The ultraviolet-visible-near infrared (UV/Vis/NIR) spectra of the sublimed and oCVD films deposited on glass slides were recorded with in a PerkinElmer Lambda 1050 spectrometer, in the transmission (T) mode, in the 300–2500 nm wavelength interval. The absorbance (A) was calculated as: A = −log(T). From the absorbance spectra, the direct optical band gap of the fused-metalloporphyrins was estimated through the Tauc plot as: (αhν)1/n = A(hν − Eg), where α is the absorbance coefficient, n = 1/2 for direct transitions, h is the Planck's constant and ν the wavelength number. The absorbance coefficient was calculated as: α = ln(10)A/l, where l is the film's thickness. The thin film thicknesses were measured using a KLA-Tencor P-17 Stylus Profiler. Additionally, the thin films were rinsed with dichloromethane (HPLC grade >99.8%, SupraSolv®) for comparison with the as-deposited films.
Scanning electron microscopy (SEM) images were recorded using a FEI Quanta 200F instrument. Transmission electron microscopy (TEM) analyses were performed with a JEOL JEM-F200 cold FEG microscope operating at an acceleration voltage of 200 kV. Energy dispersive spectroscopy (EDS) was carried out in STEM mode. For preparing the samples, the as-prepared films were scratched, and the material collected was dispersed in ethanol. A Cu mesh covered with a holey carbon film (AGS147-3H, Agar Scientific Ltd) was immersed in the dispersion and let dry until full evaporation of the solvent. X-ray photoelectron spectroscopy (XPS) measurements were performed with a Kratos Axis Ultra DLD instrument using a monochromatic Al Kα X-ray source of energy 1486.6 eV, at 105 W power. The analyses were performed under 5 × 10−9 mbar vacuum pressure. Charge calibration was accomplished by fixing the binding energy of carbon (C 1s) to 285.0 eV. Raman spectra were recorded at room temperature with an inVia Raman Microscope (RENISHAW), using 633 nm laser excitation. All the oCVD samples (as prepared and after electrochemical characterization) were stored under vacuum conditions until their subsequent analysis.
Laser desorption/ionization high-resolution mass spectrometry (LDI-HRMS) measurements were performed using an AP-MALDI UHR ion source (MassTech, Inc.) coupled to an LTQ/Orbitrap Elite (Thermo Scientific). In-source fragmentation (E = 70 V) was used to prevent the formation of clusters. The measurements were performed on Si wafer substrates and FTO-coated glass coated either with the sublimed porphyrin monomer and oCVD film, which were directly placed on the sample holder. LDI-HRMS measurements and analysis of metalloporphyrin coatings have been described in detail elsewhere.57,58,63 (link)
Scanning electron microscopy (SEM) images were recorded using a FEI Quanta 200F instrument. Transmission electron microscopy (TEM) analyses were performed with a JEOL JEM-F200 cold FEG microscope operating at an acceleration voltage of 200 kV. Energy dispersive spectroscopy (EDS) was carried out in STEM mode. For preparing the samples, the as-prepared films were scratched, and the material collected was dispersed in ethanol. A Cu mesh covered with a holey carbon film (AGS147-3H, Agar Scientific Ltd) was immersed in the dispersion and let dry until full evaporation of the solvent. X-ray photoelectron spectroscopy (XPS) measurements were performed with a Kratos Axis Ultra DLD instrument using a monochromatic Al Kα X-ray source of energy 1486.6 eV, at 105 W power. The analyses were performed under 5 × 10−9 mbar vacuum pressure. Charge calibration was accomplished by fixing the binding energy of carbon (C 1s) to 285.0 eV. Raman spectra were recorded at room temperature with an inVia Raman Microscope (RENISHAW), using 633 nm laser excitation. All the oCVD samples (as prepared and after electrochemical characterization) were stored under vacuum conditions until their subsequent analysis.
Laser desorption/ionization high-resolution mass spectrometry (LDI-HRMS) measurements were performed using an AP-MALDI UHR ion source (MassTech, Inc.) coupled to an LTQ/Orbitrap Elite (Thermo Scientific). In-source fragmentation (E = 70 V) was used to prevent the formation of clusters. The measurements were performed on Si wafer substrates and FTO-coated glass coated either with the sublimed porphyrin monomer and oCVD film, which were directly placed on the sample holder. LDI-HRMS measurements and analysis of metalloporphyrin coatings have been described in detail elsewhere.57,58,63 (link)
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