Elisabetta Achilli
University of Pavia
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Featured researches published by Elisabetta Achilli.
Chemical Science | 2014
Alessandro Minguzzi; Ottavio Lugaresi; Elisabetta Achilli; Cristina Locatelli; Alberto Vertova; Paolo Ghigna; Sandra Rondinini
In this work the oxidation states assumed by Ir in oxide systems used as heterogeneous catalysts for water oxidation are determined by means of in situ X-ray Absorption Spectroscopy (XAS). Using a highly hydrated iridium oxide film allows the maximum number of Ir sites to be involved in the electrochemical processes occurring at the catalysts during water oxidation (oxygen evolution reaction, OER). X-ray Absorption Near Edge Structure (XANES) spectra clearly indicate the co-existence of Ir(III) and Ir(V) at the electrode potentials where OER occurs. This represents a fundamental step both in the understanding of the water oxidation mechanism catalysed by heterogeneous Ir oxide systems, and in the possible tailoring of electrocatalysts for OER.
Analytical Chemistry | 2013
Alessandro Minguzzi; Ottavio Lugaresi; Cristina Locatelli; Sandra Rondinini; Francesco D’Acapito; Elisabetta Achilli; Paolo Ghigna
In this paper, the fixed energy X-ray absorption voltammetry (FEXRAV) is introduced. FEXRAV represents a novel in situ X-ray absorption technique for fast and easy preliminary characterization of electrode materials and consists of recording the absorption coefficient at a fixed energy while varying at will the electrode potential. The energy is chosen close to an X-ray absorption edge, in order to give the maximum contrast between different oxidation states of an element. It follows that any shift from the original oxidation state determines a variation of the absorption coefficient. Although the information given by FEXRAV obviously does not supply the detailed information of X-ray absorption near edge structure (XANES) or extended X-ray absorption fine structure (EXAFS), it allows to quickly map the oxidation states of the element under consideration within the selected potential windows. This leads to the rapid screening of several systems under different experimental conditions (e.g., nature of the electrolyte, potential window) and is preliminary to more deep X-ray absorption spectroscopy (XAS) characterizations, like XANES or EXAFS. In addition, the time-length of the experiment is much shorter than a series of XAS spectra and opens the door to kinetic analysis.
ACS Applied Materials & Interfaces | 2016
Tomasz Baran; Szymon Wojtyła; Cristina Lenardi; Alberto Vertova; Paolo Ghigna; Elisabetta Achilli; Martina Fracchia; Sandra Rondinini; Alessandro Minguzzi
Light-driven water splitting is one of the most promising approaches for using solar energy in light of more sustainable development. In this paper, a highly efficient p-type copper(II) oxide photocathode is studied. The material, prepared by thermal treatment of CuI nanoparticles, is initially partially reduced upon working conditions and soon reaches a stable form. Upon visible-light illumination, the material yields a photocurrent of 1.3 mA cm(-2) at a potential of 0.2 V vs a reversible hydrogen electrode at mild pH under illumination by AM 1.5 G and retains 30% of its photoactivity after 6 h. This represents an unprecedented result for a nonprotected Cu oxide photocathode at neutral pH. The photocurrent efficiency as a function of the applied potential was determined using scanning electrochemical microscopy. The material was characterized in terms of photoelectrochemical features; X-ray photoelectron spectroscopy, X-ray absorption near-edge structure, fixed-energy X-ray absorption voltammetry, and extended X-ray absorption fine structure analyses were carried out on pristine and used samples, which were used to explain the photoelectrochemical behavior. The optical features of the oxide are evidenced by direct reflectance spectroscopy and fluorescence spectroscopy, and Mott-Schottky analysis at different pH values explains the exceptional activity at neutral pH.
Journal of Synchrotron Radiation | 2016
Elisabetta Achilli; Alessandro Minguzzi; Alberto Visibile; Cristina Locatelli; Alberto Vertova; Alberto Naldoni; Sandra Rondinini; Ferdinando Auricchio; Stefania Marconi; Martina Fracchia; Paolo Ghigna
Three-dimensional printed multi-purpose electrochemical devices for X-ray absorption spectroscopy are presented in this paper. The aim of this work is to show how three-dimensional printing can be a strategy for the creation of electrochemical cells for in situ and in operando experiments by means of synchrotron radiation. As a case study, the description of two cells which have been employed in experiments on photoanodes for photoelectrochemical water splitting are presented. The main advantages of these electrochemical devices are associated with their compactness and with the precision of the three-dimensional printing systems which allows details to be obtained that would otherwise be difficult. Thanks to these systems it was possible to combine synchrotron-based methods with complementary techniques in order to study the mechanism of the photoelectrocatalytic process.
