synthesis. The small particle size obtained for nZIF-11 allowed the use of the wet MOF sample as a colloidal suspension stable in chloroform. This helped to prepare mixed matrix membranes (MMMs) by direct addition of the membrane polymer (polyimide Matrimid®) to the colloidal suspension, avoiding particle agglomeration resulting from drying. The MMMs were tested in H2/CO2 separation, improving the pure polymer membrane performance, with permeation values of 95.9 Barrer of H2 and a H2/CO2 separation selectivity of 4.4 at 35 ⁰C. When measured at 200 ⁰C, these values increased to 535 Barrer and 9.1.
    02/2015; 3(12). DOI:10.1039/C4TA06820C
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    ABSTRACT: Metal nanoparticles with precisely controlled size are highly attractive for heterogeneous catalysis. However, their poor thermal stability remains a major concern in their application at realistic operating conditions. This paper demonstrates the possibility of synthesizing gold nanoparticles with exceptional thermal stability. This has been achieved by using a simple conventional deposition-precipitation technique. The material employed as catalyst consists of gold supported on a TiO2-impregnated SiO2 bimodal mesoporous support. The resulting material shows gold nanoparticles with a narrow size distribution around 3.0 nm, homogeneously dispersed over the TiO2/SiO2 material. Most interestingly, the gold nanoparticles show exceptional thermal stability; calcination temperatures as high as 800 °C have been employed, and negligible changes in the gold particle size distribution are apparent. Additionally, the presence of an amorphous titanium silicate phase is partially preserved, and these factors lead to remarkable activity to catalyze a range of oxidation reactions.Keywords: heterogeneous catalysis; gold nanoparticles; stability; mesoporous materials; catalytic oxidation
    ACS Catalysis 02/2015; 5(2):1078-1086. DOI:10.1021/cs501741u · 7.57 Impact Factor
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    ABSTRACT: The effect of synthesis pH and H2O/EtOH molar ratio on the textural properties of different aluminium trimesate metal organic frameworks (MOFs) prepared in the presence of the well-known cationic surfactant cetyltrimethylammonium bromide (CTAB) at 120 °C was studied with the purpose of obtaining a MOF with hierarchical pore structure. Depending on the pH and the solvent used, different topologies were obtained (namely, MIL-96, MIL-100 and MIL-110). On the one hand, MIL-110 was obtained at lower temperatures than those commonly reported in the literature and without additives to control the pH; on the other hand, MIL-100 with crystallite sizes as small as 30 ± 10 nm could be easily synthesized in a mixture of H2O and EtOH with a H2O/EtOH molar ratio of 3.4 at pH 2.6 in the presence of CTAB. The resulting material displays a hierarchical porosity that combines the microporosity from the MOF and the non-ordered mesopores defined in between the MOF nanoparticles. Interestingly, the maximum of the pore size distribution could be varied between 3 and 33 nm. Finally, at pH 2.5 and using water as a solvent, platelets of MIL-96, a morphology never observed before for this MOF, were synthesized with a (001) preferential crystal orientation, the (001) plane running parallel to the bipyramidal cages of the MIL-96 topology.
    CrystEngComm 02/2015; 17(7):1693-1700. DOI:10.1039/C4CE02324B · 3.86 Impact Factor
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    ABSTRACT: A ca. one-μm single crystal of MOF MIL-53(Al) was attached to a glass support surface via covalent bonding.•The breathing behavior of MOF MIL-53(Al) was monitored in real-time with the help of environmental SEM.•This allowed the attribution of porosity to the geometry in MIL-53(Al) crystals.•The new characterization and the corresponding crystallographic calculations were in agreement with the previous related literature.
    Microporous and Mesoporous Materials 02/2015; 203. DOI:10.1016/j.micromeso.2014.10.016 · 3.21 Impact Factor
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    ABSTRACT: Complex Core@Shell and Core@Shell@Shell nanoparticles are systems that combine the functionalities of the inner core and outer shell materials together with new physico-chemical properties originated by their low (nano) dimensionality. Such nanoparticles are of primer importance in the fast growing nanotechnology as building blocks for more sophisticated systems and a plethora of applications. Here it is shown that, although conceptually simple, a modified gas aggregation approach allows the one-step generation of well-controlled complex nanoparticles. In particular it is demonstrated that the atoms of the core and shell of the nanoparticles can be easily inverted, avoiding intrinsic constraints of chemical methods.
