Marco Giorgetti

Università di Bologna, Industrial Chemistry "Toso Montanari", Faculty Member

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Marco Giorgetti was born on December, 1968 in Ancona, Italy. Graduated in Chemistry on 1993, he first served the Italian Navy as an officier, teaching Chemistry at the Scuole sottufficiali MM in Taranto, Italy (1994). He got his Ph.D. on Chemical Sciences in 1998 where he was involved in a joint collaboration between the University of Camerino, Italy and the Université de Paris-Sud, France (1995-1998) working on spectroelectrochemical X-Ray Absorption Spectroscopy (XAS) studies. During the Ph.D. thesis, he worked at LURE, Université de Paris-Sud (Orsay, France) for 18 months for several stages. In 1998 he joined the group of Prof. Smyrl of the University of Minnesota, Minneapolis, USA for a two-years post-doc position, working on the synthesis, electrochemical and structural characterization of materials for secondary lithium batteries. In 2000 he draw up a research fellowship with the University of Camerino, Italy, working on the development of an in-situ electrochemical cell for XRD measurements on battery materials. From October 2000 he was appointed Assistant Professor at the University of Bologna at the Department of Inorganic and Physical Chemistry and from November 2014 he is Associate Professor at the department of Industrial Chemistry (University of Bologna). He is teaching in the field of Analytical Chemistry and Instrumental Techniques since 2001, and from 2009 to the Doctorate school. He's member of the Faculty Teaching Committee (Faculty of Industrial Chemistry) since 2005 and local coordinator of the Analytical Chemistry Teaching staff since 2007. Since september 2011 he has been contact teacher of the European Master in Advanced Spectroscopy on Chemistry (ACS) and from December 2014 he is the Local coordinator.

He is member of the Peer Review Committee of synchrotron SOLEIL, Gif-sur-Yvette, Paris, France (PRC 4 “Chemisty & Physico-Chemistry, In situ reactivity, Soft matter) since January 2012. He has been evaluator for the School of Advanced Studies (PhD program) of the University of Camerino in thecohorts 2012-2013. He has been Referee for the research evaluation Italian Programme (VQR 2004-2010), and also evaluator of project proposals of the Latvian Science Council in 2012 and 2013.

His current research interest covers the field of the structural characterization of materials and solutions by X-Ray Absorption Spectroscopy, the applied electrochemistry and sensors, the synthesis and characterization of mixed hexacyanoferrates. He handled several projects in synchrotron radiation facilities including the LURE (Orsay, France), SRS-Daresbury (Warrington, UK), ESRF (Grenoble, France), Brookhaven National Laboratory (Upton, NY, USA), ELETTRA (Trieste, Italy) as a project leader. He's author about 65 papers published on international journals, 20 Large Scale Facility (LSF) reports, 5 book chapters, 4 publication on national journals, 3 highlights, and about 60 communications at scientific meetings, including 20 oral communications. He has published cover articles in Dalton (2011) and ChemElectroChem (2015). One of his research has been highlighted in the ELETTRA highlights 2011 volume and other two in the ELETTRA web site on 2011 and 2012.

He is embodied in the Referee Panel of several international chemistry journals (Journal of the American Chemical Society, Inorganic Chemistry, Chemistry of Materials, Journal of Physical Chemistry, Electrochimica Acta, Journal of Solid State Chemistry, Journal of Solid State Electrochemistry Journal of Alloys and Compounds, Materials Chemistry and Physics, Waste Management, Applied Surface Science, Science Advanced Material, Journal of Power Sources, Acta Physica Polonica A, ChemElectroChem, Advanced Science, Sensors and Actuators B: Chemical) . From 2012 he is on the Editorial Board of 3 scientific Journals: The Scientific World Journal, Inorganic Chemistry Division; Dataset Papers in Chemistry - Analytical Chemistry Section; ISRN Electrochemistry.
Phone: ph: +39 051 2093666 fax: +39 051 2093690
Address: Department of Industrial Chemistry “Toso Montanari”
University of Bologna
Viale del Risorgimento, 4
40136 Bologna, Italy
web: http://www.unibo.it/faculty/marco.giorgetti
Local Coordinator of ASC Master (Advanced Spectroscopy in Chemistry)
info @ http://www.master-asc.org/

