Silvia Bordiga

2005-present
Catalysis (bachelor and master), University of Turin, Italy
1996-present
Physical Chemistry (bachelor and master), University of Turin, Italy
2013-present
Materials for Energy (bachelor), University of Turin, Italy
2013-present
Materials today (bachelor), University of Turin, Italy
20014-present
Metallorganic Frameworks, PhD school in Science and innovative technologies
2010-2014
Scuola di Studi Superiori dell’Università di Torino Energy and Clime III

My scientific activity in the last 10 years has been mainly devoted to the characterization of physical-chemical properties of nanostructured materials with large surface area used as heterogeneous catalysts, photo-catalysts, materials for adsorption, separation and storage of gases. Simple oxides, synthetic zeolites and, more recently, metallorganic frameworks (MOFs) are the major topics of interest. The work strategy is to merge pieces of information from experiments (mostly spectroscopies) with data obtained from molecular modelling in order to understand structural and functional behaviours of the materials under study and correlate them with their performances in respect of a specific application. The rational use of complementary characterization techniques allowed me to increase the knowledge on the structure of the active sites and to observe labile reaction intermediates, with relevant implication in the understanding of reaction mechanisms. My recent challenge is to detect and monitor active sites “in action”, being able to perform experiments not only in situ but adopting extensively operando approaches.
 

2013-2016
Energy2013-3.5.1.2 Collaborative Project “Advanced Materials and Electric Swing Adsorption Process for CO2 Capture”. PI of Turin unit and leader of WP7
2012-2014
FCH JU platform (Fuel Cells and Hydrogen Joint Undertaking) entitled “Novel H2 storage materials for stationary and portable applications” (Bor4Store).
2011-2014
FCH JU platform (Fuel Cells and Hydrogen Joint Undertaking) entitled “Fuel Cell Coupled Solid State Hydrogen Storage Tank” (SSH2S).
2009-2013
NMP-2008-2.4-1 Inorganic-Organic Hybrid Materials. “Nanoporous Metal-Organic Frameworks for production”.

2015- University of Turin: Open access-Lab: Up-date Raman Laboratory.
2014-2015
Regione Piemonte IV programma Poli di innovazione “HEAT”.
2013-2016
MIUR: Mechanisms of CO2 activation for the design of new materials for energy and resource efficiency.
2012-2013
University of Turin: “Advances in nanostructured materials and interfaces for key technologies..

The process of carbon capture and sequestration has been proposed as a method of mitigating the build-up of green house gases in the atmosphere. If implemented, the cost of electricity generated by a fossil fuel-burning power plant would rise substantially, owing to the expense of removing CO2 fromthe effluent stream. There is therefore an urgent need for more efficient gas separation technologies, such as those potentially offered by advanced solid adsorbents. Here we show that diamine-appended metal-organic frameworks can behave as ‘phase-change’ adsorbents, with unusual step-shaped CO2 adsorption isotherms that shift markedly with temperature. Results from spectroscopic, diffraction and computational studies show that the origin of the sharp adsorption step is an unprecedented cooperative process in which,  above a metal-dependent threshold pressure,CO2 molecules insert into metal-amine bonds, inducing a reorganization of the amines into well-ordered chains of ammonium carbamate. As a consequence, large CO2 separation capacities can be achieved with small temperature swings, and regeneration energies appreciably lower than achievable with state-of-the-art aqueous amine solutions become feasible. The results provide a mechanistic framework for designing highly efficient  adsorbents for removing CO2 from various gas mixtures, and yield insights into the conservation of Mg within the ribulose-1,5-bisphosphate carboxylase/oxygenase family of enzymes.

PAHs are hazardous and persistent pollutants, also found as byproducts of some petrolchemical reaction (e.g., MTH) in relation to the catalyst deactivation, i.e.,  to the formation of coke species. The analysis of such deactivation products is typically performed by means of chromatographic techniques, with some drawbacks: the extraction and separation of the molecules from the matrix (the catalyst) is always required, and the solubility of the larger ones is often very low also in nonpolar solvents, so that their analysis is not possible with a standard approach. Spectroscopies can represent an interesting alternative for the qualitative analysis of PAHs: in particolar Raman spectroscopy has been demonstrated to be a powerful tool in the characterization of carbonaceous materials and PAHs, and the possibility to exploit the resonance effect (allowing the selective enhancement of vibrational features of the resonant species) can be a considerable advantage in the analysis of very diluted species. An ongoing workline, attempts to monitor the formation of PAHs by means of UV Raman spectroscopy (the 244 nm excitation wavelength allowed to exploit the resonance effect and in the meantime to avoid interference due to the visible fluorescence typical of these molecole) on a relevant set of zeolites used for hydrocarbon corvesion .

