FRANCESCO TAVANI

Dottore di ricerca

ciclo: XXXV


supervisore: Paola D'Angelo

Titolo della tesi: Advanced experimental, theoretical and data analysis methods for the investigation of chemical processes by X-ray spectroscopy

Achieving accurate chemical knowledge of dynamic chemical processes is of considerable interest both for fundamental understanding and applications. This task however may prove to be challenging, especially when trying to rationalize the often intricate mechanisms of chemical transformations that may involve labile intermediates. The main aim of the dissertation that follows is to address the need of new methods capable of shedding light onto chemical processes whose previously proposed mechanisms are still controversial, also by accurately determining the structural and electronic properties of the key intermediates. Herein, this problem is tackled through the combination of advanced spectroscopic, theoretical and data analysis methods. Specifically, a variety of chemical systems are investigated with such experimental and theoretical approach, such as different chemical reactions occurring in solution on the hour to millisecond time scales and chemical processes occurring in the solid phase and on the surface of materials. The main spectroscopic technique employed to study all the investigated systems is X-ray Absorption Spectroscopy (XAS), which is a sensitive and element-specific probe of both the structural and electronic properties of the given photoabsorbing species. The complexity of the investigated systems was addressed in the first place by leveraging advanced experimental setups, such as those allowing energy dispersive and surface-selective XAS measurements. In addition, coupling XAS with other spectroscopic techniques such as UV-Vis and Nuclear Magnetic Resonance (NMR) provided important complementary information that could not be accessible with either one of the techniques alone. The experimental XAS data capturing the evolution of the given system of chemical interest were then thoroughly analyzed employing multivariate and theoretical tools. In particular, Principal Component Analysis (PCA) and Multivariate Curve Resolution (MCR) spectral un-mixing techniques were employed to determine the number, nature, and concentration time evolution of the key species contributing to the given chemical process. In addition, theoretical methods relying on the Multiple Scattering (MS) and Density Functional Theory (DFT) approaches were applied to interpret the experimental XAS data, focusing on the X-ray Absorption Near Edge Structure (XANES) region. In all the presented studies, the theoretical modeling allowed a quantitative interpretation of the XAS data and provided extensive structural and electronic insights into the given chemical transformation. In particular, the dissertation contains the following studies: (i) XAS-NMR investigations of transition metal exchange processes between prototypical coordination complexes, (ii) a study of the Belousov-Zhabotinskii oscillating reaction by employing Br K-edge XAS and UV-Vis spectroscopies, (iii) investigations of the reactivity of a class of nonheme iron complexes on the second to millisecond time scales; (iv) studies of transition metal-based high entropy oxides (HEOs), an emerging class of multicomponent materials, as anodes for Li–ion batteries and catalytic platforms for the low-temperature CO oxidation; (v) an analysis of the nature of the defective sites of the Cu-based metal-organic framework (MOF) HKUST-1 made possible by surface-sensitive soft XAS; (vi) an investigation of the interfacial solvation of Mg(II) ions on the magnesium oxide surface exposed to water and methanol vapour fluxes; (vii) a study of the interaction established between water and the magnesium chloride surface at elevated temperatures. Altogether, it is shown that the combination of complementary spectroscopic techniques, rooted in XAS and supported by theory, enables a detailed comprehension of the investigated processes. The implement experimental and theoretical method can provide a protocol of general interest that may be extended to investigate interfacial, liquid- and solid-phase systems of chemical relevance.

Produzione scientifica

11573/1691301 - 2023 - Unraveling the Ag+ ion coordination and solvation thermodynamics in the 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid
Busato, M; D'angelo, P; Lapi, A; Tavani, F; Veclani, D; Tolazzi, M; Melchior, A - 01a Articolo in rivista
rivista: JOURNAL OF MOLECULAR LIQUIDS (Amsterdam, Netherlands: Elsevier BV) pp. 122654- - issn: 0167-7322 - wos: WOS:001052460400001 (0) - scopus: 2-s2.0-85166642907 (0)

11573/1691313 - 2023 - Investigating the High-Temperature Water/MgCl2 Interface through Ambient Pressure Soft X-ray Absorption Spectroscopy
Tavani, Francesco; Busato, Matteo; Veclani, Daniele; Braglia, Luca; Mauri, Silvia; Torelli, Piero; D'angelo, Paola - 01a Articolo in rivista
rivista: ACS APPLIED MATERIALS & INTERFACES (Washington, DC : American Chemical Society) pp. 26166-26174 - issn: 1944-8244 - wos: WOS:001014300900001 (1) - scopus: 2-s2.0-85160700578 (2)