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Papers by Marco Giorgetti

Structural Modification of Partially Ni-substituted MnHCF Cathode Material for Aqueous Zn-ion Batteries

Advanced materials science and technology, 2024

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$Research paper thumbnail of Manganese hexacyanoferrate cathode for Li and Na batteries: structural studies by operando X-ray Powder Diffraction$

Manganese hexacyanoferrate cathode for Li and Na batteries: structural studies by operando X-ray Powder Diffraction

X-ray powder diffraction experiments (XRPD) will be used to study a newly-synthesized manganese h... more X-ray powder diffraction experiments (XRPD) will be used to study a newly-synthesized manganese hexacyanoferrate cathode for rechargeable Li and Na batteries. This study will be performed in operando mode and will permit to monitor the structural modifications and to check the crystalline domain size, shape, and lattice defects of the cathode materials during a full galvanostatic cycles, and at different cycle numbers

Structural study of novel copper sub-microparticles deposited on ITO and sensor mechanism towards the oxidation of L-tyrosine

XANES and EXAFS spectra of fresh prepared copper sub-microparticle thin films have been recorded ... more XANES and EXAFS spectra of fresh prepared copper sub-microparticle thin films have been recorded at the XAFS beamline. The charge associated to the metal and the local atomic structure have been checked out in the pristine sample as well as after addition of a selected amount of L-tyrosine. A selection of spectra evidenced little but detectable differences in the local structure of Cu of the studied electrod

$Research paper thumbnail of Copper nitroprusside cathode for Li and Na batteries: structural and electronic studies by operando X-ray Powder Diffraction and XAFS (RT)$

Copper nitroprusside cathode for Li and Na batteries: structural and electronic studies by operando X-ray Powder Diffraction and XAFS (RT)

Metal hexacyanoferrates-based cathodes for rechargeable batteries: structural and electronic studies by operando XAFS. (RT)

International symposium on enhanced electrochemical capacitors, ISEECap 2022 foreword

Electrochimica Acta

The 7th International Conference on Advances in Machinery, Material Science and Engineering Application (MMSE 2021): 7th MMSE 2021

7th International Conference on Advances in Machinery, Materials Science and Engineering Applications, Aug 24, 2021

Synthesis of gold nanoparticles supported on silica-polyethylenimine beads and their catalytic activity

XI Giornata della chimica dell'Emilia Romagna (Atti), 2011

Aging Mechanism of Mn-Based Prussian Blue Cathode Material by Synchrotron 2D X-ray Fluorescence

Batteries, Apr 5, 2024

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Sodium Insertion into Fe[Fe(CN) 6 ] Framework Prepared by Microwave‐Assisted Co‐Precipitation

ChemElectroChem, Mar 9, 2023

Prussian blue analogues (PBAs) are interesting materials for Na electrochemical insertion, owing ... more Prussian blue analogues (PBAs) are interesting materials for Na electrochemical insertion, owing to their ease of synthesis, rigid open framework and large interstitial space. In this work, iron hexacyanoferrate nanoparticles, FeIII[FeIII(CN)6], also known as Berlin green (BG), where both Fe centers are in the Fe(III) configuration, have been synthesized by an easy microwave assisted co‐precipitation method, with an average particle size of around 44 nm. The BG nanoparticles exhibited a 120 mAh g−1 specific capacity with a capacity retention of 84.8 % over 100 cycles at 20 mA g−1 current and up to 80 mAh g−1 at 10 C rate. The initial charge and discharge processes were fully investigated by ex‐situ X‐ray absorption spectroscopy (XAS). The XAS results reveal that there is some irreversibility in the initial electrochemical processes and the Fe−C and Fe−N bond lengths change during the first charge/discharge cycle. This effect was attributed to BG electrode activation processes, and partly explained the observed capacity fading.