    Nanoscale 11/2014; 6(22):13483. DOI:10.1039/c4nr02913e · 6.74 Impact Factor
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    ABSTRACT: The functionalization with amine groups was developed on the SBA-15, and its effect in the laccase immobilization was compared with that of a Periodic Mesoporous Aminosilica. A method to encapsulate the laccase in situ has now been developed. In this work, spherical aberration (Cs) corrected scanning transmission electron microscopy combined with high angle annular dark field detector and electron energy loss spectroscopy were applied to identify the exact location of the enzyme in the matrix formed by the ordered mesoporous solids.
    10/2014; 2(11):113304. DOI:10.1063/1.4897281
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    ABSTRACT: Nowadays, there is a great interest in the synthesis of colloidal dispersions of nanoparticles of elements with high atomic weight because of their potential application as contrast agents in X-ray imaging. Therefore, we have attempted to synthesize water-dispersible tungsten and bismuth nanoparticles by scanning-assisted pulsed laser ablation of pure tungsten and bismuth bulk targets immersed in a liquid medium. To this end, a battery of techniques has been used to characterize the products obtained under different experimental conditions. Results showed that laser ablation of tungsten or bismuth targets in distilled water by non-overlapping nanosecond laser pulses yielded large aggregates of amorphous tungsten or bismuth oxide/hydroxide nanoparticles, whereas the use of femtosecond laser pulses always produced well defined tungsten(III) oxide or bismuth(III) oxide nanocrystals. On the other hand, the use of short-chain alcohols (methanol, ethanol and n-propanol) as solvent produced colloidal dispersions of crystalline tungsten or bismuth-based nanoparticles. We have found that the crystalline structure of these nanoparticles depends on the pulse duration and pulse overlap degree. Thus, small tungsten(III) or bismuth(III) oxide nanocrystals were obtained by using non-overlapping nanosecond laser pulses. However, laser ablation by overlapping nanosecond laser pulses yielded tungsten-tungsten(III) oxide or bismuth-bismuth(III) oxide core-shell nanoparticles; the use of femtosecond laser pulses always produced well constructed core-shell nanoparticles independently of the pulse overlap. Pulse irradiance time frequency also played a significant role in controlling the rate production, size and dispersity of the as-synthesized nanoparticles; thus, the increase in the irradiance resulted in an increase in the size and particle rate production together with a significant decrease in the dispersity of the final nanoparticles. In conclusion, we have demonstrated the ability to pulsed laser ablation in liquid media to synthesize water-dispersible tungsten and bismuth based-nanopaticles with an adequate control of their crystalline structure, composition, particle size, dispersity and colloidal stability.
    Materials science and engineering congress 2014, Darmstadt; 09/2014
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    ABSTRACT: This work investigates the synthesis of water dispersible core-shell iron-iron oxide nanoparticles by using scanning-assisted, pulsed laser ablation of a pure iron bulk target immersed in a liquid medium. We have also explored the dependence of the structure, size, size distribution, aggregation degree and colloidal stability of the as-synthesized nanoparticles on the laser parameters (wavelength, irradiance time frequency pulse, and laser pulse overlap) and the characteristics of the liquid medium (solvent composition and presence of hydrophilic polymers). A battery of techniques has been used to characterize the as-synthesized nanoparticles. Results showed that laser ablation of the iron target in distilled water by nanosecond laser pulses yielded small iron oxide nanoparticles [magnetite or maghemite] embedded in a matrix of amorphous hematite, whereas the use of femtosecond laser pulses produced well isolated crystalline iron oxide nanoparticles. On the other hand, the use of organic solvents yielded colloidal dispersions consist mainly of iron-iron oxide (maghemite/magnetite) core-shell nanoparticles. In this case, the increase in the pulse irradiance time frequency resulted in an increase in the particle size together with a significant decrease in the dispersity of these nanoparticles; moreover, most of the nanoparticles synthesized at high irradiance values showed an amorphous carbon coating on their surface. On the other hand, the decrease in the pulse laser overlap degree produced an important reduction in the size of the obtained nanoparticles. Pulse duration also played a significant role in controlling the particle aggregation, thus the use of femtosecond laser pulses always produced well isolated and homogeneous core-shell nanoparticles. Moreover, we found that the use as solvent of a mixture of hydrophilic polymers (Polyvinylpyrrolidone and Tetraethylene glycol) dissolved in ethanol resulted in a strong decrease of the particle aggregation and improved their colloidal stability in water.
    materials science and engineering congress 2014, Darmstadt; 09/2014
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    ABSTRACT: We describe the preparation of an effective and reusable heterogeneous asymmetric catalyst. A novel chiral periodic mesoporous phenylene-silica containing high density of bis(oxazoline) moieties is prepared by co-condensation method with 1,4-bis(triethoxysilyl)benzene. After copper(II) coordination, the material is extremely efficient on the kinetic resolution of the 1,2-diphenylethane-1,2-diol with persistent high enantioselectivities (91 - > 99%) and yields (46-43% in maximum 50% resolution) at least for five consecutive cycles. Characterization of the material after the catalytic experiments showed that the heterogeneous catalyst was very robust keeping the integrity of the structure.
