For a future hydrogen economy, non‐precious metal catalysts for the water splitting reactions are needed that can be implemented on a global scale. Metal‐nitrogen‐carbon (MNC) catalysts with active sites constituting a metal center with fourfold coordination of nitrogen (MN₄) show promising performance, but an optimization rooted in structure‐property relationships has been hampered by their low structural definition. Porphyrin model complexes are studied to transfer insights from well‐defined molecules to MNC systems. This work combines experiment and theory to evaluate the influence of porphyrin substituents on the electronic and electrocatalytic properties of MN₄ centers with respect to the hydrogen evolution reaction (HER) in aqueous electrolyte. We found that the choice of substituent affects their utilization on the carbon support and their electrocatalytic performance. We propose an HER mechanism for supported iron porphyrin complexes involving a [Fe^II(P⋅)]⁻ radical anion intermediate, in which a porphinic nitrogen atom acts as an internal base. While this work focuses on the HER, the limited influence of a simultaneous interaction with the support and an aqueous electrolyte will likely be transferrable to other catalytic applications.

Thin and transparent films of doped cadmium sulfide (CdS) were obtained on commercial glass substrates by Chemical Bath Deposition (CBD) technique. The films were doped with low concentration of Sn, and annealed in air at 300 °C for 45 min. The morphological characterization of the films with different amounts of dopant was made using SEM and EDAX analysis. Optical properties of the films were evaluated by measuring transmittance using the UV-vis spectrophotometer. A comparison of the results revealed that lower concentration of Sn doping improves transmittance of CdS films and makes them suitable for application as window layer of CdTe/CIGS solar cells.

Two different concentrations of CdCl₂ and (NH₂)₂CS were used to prepare CdS thin films, to be deposited on glass substrate by chemical bath deposition (CBD) technique. CdCl₂ (0.000312 M and 0.000625 M) was employed as a source of Cd²⁺ while (NH₂)₂CS (0.00125 M and 0.000625 M) for S²⁻ at a constant bath temperature of 70 °C. Adhesion of the deposited films was found to be very good for all the solution concentrations of both reagents. The films were air-annealed at a temperature between 200 °C to 360 °C for one hour. The minimum thickness was observed to be 33.6 nm for film annealed at 320 °C. XRD analyses reveal that the films were cubic along with peaks of hexagonal phase for all film samples. The crystallite size of the films decreased from 41.4 nm to 7.4 nm with the increase of annealing temperature for the CdCl₂ (0.000312 M). Optical energy band gap (E_g), Urbach energy (E_u) and absorption coefficient (α) have been calculated from the transmission spectral data. These parameters have been discussed as a function of annealing temperature and solution concentration. The best transmission (about 97%) was obtained for the air-annealed films at higher temperature at CdCl₂ (0.000312 M).

Nuclear forward scattering (NFS) is a synchrotron-based technique relying on the recoil-free nuclear resonance effect similar to Mössbauer spectroscopy. In this work, we introduce NFS for in situ and operando measurements during electrocatalytic reactions. The technique enables faster data acquisition and better discrimination of certain iron sites in comparison to Mössbauer spectroscopy. It is directly accessible at various synchrotrons to a broad community of researchers and is applicable to multiple metal isotopes. We demonstrate the power of this technique with the hydrogen evolution mechanism of an immobilized iron porphyrin supported on carbon. Such catalysts are often considered as model systems for iron-nitrogen-carbon (FeNC) catalysts. Using in situ and operando NFS in combination with theoretical predictions of spectroscopic data enables the identification of the intermediate that is formed prior to the rate-determining step. The conclusions on the reaction mechanism can be used for future optimization of immobilized molecular catalysts and metal-nitrogen-carbon (MNC) catalysts.

CdTe film was deposited using the electrophoretic deposition technique onto an ITO glass at various bath temperatures. Four batch film compositions were used by mixing 1 to 4 wt% concentration of CdTe powder with 10 mL of a solution of methanol and toluene. X-ray Diffraction analysis showed that the films exhibited polycrystalline nature of zinc-blende structure with the (111) orientation as the most prominent peak. From the Atomic Force Microscopy, the thickness and surface roughness of the CdTe film increased with the increase of CdTe concentration. The optical energy band gap of film decreased with the increase of CdTe concentration, and with the increase of isothermal bath temperature. The film thickness increased with respect to the increase of CdTe concentration and bath temperature, and following, the numerical expression for the film thickness with respect to these two variables has been established.