Influence of Vacancies in Manganese Hexacyanoferrate Cathode for Organic Na‐ion Batteries: A Structural Perspective

Chemsuschem, Apr 19, 2023

Manganese hexacyanoferrates (MnHCF) are promising positive electrode materials for non‐aqueous ba... more Manganese hexacyanoferrates (MnHCF) are promising positive electrode materials for non‐aqueous batteries, including Na‐ion batteries, due to their large specific capacity (&gt;130 mAh g−1), high discharge potential and sustainability. Typically, the electrochemical reaction of MnHCF associates with phase and structural changes, due to the Jahn‐Teller (JT) distortion of Mn sites upon the charge process. To understand the effect of the MnHCF structure on its electrochemical performance, two MnHCF materials with different vacancies content are investigated herein. The electrochemical results show that the sample with lower vacancy content (4 %) exhibits relatively higher capacity retention of 99.1 % and 92.6 % at 2nd and 10th cycles, respectively, with respect to 97.4 % and 79.3 % in sample with higher vacancy content (11 %). Ex‐situ X‐ray absorption spectroscopy (XAS) and ex situ X‐ray diffraction (XRD) characterization results show that a weaker cooperative JT‐distortion effect and relatively smaller crystal structure modification occurred for the material with lower vacancies, which explains the better electrochemical performance in cycled electrodes.

Charge Storage Mechanism in Electrospun Spinel‐Structured High‐Entropy (Mn0.2Fe0.2Co0.2Ni0.2Zn0.2)3O4 Oxide Nanofibers as Anode Material for Li‐Ion Batteries

Small, Jul 19, 2023

High‐entropy oxides (HEOs) have emerged as promising anode materials for next‐generation lithium‐... more High‐entropy oxides (HEOs) have emerged as promising anode materials for next‐generation lithium‐ion batteries (LIBs). Among them, spinel HEOs with vacant lattice sites allowing for lithium insertion and diffusion seem particularly attractive. In this work, electrospun oxygen‐deficient (Mn,Fe,Co,Ni,Zn) HEO nanofibers are produced under environmentally friendly calcination conditions and evaluated as anode active material in LIBs. A thorough investigation of the material properties and Li+ storage mechanism is carried out by several analytical techniques, including ex situ synchrotron X‐ray absorption spectroscopy. The lithiation process is elucidated in terms of lithium insertion, cation migration, and metal‐forming conversion reaction. The process is not fully reversible and the reduction of cations to the metallic form is not complete. In particular, iron, cobalt, and nickel, initially present mainly as Fe3+, Co3+/Co2+, and Ni2+, undergo reduction to Fe0, Co0, and Ni0 to different extent (Fe &lt; Co &lt; Ni). Manganese undergoes partial reduction to Mn3+/Mn2+ and, upon re‐oxidation, does not revert to the pristine oxidation state (+4). Zn2+ cations do not electrochemically participate in the conversion reaction, but migrating from tetrahedral to octahedral positions, they facilitate Li‐ion transport within lattice channels opened by their migration. Partially reversible crystal phase transitions are observed.

Soft X-Ray Microscopy of Manganese Hexacyanoferrate Cathode Materials for Lithium and Sodium Batteries" (ise202741)

A very interesting, durable and cheap class of active intercalation cathode materials is represen... more A very interesting, durable and cheap class of active intercalation cathode materials is represented by open-framework structures such as Prussian blue analogues (PBAs). Manganese hexacyanoferrate (MnHCF) with nominal formula Na2Mn[Fe(CN)6]¿zH2O, only includes abundant elements and is safely and easily synthesized. The material features high specific capacities at high potentials when compared to other PBAs [1]. A combined XAS and XRD study has demonstrated that both Fe and Mn sites are involved in the electrochemical process but a capacity fading is observed during the charge and discharge steps, due to a Jahn-Teller (J-T) effect [2]. Using energy-dependent soft x-ray microscopy [3,4] in this study we reveal and visualize the spatial distribution of the oxidation state of Mn, Fe and N at different electrode composition and after 50 cycles in a Li and in a Na battery. The high-resolution access to the metal L edge provided complementary details on the metal-ligand characteristic to the one already available by hard x-ray absorption, while the images demonstrate particles at different state of charge, likely caused by J-T-related passivations, in particular in the cycled lithiated samples. This confirms the superior stability to sodiation and provides an important support for strategies aimed to the suppression of fading

