Facilities
Analytical Microscopy and Spectroscopy

SFG

General informations

Location
TASC laboratory, Trieste, Italy
Main techniques and methods
in-situ IR-Vis Sum Frequency Generation spectroscopy (IR-Vis SFG), Low Energy Electron Diffraction (LEED), Auger Electron Spectroscopy (AES)
Key instumentation
- 50 Hz, 30 ps laser (1064 nm), 1 GW peak power;
- second harmonic units (532 nm);
- parametric generator (1000-4000 cm-1 IR radiation);
- SFG detector and polarization modules;
- near ambient pressure spectroscopy cell.

The SFG laboratory exploits non-linear laser spectroscopy for the atomic-level investigation of (electro)catalytic interfaces and 2D materials from UHV to near-ambient pressure and liquid environments

Technical description

The Laboratory was designed in 2012, and commissioned in 2013, within the framework of the MIUR FIRB2010 project RBFR10J4H7. The installed spectrometer (Ekspla) allows for IR-Vis SFG vibronic spectroscopy investigation of solid-gas, solid-liquid, and liquid-gas interfaces. An IR pulsed laser beam (50 Hz, 30 ps, 1064 nm) is converted into visible (532 nm) and tunable IR (1200-4000 cm-1) radiation that is temporally and spatially overlapped at the sample’s surface. A monochromator and a CCD detector yield scanning-mode data collection. The polarization of the beams can be selected (p and s modes).

An ultra-high vacuum (UHV) system is coupled to the spectrometer. The base pressure of 7x10-11 mbar allows for standard surface science sample preparation, pre- and post-analysis. The installed instrumentation includes an ion gun (Eurovac), a gas line, LEED and AES optics (OCI), RGA, and fast-entry lock for sample loading. The sample can be resistively heated up to 1300 K. Liquid nitrogen cooling is available. Without breaking the vacuum, the sample can be transferred into a reaction cell that is directly aligned with SFG spectrometer (5 degrees of freedom manipulator). Impinging and outgoing light is transferred through BaF2 windows. Achievable reaction conditions in the measurement cell are in the 10-10 103 mbar and 300 1000 K ranges. Up to three different gas-phase reactants can be used in parallel and mixed.

A dedicated cell is also available for electrochemistry measurements. The setup was initially developed in collaboration with CNR-ICCOM and UniSalento, an updated prototype is being designed in collaboration with PoliMi. Measurements in situ and operando can be performed at an electrode’s surface in the -5/+5 V range at the solid-liquid interface. Electrolyte’s recycling and gas bubbling devices are available. The optical configuration includes a CaF2 prism with micro-channels for the handling of both the electrolyte and the gas bubbles.

Development of new methods, instrumentation, software

Software: The control and data acquisition program of the IR-Vis SFG setup has been customized and further developed in house. Data analysis routines for the normalization and deconvolution of the SFG spectra have been implemented in the Wavemetrics IGOR Pro environment.

Instrumentation: In collaboration with the IOM technical services, we designed, built, and commissioned the cell for the in situ spectroscopy measurements from UHV up to ambient pressure

Research Activity

Nature performs catalytic reactions for the synthesis of energy vectors and organic compounds by exploiting nano-sized or single-atom photosystem and enzymatic catalytic centers, where metals (Mn, Cu, Ni, Fe...) are supported by C, S, or N linkers. Our research is focused on heterogeneous catalytic reaction mechanisms, investigated at the atomic level detail from UHV to near-ambient pressure conditions, occurring at single crystals, nanostructured surfaces, and model catalysts, with an extension to the electro-catalytic environment.

The chemical, electronic, and structural properties are studied experimentally by means of surface science approaches, synchrotron radiation spectroscopies, and in situ and operando IR-Vis Sum-Frequency generation vibronic spectroscopy as implemented in the facility hosted by our lab. Fostering external collaborations, the group exploits ab initio simulations within the framework of Density Functional Theory to yield insight and proper interpretation of the experimental results.