11573/1691319 - 2023 - Combining X-ray Absorption and NMR spectroscopies to investigate a chemical reaction in solution
Tavani, Francesco; Del Giudice, Daniele; Di Berto Mancini, Marika; Frateloreto, Federico; Busato, Matteo; Lanzalunga, Osvaldo; Di Stefano, Stefano; D’Angelo, Paola - 01a Articolo in rivista
rivista: RADIATION PHYSICS AND CHEMISTRY (Elsevier Science Limited:Oxford Fulfillment Center, PO Box 800, Kidlington Oxford OX5 1DX United Kingdom:011 44 1865 843000, 011 44 1865 843699, EMAIL: asianfo@elsevier.com, tcb@elsevier.co.UK, INTERNET: http://www.elsevier.com, http://www.elsevier.com/locate/shpsa/, Fax: 011 44 1865 843010) pp. 111199-1-111199-6 - issn: 0969-806X - wos: (0) - scopus: 2-s2.0-85168825418 (0)

11573/1691315 - 2023 - Exploring the Methane to Methanol Oxidation over Iron and Copper Sites in Metal–Organic Frameworks
Tavani, Francesco; Tofoni, Alessandro; D’Angelo, Paola - 01a Articolo in rivista
rivista: CATALYSTS (Basel: Molecular Diversity Preservation International) pp. 1338- - issn: 2073-4344 - wos: WOS:001119522500001 (0) - scopus: 2-s2.0-85175432915 (0)

11573/1691320 - 2023 - Insights into structure and reactivity of MOFs by ambient pressure soft X-ray absorption spectroscopy
Tofoni, Alessandro; Tavani, Francesco; Braglia, Luca; Colombo, Valentina; Torelli, Piero; D’Angelo, Paola - 01a Articolo in rivista
rivista: RADIATION PHYSICS AND CHEMISTRY (Elsevier Science Limited:Oxford Fulfillment Center, PO Box 800, Kidlington Oxford OX5 1DX United Kingdom:011 44 1865 843000, 011 44 1865 843699, EMAIL: asianfo@elsevier.com, tcb@elsevier.co.UK, INTERNET: http://www.elsevier.com, http://www.elsevier.com/locate/shpsa/, Fax: 011 44 1865 843010) pp. 111243- - issn: 0969-806X - wos: (0) - scopus: 2-s2.0-85170436115 (0)

11573/1691317 - 2023 - P K-Edge XANES Calculations of Mineral Standards: Exploring the Potential of Theoretical Methods in the Analysis of Phosphorus Speciation
Tofoni, Alessandro; Tavani, Francesco; Persson, Ingmar; D’Angelo, Paola - 01a Articolo in rivista
rivista: INORGANIC CHEMISTRY (Washington, DC: American Chemical Society) pp. 11188-11198 - issn: 0020-1669 - wos: WOS:001020622000001 (0) - scopus: 2-s2.0-85164704224 (0)

11573/1691321 - 2023 - Full Spectroscopic Characterization of the Molecular Oxygen-Based Methane to Methanol Conversion over Open Fe(II) Sites in a Metal-Organic Framework
Tofoni, Alessandro; Tavani, Francesco; Vandone, Marco; Braglia, Luca; Borfecchia, Elisa; Ghigna, Paolo; Stoian, Dragos Costantin; Grell, Toni; Stolfi, Sara; Colombo, Valentina; D'angelo, Paola - 01a Articolo in rivista
rivista: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (Washington, DC : American Chemical Society, 1879-) pp. 21040-21052 - issn: 1520-5126 - wos: WOS:001068695700001 (2) - scopus: 2-s2.0-85172712048 (1)

11573/1670830 - 2022 - Solubilization and coordination of the HgCl2 molecule in water, methanol, acetone, and acetonitrile: an X-ray absorption investigation
Busato, Matteo; Fazio, Giuseppe; Tavani, Francesco; Pollastri, Simone; D'angelo, Paola - 01a Articolo in rivista
rivista: PHYSICAL CHEMISTRY CHEMICAL PHYSICS (Thomas Graham House, Science Park, Cambridge: Royal Society of Chemistry) pp. 18094-18102 - issn: 1463-9076 - wos: WOS:000830012400001 (0) - scopus: 2-s2.0-85134672833 (1)

11573/1640977 - 2022 - On the Role of Water in the Formation of a Deep Eutectic Solvent Based on NiCl2·6H2O and Urea
Busato, Matteo; Tofoni, Alessandro; Mannucci, Giorgia; Tavani, Francesco; Del Giudice, Alessandra; Colella, Andrea; Giustini, Mauro; D'angelo, Paola - 01a Articolo in rivista
rivista: INORGANIC CHEMISTRY (Washington, DC: American Chemical Society) pp. - - issn: 0020-1669 - wos: WOS:000818965900001 (9) - scopus: 2-s2.0-85131809470 (8)