    Journal of Catalysis 09/2014; 320:63-69. DOI:10.1016/j.jcat.2014.09.017 · 6.07 Impact Factor
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    ABSTRACT: Gold nanoparticles have received much attention in recent years due to their unique size-dependent properties, as they find useful applications in materials science [Mayoral et al. (Nanoscale 2:335-342, 2010)], catalysis [Schwerdtfeger (Angew Chem Int Ed 42:1892-1895, 2003)] [Hashmi and Hutchings (Angew Chem Int Ed 45:7896-7936, 2006)] and biology [Sperling et al. (Chem Soc Rev 37:1896-1908, 2008)]. The preparation of such nanoparticles benefits from modern chemical knowledge, and a large variety of several procedures have been developed aiming at controlling the size and shape of these metal nanoparticles. Here, we show that two eighteenth-century recipes (Online Resource 1) used at that time to prepare drinkable solutions of gold, used as drugs, actually generate gold nanoparticles, clusters and even monoatomic species of gold. These simple methods involve the dissolution of gold in a solution of ammonium chloride in nitric acid (aqua regia) and the mixing of the resulting solution with rosemary or cinnamon essential oils. The complex mixture of compounds resulting from the fast reaction between aqua regia and the essential oils behave simultaneously as reductants and stabilisers of the nascent gold particles. These results not only prove that historical speculations on the presence of finely divided gold particles floating in these solutions were basically correct but they could also serve as a source of inspiration for new experimental approaches procuring the generation of stable sub-nanometer gold nanoparticles.
    09/2014; 47(3):161-165. DOI:10.1007/s13404-014-0139-8
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    ABSTRACT: The use of hydrogen as an energy vector leads to the development of materials with high hydrogen adsorption capacity. In this work, a new layered stannosilicate, UZAR-S3, is synthesized and delaminated, producing UZAR-S4. UZAR-S3, with the empirical formula Na4SnSi5O14 3.5H2Oand lamellar morphology, is a layered stannosilicate built from SnO6 and SiO4 polyhedra.Thedelamination processused herecomprises three stages: protonation with acetic acid, swelling with nonylamine and the delamination itself with an HCl/H2O/ethanol solution. UZAR-S4 is composed of sheets a few nanometers thick with a high aspect ratio and a surface area of 236 m2/g, twenty times higher than that of UZAR-S3. At �196 �C forUZAR-S4, H2 adsorption reached remarkable values of 3.7 and 4.2 wt% for 10 and 40 bar, respectively, the latter value giving a high volumetric H2 storage capacity of 26.2 g of H2/L.
    International Journal of Hydrogen Energy 08/2014; 39(25):13180–13188. DOI:10.1016/j.ijhydene.2014.06.149 · 2.93 Impact Factor
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    Tom Willhammar, Alvaro Mayoral, Xiaodong Zou
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    ABSTRACT: High-resolution transmission electron microscopy (HRTEM) has shown to be very powerful for solving three-dimensional (3D) structures of unknown crystals. HRTEM has a unique advantage over diffraction for solving structures. Crystallographic structure factor phases, which are lost in diffraction can be directly obtained from HRTEM images. For the determination of a 3D crystalline structure by HRTEM, the crystallographic structure factor amplitudes and phases extracted from HRTEM images along different zone axes are combined to reconstruct a 3D electrostatic potential map. In recent years, scanning transmission electron microscopy (STEM) has reached the atomic resolution, which is comparable to that of HRTEM. Here we show, for the first time, that the structure factor phases can be also obtained from high angle annular dark-field (HAADF)-STEM images and used for 3D reconstruction of atomic structures. This is applied to the complex zeolite structure, silicalite-1 (Formula SiO2, framework code MFI, Pnma, a = 20.090 Å, b = 19.738 Å and c = 13.142 Å). We have compared the amplitudes and phases obtained from HAADF-STEM images with those from HRTEM images.