Spectroscopy | 2014
Elisabetta Achilli; Alessandro Minguzzi; Ottavio Lugaresi; Cristina Locatelli; Sandra Rondinini; Giorgio Spinolo; Paolo Ghigna
An in situ study with dispersive EXAFS (Extended X-Ray Absorption Spectroscopy) at the Ir- edge is performed to characterize Electrodeposited Iridium Oxide Films (EIROF) under chronoamperometric conditions. The technique monitors the local chemical environment and electronic structure of iridium during the oxidation of Ir(III) to Ir(IV) with a time resolution of milliseconds. The study is performed in both acidic and basic media. The Fourier transforms of the time-resolved EXAFS signals clearly show that the short-range structure of Ir is similar to that of rutile-type IrO2 and is maintained during the reaction, thus accounting for the flexibility of the structure of the electrode material in accommodating different oxidation states. From a more general point of view, the work demonstrates the capabilities of in situ experiments based on state-of-the-art dispersive EXAFS in clarifying the mechanistic aspects of electrochemical processes.
Inorganic Chemistry | 2017
Elisabetta Achilli; Alberto Vertova; Alberto Visibile; Cristina Locatelli; Alessandro Minguzzi; S. Rondinini; Paolo Ghigna
Energy-dispersive X-ray absorption spectroscopy was applied, aimed at solving the problem of the structure and stability of a copper(II) lactate complex in alkaline solution, used as a precursor for the electrodeposition of Cu2O. The application of multiple scattering calculations to the simulation of the X-ray absorption near-edge structure part of the spectra allowed an accurate resolution of the structure: the copper(II) cation is surrounded by four lactate ions in a distorted tetrahedral environment, with the lactate anions acting as monodentate ligands. This results in an atomic arrangement where copper is surrounded by four oxygen atoms located at quite a short distance (ca. 1.87 Å) and four oxygen atoms located quite far apart (ca. 3.1-3.2 Å). The complex was finally found to be stable in a wide range of applied potentials.
Acta Crystallographica Section A | 2014
Serena C. Tarantino; Paolo Ghigna; Elisabetta Achilli; Sonia Pin; Michele Zema; Giorgio Spinolo
The mechanism of a solid state reaction in its early stages can be explored by investigating the time evolution of a model reactive system made of a thin layer of one reagent deposited onto a single crystal slab of the other reagent. Insights can be retrieved by comparing results at both local and long length scales obtained with films of different thicknesses and deposited onto different crystal orientations. In particular, reaction between ZnO and Al2O3 has been chosen, as the spinel-forming reactions have been and still remain a model experimental system for investigating solid state reactions and because in the ZnO/Al2O3 phase diagram, spinel is the only stable compound. The reaction initial steps have been investigated by using synchrotron X-ray diffraction, atomic force microscopy and X-ray absorption spectroscopy at the Zn-K edge starting from zincite films deposited onto (110)-, (012)-, (001)oriented corundum single crystals [1,2]. The reaction eventually yields ZnAl2O4 spinel but via a complex mechanism involving side and intermediate non-equilibrium compounds that do not appear in the equilibrium phase diagram of the pseudo-binary system. Spinel, when occurs, is polycrystalline at the end but initially forms with a few preferred orientations. Intermediate phases form before and in parallel with the growth of the spinel. Their number, composition, structure and kinetic role strongly depend on substrate orientation and film thickness. A more detailed understanding of the reactivity can be inferred by comparing EXAFS results to those of grazing incidence diffraction experiments of the films deposited on the (001) face of Al2O3 and heat-treated at 1000 °C for different lengths of time. Information on the structure of the intermediate phases is given and results are discussed by comparing different films thickness to clarify the role of interfacial free energy and crystallographic orientation.
ACS Catalysis | 2015
Alessandro Minguzzi; Cristina Locatelli; Ottavio Lugaresi; Elisabetta Achilli; Giuseppe Cappelletti; Marco Scavini; Mauro Coduri; Paolo Masala; Benedetta Sacchi; Alberto Vertova; Paolo Ghigna; Sandra Rondinini
Electrochimica Acta | 2016
Tomasz Baran; Martina Fracchia; Alberto Vertova; Elisabetta Achilli; Alberto Naldoni; Francesco Malara; Giacomo Rossi; Sandra Rondinini; Paolo Ghigna; Alessandro Minguzzi; Francesco D’Acapito
Electrochimica Acta | 2016
Sandra Rondinini; Alessandro Minguzzi; Elisabetta Achilli; Cristina Locatelli; Giovanni Agostini; S. Pascarelli; Giorgio Spinolo; Alberto Vertova; Paolo Ghigna