11573/1603364 - 2022 - Two Faces of the Same Coin: Coupling X-Ray Absorption and NMR Spectroscopies to Investigate the Exchange Reaction Between Prototypical Cu Coordination Complexes
Del Giudice, D.; Tavani, F.; Di Berto Mancini, M.; Frateloreto, F.; Busato, M.; Oliveira De Souza, D.; Cenesi, F.; Lanzalunga, O.; Di Stefano, Stefano; D'angelo, P. - 01a Articolo in rivista
rivista: CHEMISTRY-A EUROPEAN JOURNAL (Wiley-VCH Verlag GmBH:PO Box 101161, D 69451 Weinheim Germany:011 49 6201 606147, EMAIL: service@wiley-vch.de, INTERNET: http://www.wiley-vch.de, Fax: 011 49 6201 606328) pp. - - issn: 0947-6539 - wos: WOS:000730219700001 (8) - scopus: 2-s2.0-85121358737 (6)

11573/1670870 - 2022 - Following a Silent Metal Ion: A Combined X-ray Absorption and Nuclear Magnetic Resonance Spectroscopic Study of the Zn2+ Cation Dissipative Translocation between Two Different Ligands
Frateloreto, Federico; Tavani, Francesco; Di Berto Mancini, Marika; Del Giudice, Daniele; Capocasa, Giorgio; Kieffer, Isabelle; Lanzalunga, Osvaldo; Di Stefano, Stefano; D'angelo, Paola - 01a Articolo in rivista
rivista: THE JOURNAL OF PHYSICAL CHEMISTRY LETTERS (Washington, DC: American Chemical Society) pp. 5522-5529 - issn: 1948-7185 - wos: WOS:000819338000001 (7) - scopus: 2-s2.0-85133100528 (9)

11573/1670868 - 2022 - Caught while Dissolving: Revealing the Interfacial Solvation of the Mg2+ Ions on the MgO Surface
Tavani, Francesco; Busato, Matteo; Braglia, Luca; Mauri, Silvia; Torelli, Piero; D'angelo, Paola - 01a Articolo in rivista
rivista: ACS APPLIED MATERIALS & INTERFACES (Washington, DC : American Chemical Society) pp. 38370-38378 - issn: 1944-8244 - wos: WOS:000848081300001 (5) - scopus: 2-s2.0-85136711634 (6)

11573/1577169 - 2021 - Catching the Reversible Formation and Reactivity of Surface Defective Sites in Metal-Organic Frameworks: An Operando Ambient Pressure-NEXAFS Investigation
Braglia, L.; Tavani, F.; Mauri, S.; Edla, R.; Krizmancic, D.; Tofoni, A.; Colombo, V.; D'angelo, P.; Torelli, P. - 01a Articolo in rivista
rivista: THE JOURNAL OF PHYSICAL CHEMISTRY LETTERS (Washington, DC: American Chemical Society) pp. 9182-9187 - issn: 1948-7185 - wos: WOS:000702017200036 (13) - scopus: 2-s2.0-85116004704 (13)

11573/1603368 - 2021 - Estimating a Set of Pure XANES Spectra from Multicomponent Chemical Mixtures Using a Transformation Matrix-Based Approach
Martini, A.; Guda, A. A.; Guda, S. A.; Dulina, A.; Tavani, F.; D'angelo, P.; Borfecchia, E.; Soldatov, A. V. - 04b Atto di convegno in volume
congresso: Meeting of the Italian Synchrotron Radiation Society, SILS 2019 (ita)
libro: Springer Proceedings in Physics - (978-3-030-72004-9; 978-3-030-72005-6)

11573/1506172 - 2021 - Solubilization properties and structural characterization of dissociated HgO and HgCl2 in deep eutectic solvents
Migliorati, Valentina; Fazio, Giuseppe; Pollastri, Simone; Gentili, Alessandra; Tomai, Pierpaolo; Tavani, Francesco; D'angelo, Paola - 01a Articolo in rivista
rivista: JOURNAL OF MOLECULAR LIQUIDS (Amsterdam, Netherlands: Elsevier BV) pp. - - issn: 0167-7322 - wos: WOS:000636646200024 (12) - scopus: 2-s2.0-85100650045 (14)