    Dalton Transactions 08/2014; 43(37). DOI:10.1039/c4dt01904k · 4.10 Impact Factor
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    ABSTRACT: A set of catalysts comprised of gold on different CeO2 supports has been prepared by a nanocasting route and characterized by several physicochemical techniques. These catalysts have been tested for CO oxidation and show outstanding catalytic activity. Higher calcination temperatures of the hard template, producing a poorly ordered silica template, have led to a higher amount of oxygen vacancies on the surface of CeO2. The presence of surface oxygen defects in the support combined with the deposition of Au nanoparticles (ca. 3 nm) homogeneously dispersed on the CeO2 support may explain the excellent behaviour for low temperature CO oxidation. Surprisingly, it has been observed that the degree of inverse replication of the template is not relevant in the catalytic performance, as in all cases neither the characteristics of the ceria surface nor the dispersion and oxidation state of gold are greatly modified by the formation of inter-particle bridges.
    Journal of Catalysis 08/2014; 317:167–175. DOI:10.1016/j.jcat.2014.06.021 · 6.07 Impact Factor
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    ABSTRACT: In this paper, we report on the self-assembly of chemically synthesized metallic magnetic CoFeC nanoparticles (MNPs) stabilized by a mixture of long chain amine and acid surfactants. To control the self-assembly of the MNPs on a substrate, and to prevent the oxidation of the NPs, we have developped a dedicated set-up based on a home made dip coating machine in a glove box coupled to a sputtering chamber. This setup is specially designed to perfom self-assembly on clean substrates in inert atmosphere. We systematically investigated the role of MNP concentration, withdrawal speed, amount and nature (amino and acid groups) of free surfactants in the colloidal solution, and plasma treatments of the substrates (SiO2 or Au). Upon optimising these parameters, the self assembly of MNPs can be tuned from regular stripe to continuous thin films. Moreover, magnetization measurements on the self assembled MNPs confirmed that our set-up prevent significant oxidation of the MNPs.
    Langmuir 07/2014; 30(30). DOI:10.1021/la404044e · 4.38 Impact Factor
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    ABSTRACT: Few-layer graphene has been achieved in liquid dispersion from graphite by the assistance of titanosilicate JDF-L1, using ultrasound and methanol as dispersive media. After a sedimentation step, both the dispersed and the sedimented phases were collected and then the titanosilicate was removed by alkaline hydrothermal dissolution from the mixed materials to obtain few-layer graphene (FLG) and sedimented material, respectively. The production of smaller particles was confirmed by means of N2 adsorption and zeta-potential measurements, so that the BET specific surface area increased from 20 m2/g of the raw graphite to 333 ± 22 m2/g in FLG. Raman spectroscopy shows a decrease in the ratio of intensities of the peaks G and 2D from 3.8 in the raw material to 2.5 in FLG. Particles as fine as 1.3 nm, corresponding to 4-layered FLG, were observed by AFM, while high-resolution TEM showed defect-free regions of graphene.
    Carbon 07/2014; 73:99–105. DOI:10.1016/j.carbon.2014.02.044 · 6.16 Impact Factor
  • Alvaro Mayoral, Paul A Anderson, Isabel Diaz
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    ABSTRACT: Transmission electron microscopy is undoubtedly an indispensable tool for materials characterization, which can currently reach sub-angstrom resolution down to the elemental building blocks of matter, isolated single atoms of most elements. In addition to the phenomenal image resolution, if the material is strong enough, it can be accompanied with chemical information, converting electron microscopy into a unique method for the analysis of a great variety of materials. Unfortunately, extracting all this valuable information is not simple as most materials in one way or another are affected by the strong and localized electron beam. Radiolysis is one kind of reaction between electrons and matter than can cause irreversible structural transformations in our materials. This effect is the predominant factor in zeolites, zeotypes and the majority of molecular sieves. In the present work some results, taken at high voltage (300kV) and minimizing the exposure to the beam, are presented proving the feasibility of the technique to obtain unprecedented atomic resolution information of different zeolites and microporous solids.
    Micron 06/2014; 68. DOI:10.1016/j.micron.2014.05.009 · 2.06 Impact Factor

Publication Stats

355 Citations
306.81 Total Impact Points


  • 2010–2015
    • University of Zaragoza
      • Department of Chemical Engineering and Environmental Technology
      Caesaraugusta, Aragon, Spain
  • 2014
    • Klinikum Darmstadt
      Darmstadt, Hesse, Germany
  • 2013
    • Spanish National Research Council
      Madrid, Madrid, Spain
  • 2009–2012
    • University of Texas at San Antonio
      • Department of Physics and Astronomy
      San Antonio, Texas, United States
  • 2007–2010
    • University of Birmingham
      • School of Chemistry
      Birmingham, England, United Kingdom
  • 2008
    • Stockholm University
      • Department of Materials and Environmental Chemistry
      Tukholma, Stockholm, Sweden