Projects

  • PRIN 2017, 2017KFY7XF, 2019-2022 

Main collaborations

  • Dept. of Energy, Politecnico di Milano, Italy
  • CNR-ICCOM, Firenze, Italy
  • Institute of Materials Chemistry, Vienna University of Technology, Austria
  • Fritz Haber Institute of Max Planck Society, Berlin, Germany
  • Forschungszentrum Jülich, Germany
  • Department of Surface and Plasma Science, Charles University, Prague, Czech Republic

Key publications

Topics in Catalysis, 63-15-18:1585-1595, 2020 doi:10.1007/s11244-020-01333-9

Dioxygen at Biomimetic Single Metal-Atom Sites: Stabilization or Activation? The Case of CoTPyP/Au(111)

Armillotta F., Pividori A., Stredansky M., Seriani N., Vesselli E.
Journal of Physical Chemistry C, 123-6:3916-3922, 2019 doi:10.1021/acs.jpcc.8b11871

Learning from Nature: Charge Transfer and Carbon Dioxide Activation at Single Biomimetic Fe Sites in Tetrapyrroles on Graphene

Corva M., Mohamed F., Tomsic E., Rinaldi M., Cepek C., Seriani N., Peressi M., Vesselli E.
Nature Communications, 9-1, 2018 doi:10.1038/s41467-018-07190-1

Vibrational fingerprint of localized excitons in a two-dimensional metal-organic crystal

Corva M., Ferrari A., Rinaldi M., Feng Z., Roiaz M., Rameshan C., Rupprechter G., Costantini R., Dell’Angela M., Pastore G., Comelli G., Seriani N., Vesselli E.
ACS Nano, 12-11:10755-10763, 2018 doi:10.1021/acsnano.8b05992

Substrate- to Laterally-Driven Self-Assembly Steered by Cu Nanoclusters: The Case of FePcs on an Ultrathin Alumina Film

Corva M., Mohamed F., Tomsic E., Feng Z., Skala T., Comelli G., Seriani N., Peressi M., Vesselli E.
Journal of Electroanalytical Chemistry, 855, 2019 doi:10.1016/j.jelechem.2019.113641

An in situ IR-Vis Sum Frequency Generation Spectroscopy study of cyanide adsorption during zinc electrodeposition

Rossi F., Bevilacqua M., Busson B., Corva M., Tadjeddine A., Vizza F., Vesselli E., Bozzini B.
Electrochimica Acta, 174:532-541, 2015 doi:10.1016/j.electacta.2015.05.173

An in situ near-ambient pressure X-ray Photoelectron Spectroscopy study of Mn polarised anodically in a cell with solid oxide electrolyte

Bozzini B., Amati M., Bocchetta P., Dal Zilio S., Knop-Gericke A., Vesselli E., Kiskinova M.
Journal of Chemical Physics, 146-22, 2017 doi:10.1063/1.4985657

Tunability of the CO adsorption energy on a Ni/Cu surface: Site change and coverage effects

Vesselli E., Rizzi M., Furlan S., Duan X., Monachino E., Dri C., Peronio A., Africh C., Lacovig P., Baldereschi A., Comelli G., Peressi M.
Journal of Physical Chemistry C, 121-17:9381-9393, 2017 doi:10.1021/acs.jpcc.7b01449

Experimental and Theoretical Investigation on the Catalytic Generation of Environmentally Persistent Free Radicals from Benzene

D'Arienzo M., Gamba L., Morazzoni F., Cosentino U., Greco C., Lasagni M., Pitea D., Moro G., Cepek C., Butera V., Sicilia E., Russo N., Muñoz-García A.B., Pavone M.
Journal of the American Chemical Society, 138-12:4146-4154, 2016 doi:10.1021/jacs.5b13366

Reverse Water-Gas Shift or Sabatier Methanation on Ni(110)? Stable Surface Species at Near-Ambient Pressure

Roiaz M., Monachino E., Dri C., Greiner M., Knop-Gericke A., Schlögl R., Comelli G., Vesselli E.
Physical Chemistry Chemical Physics, 18-9:6763-6772, 2016 doi:10.1039/c5cp07906c

Carbon dioxide reduction on Ir(111): Stable hydrocarbon surface species at near-ambient pressure

Corva M., Feng Z., Dri C., Salvador F., Bertoch P., Comelli G., Vesselli E.