11573/1603362 - 2021 - Structural and mechanistic insights into low-Temperature CO oxidation over a prototypical high entropy oxide by Cu L-edge operando soft X-ray absorption spectroscopy
Tavani, F.; Fracchia, M.; Tofoni, A.; Braglia, L.; Jouve, A.; Morandi, S.; Manzoli, M.; Torelli, P.; Ghigna, P.; D'angelo, P. - 01a Articolo in rivista
rivista: PHYSICAL CHEMISTRY CHEMICAL PHYSICS (Thomas Graham House, Science Park, Cambridge: Royal Society of Chemistry) pp. 26575-26584 - issn: 1463-9076 - wos: WOS:000721515900001 (16) - scopus: 2-s2.0-85120728010 (16)

11573/1603366 - 2021 - Insights into the Structure of Reaction Intermediates Through Coupled X-ray Absorption/UV-Vis Spectroscopy
Tavani, F.; Martini, A.; Sessa, F.; Capocasa, G.; Olivo, G.; Lanzalunga, O.; Di Stefano, Stefano; D'angelo, P. - 04b Atto di convegno in volume
congresso: Meeting of the Italian Synchrotron Radiation Society, SILS 2019 (ita)
libro: Springer Proceedings in Physics - (978-3-030-72004-9; 978-3-030-72005-6)

11573/1476321 - 2021 - Direct structural and mechanistic insights into fast bimolecular chemical reactions in solution through a coupled XAS/UV-Vis multivariate statistical analysis
Tavani, Francesco; Capocasa, Giorgio; Martini, Andrea; Sessa, Francesco; Di Stefano, Stefano; Lanzalunga, Osvaldo; D'angelo, Paola - 01a Articolo in rivista
rivista: DALTON TRANSACTIONS (Royal Society of Chemistry:Thomas Graham House, Science Park, Cambridge CB4 0WF United Kingdom:011 44 1223 432360, EMAIL: sales@rsc.org, INTERNET: http://www.rsc.org, http://www.chensoc.org, Fax: 011 44 1223 423429) pp. 131-142 - issn: 1477-9226 - wos: WOS:000605666100014 (8) - scopus: 2-s2.0-85098985805 (9)

11573/1490551 - 2021 - Activation of C-H bonds by a nonheme iron(iv)-oxo complex: mechanistic evidence through a coupled EDXAS/UV-Vis multivariate analysis
Tavani, Francesco; Capocasa, Giorgio; Martini, Andrea; Sessa, Francesco; Di Stefano, Stefano; Lanzalunga, Osvaldo; D'angelo, Paola - 01a Articolo in rivista
rivista: PHYSICAL CHEMISTRY CHEMICAL PHYSICS (Thomas Graham House, Science Park, Cambridge: Royal Society of Chemistry) pp. 1188-1196 - issn: 1463-9076 - wos: WOS:000610150200041 (7) - scopus: 2-s2.0-85100039889 (9)

11573/1453030 - 2020 - Multivariate curve resolution analysis of operando XAS data for the investigation of the lithiation mechanisms in high entropy oxides
Tavani, F.; Fracchia, M.; Pianta, N.; Ghigna, P.; Quartarone, E.; D'angelo, P. - 01a Articolo in rivista
rivista: CHEMICAL PHYSICS LETTERS (Elsevier BV:PO Box 211, 1000 AE Amsterdam Netherlands:011 31 20 4853757, 011 31 20 4853642, 011 31 20 4853641, EMAIL: nlinfo-f@elsevier.nl, INTERNET: http://www.elsevier.nl, Fax: 011 31 20 4853598) pp. 1-5 - issn: 0009-2614 - wos: WOS:000596937600001 (23) - scopus: 2-s2.0-85091510182 (25)

11573/1438571 - 2020 - Direct Mechanistic Evidence for a Nonheme Complex Reaction through a Multivariate XAS Analysis
Tavani, F.; Martini, A.; Capocasa, G.; Di Stefano, Stefano; Lanzalunga, O.; D'angelo, P. - 01a Articolo in rivista
rivista: INORGANIC CHEMISTRY (Washington, DC: American Chemical Society) pp. 9979-9989 - issn: 0020-1669 - wos: WOS:000552287100052 (10) - scopus: 2-s2.0-85087640152 (13)

11573/1236047 - 2019 - Coupled X-ray absorption/UV-vis monitoring of fast oxidation reactions involving a nonheme Iron-Oxo complex
Capocasa, Giorgio; Sessa, Francesco; Tavani, Francesco; Monte, Manuel; Olivo, Giorgio; Pascarelli, Sakura; Lanzalunga, Osvaldo; Di Stefano, Stefano; D'angelo, Paola - 01a Articolo in rivista
rivista: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (Washington, DC : American Chemical Society, 1879-) pp. 2299-2304 - issn: 1520-5126 - wos: WOS:000459222100021 (25) - scopus: 2-s2.0-85061493425 (26)

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