Combined use of spectroscopies to disclose reaction mechanism on an heterogeneous catalysts:.Case study: A Consistent Reaction Scheme for the Selective Catalytic Reduction of Nitrogen Oxides with Ammonia

For the first time, the standard and fast selective catalytic reduction (SCR)  of NO by NH3 are described in a complete catalytic cycle that is able to produce the correct stoichiometry while allowing adsorption and desorption of stable molecules only. The standard SCR reaction is a coupling of the activation of NO by O2 with the fast SCR reaction, enabled by the release of NO2. According to the scheme, the SCR reaction can be divided into an oxidation of the catalyst by NO + O2 and a reduction by NO + NH3; these steps together constitute a complete catalytic cycle. Furthermore, both NO and NH3 are required in the reduction, and finally, oxidation by NO + O2 or NO2 leads to the same state of the catalyst. These points are shown experimentally for a Cu-CHA catalyst by combining in situ X-ray absorption spectroscopy (XAS), electron paramagnetic resonance (EPR), and Fourier transform infrared spectroscopy (FTIR). A consequence of the reaction scheme is that all intermediates in fast SCR are also part of the standard SCR cycle. The activation energy calculated by density functional theory (DFT) indicates that the oxidation of an NO molecule by O2 to a bidentate nitrate ligand is rate-determining for standard SCR. Finally, the role of a nitrate/nitrite equilibrium and the possible influence of Cu dimers and Brønsted sites are discussed, and an explanation is offered as to how a catalyst can be effective for SCR while being a poor catalyst for NO oxidation to NO2.
 

1. Bonino, F.; Chavan, S.; Vitillo, J. G.; Groppo, E.; Agostini, G.; Lamberti, C.; Dietzel, P. D. C.; Prestipino, C.; Bordiga, S., Local structure of CPO-27-Ni metallorganic framework upon dehydration and coordination of NO. Chem. Mat. 2008, 20, 4957-4968. Times Cited: 52.
2. Bordiga, S.; Regli, L.; Bonino, F.; Groppo, E.; Lamberti, C.; Xiao, B.; Wheatley, P. S.; Morris, R. E.; Zecchina, A., Adsorption properties of HKUST-1 toward hydrogen and other small molecules monitored by IR. Phys. Chem. Chem. Phys. 2007, 9, 2676-2685. Times Cited: 149.
3. Prestipino, C.; Regli, L.; Vitillo, J. G.; Bonino, F.; Damin, A.; Lamberti, C.; Zecchina, A.; Solari, P. L.; Kongshaug, K. O.; Bordiga, S., Local structure of framework Cu(II) in HKUST-1 metallorganic framework: Spectroscopic characterization upon activation and interaction with adsorbates. Chem. Mat. 2006, 18, 1337-1346. Times Cited: 222.
4. Vitillo, J. G.; Regli, L.; Chavan, S.; Ricchiardi, G.; Spoto, G.; Dietzel, P. D. C.; Bordiga, S.; Zecchina, A., Role of exposed metal sites in hydrogen storage in MOFs. J. Am. Chem. Soc. 2008, 130, 8386-8396. Times Cited: 216.
5. Dani, A.; Groppo, E.; Barolo, C.; Vitillo, J. G.; Bordiga, S., Design of high surface area poly(ionic liquid)s to convert carbon dioxide into ethylene carbonate. J. Mater. Chem. A 2015, 3, 8508-8518. Times Cited: 2.
6. Janssens, T. V. W.; Falsig, H.; Lundegaard, L. F.; Vennestrom, P. N. R.; Rasmussen, S. B.; Moses, P. G.; Giordanino, F.; Borfecchia, E.; Lomachenko, K. A.; Lamberti, C.; Bordiga, S.; Godiksen, A.; Mossin, S.; Beato, P., A Consistent Reaction Scheme for the Selective Catalytic Reduction of Nitrogen Oxides with Ammonia. ACS Catal. 2015, 5, 2832-2845. Times Cited: 13.
7. Lamberti, C.; Zecchina, A.; Groppo, E.; Bordiga, S., Probing the surfaces of heterogeneous catalysts by in situ IR spectroscopy. Chem. Soc. Rev. 2010, 39, 4951-5001. Times Cited: 106
8. Cavka, J. H.; Jakobsen, S.; Olsbye, U.; Guillou, N.; Lamberti, C.; Bordiga, S.; Lillerud, K. P., A new zirconium inorganic building brick forming metal organic frameworks with exceptional stability. J. Am. Chem. Soc. 2008, 130, 13850-13851. Times Cited: 845.
9. McDonald, T. M.; Mason, J. A.; Kong, X. Q.; Bloch, E. D.; Gygi, D.; Dani, A.; Crocella, V.; Giordanino, F.; Odoh, S. O.; Drisdell, W. S.; Vlaisavljevich, B.; Dzubak, A. L.; Poloni, R.; Schnell, S. K.; Planas, N.; Lee, K.; Pascal, T.; Wan, L. W. F.; Prendergast, D.; Neaton, J. B.; Smit, B.; Kortright, J. B.; Gagliardi, L.; Bordiga, S.; Reimer, J. A.; Long, J. R., Cooperative insertion of CO2 in diamine-appended metal-organic frameworks. Nature 2015, 519, 303-308. Times Cited: 61.
10. Xiao, D. J.; Bloch, E. D.; Mason, J. A.; Queen, W. L.; Hudson, M. R.; Planas, N.; Borycz, J.; Dzubak, A. L.; Verma, P.; Lee, K.; Bonino, F.; Crocella, V.; Yano, J.; Bordiga, S.; Truhlar, D. G.; Gagliardi, L.; Brown, C. M.; Long, J. R., Oxidation of ethane to ethanol by N2O in a metal-organic framework with coordinatively unsaturated iron(II) sites. Nat. Chem. 2014