High Voltage High Capacity Cathode Material for Li Battery: An X-ray Absorption Spectroscopy Investigation

ChemInform Abstract: In situ X-Ray Absorption Spectroscopy Characterization of V2O5 Xerogel Cathodes Upon Lithium Intercalation

ChemInform, Jun 13, 2010

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Characterization of partially Ni substituted manganese hexacyanoferrate cathode material

Materials Letters, 2023

Lattice Compensation to Jahn–Teller Distortion in Na-Rich Manganese Hexacyanoferrate for Li-Ion Storage: An Operando Study

ACS applied energy materials, May 22, 2020

Manganese hexacyanoferrate (MnHCF) has received increasing attention as a positive electrode for ... more

$Research paper thumbnail of Beyond the Oxygen Redox Strategy in Designing Cathode Material for Batteries: Dynamics of a Prussian Blue-like Cathode Revealed by Operando X-ray Diffraction and X-ray Absorption Fine Structure and by a Theoretical Approach$

Beyond the Oxygen Redox Strategy in Designing Cathode Material for Batteries: Dynamics of a Prussian Blue-like Cathode Revealed by Operando X-ray Diffraction and X-ray Absorption Fine Structure and by a Theoretical Approach

The Journal of Physical Chemistry C, 2019

The dynamics of the lithiation/delithiation process and the nitrosyl electroactivity in copper ni... more The dynamics of the lithiation/delithiation process and the nitrosyl electroactivity in copper nitroprusside were studied by operando X-ray diffraction (XRD) and operando X-ray absorption fine structure (XAFS). Data were interpreted based on a joint study performed by means of density functional theory (DFT) calculations. This approach allows retrieving the relevant structural and electronic information from the measured scattering and absorption data and therefore to untangle the lithiation mechanism in copper nitroprusside, which occurs with the reduction of both metals generating a lattice basal plane contraction and an axial elongation. An increase of the Debye-Waller factors for Cu-N bonds and a decreasing trend for the Cu-NC-Fe linear chains along with lithium insertion reveal a general increase in the Cu local disorder, which is thought to be the main cause of the rapid capacity fading observed during cycling. The ligand electroactivity of the nitrogen atom, detected by following vibrational frequencies, delivers an extra capacity and represents an alternative path to cationic and oxygen redox.

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The peculiar redox mechanism of copper nitroprusside disclosed by a multi-technique approach

Radiation Physics and Chemistry, 2019

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Caratterizzazione XPS di esacianoferrati ed esacianocobaltati dispersi in matrice di biossido di titanio

Structural Modification of Partially Ni-substituted MnHCF Cathode Material for Aqueous Zn-ion Batteries

Advanced materials science and technology, 2024

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$Research paper thumbnail of Manganese hexacyanoferrate cathode for Li and Na batteries: structural studies by operando X-ray Powder Diffraction$

Manganese hexacyanoferrate cathode for Li and Na batteries: structural studies by operando X-ray Powder Diffraction

Structural study of novel copper sub-microparticles deposited on ITO and sensor mechanism towards the oxidation of L-tyrosine

$Research paper thumbnail of Copper nitroprusside cathode for Li and Na batteries: structural and electronic studies by operando X-ray Powder Diffraction and XAFS (RT)$

Copper nitroprusside cathode for Li and Na batteries: structural and electronic studies by operando X-ray Powder Diffraction and XAFS (RT)