Studying effects of external conditions of electrochemical measurements on the photoelectrochemical properties of semiconductors: cyclic voltammetry, impedance spectroscopy, and Mott – Schottky method

In this paper, the dependences of the semiconductors’ photoelectrochemical properties on the experimental conditions were studied for the solid solution of CdS and ZnS, graphitic carbon nitride, and the platinized carbon nitride. The cyclic voltammograms were obtained under different scan rates. The sample investigations were carried out by two ways, at the constant external voltage and varied amplitudes and at different external voltages and the fixed amplitude. The Mott – Schottky dependences were studied at different frequencies. The basic dependences of the changes in the photoelectrode target characteristics on the experimental condition were found. Some recommendations for the correct comparison of qualitative and quantitative photoelectrochemical data were formulated.https://doi.org/10.15826/elmattech.2023.2.01

Comprehensive Review on g-C₃N₄-Based Photocatalysts for the Photocatalytic Hydrogen Production under Visible Light

Currently, the synthesis of active photocatalysts for the evolution of hydrogen, including photocatalysts based on graphite-like carbon nitride, is an acute issue. In this review, a comprehensive analysis of the state-of-the-art studies of graphic carbon nitride as a photocatalyst for hydrogen production under visible light is presented. In this review, various approaches to the synthesis of photocatalysts based on g-C3N4 reported in the literature were considered, including various methods for modifying and improving the structural and photocatalytic properties of this material. A thorough analysis of the literature has shown that the most commonly used methods for improving g-C3N4 properties are alterations of textural characteristics by introducing templates, pore formers or pre-treatment method, doping with heteroatoms, modification with metals, and the creation of composite photocatalysts. Next, the authors considered their own detailed study on the synthesis of graphitic carbon nitride with different pre-treatments and respective photocatalysts that demonstrate high efficiency and stability in photocatalytic production of hydrogen. Particular attention was paid to describing the effect of the state of the platinum cocatalyst on the activity of the resulting photocatalyst. The decisive factors leading to the creation of active materials were discussed

Solid solutions of CdS and ZnS: Comparing photocatalytic activity and photocurrent generation

The series of Cd1-xZnxS (x = 0–1.0) photocatalysts and Cd1-xZnxS/FTO thin film photoelectrodes were prepared. The obtained samples were studied by X-ray diffraction method (XRD), diffuse reflectance spectroscopy (DRS), scanning electron microscopy (SEM), and N2 low temperature adsorption. The photocatalysts were tested in the reaction of hydrogen production from Na2S/Na2SO3 solution under visible light irradiation. The photocurrents were measured in aqueous solution of Na2Sn and NaCl. It was shown that the target properties in the hydrogen evolution and photocurrent production are changed differently dependent on the composition of the mixed solid solutions. The highest photocatalytic hydrogen production rate was observed over Cd0.3Zn0.7S while the most effective photoelectrode was Cd0.8Zn0.2S/FTO. The Cd1-xZnxS/FTO samples were studied by the electrochemical methods in details. The factors affecting the photocatalytic activity and the photocurrent generation were found and listed for the first time. Conduction band potential (or flat band potential) and electron lifetime play a crucial role for effective photocatalytic hydrogen production over Cd1-xZnxS. Optimal photoelectrochemical characteristics were obtained in case of high values of electron lifetime. If the electron lifetimes of the tested samples have similar values, the high concentration of charge carriers is required for high photocurrent generation over Cd1-xZnxS/FTO photoelectrodes

Selectivity Control of CO₂ Reduction over Pt/g-C₃N₄ Photocatalysts under Visible Light

Photocatalysts based on g-C3N4 have been investigated in the CO2 reduction reaction under visible light irradiation (λ = 397, 427, 452 nm). Photocatalysts were prepared by melamine calcination at 500–600 °C with further platinum deposition (0.1–1.0 wt.%). The effect of the preparation conditions of g-C3N4 and the method of platinum deposition on the physicochemical properties and activity of photocatalysts was studied. The photocatalysts were investigated by X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, X-ray diffraction, high resolution transmission electron microscopy, UV-Vis spectroscopy, and low temperature nitrogen adsorption techniques. It has been found that the efficiency of CO2 reduction is governed by the surface area of g-C3N4 and the presence of platinum in the metallic state, while the optimal content of platinum is 0.5 wt. %. The highest rate of CO2 reduction achieved over Pt/g-C3N4 photocatalyst is 13.2 µmol h−1 g−1 (397 nm), which exceeds the activity of pristine g-C3N4 by 7 times. The most active photocatalysts was prepared by calcining melamine in air at 600 °C, followed by modification with platinum (0.5 wt.%)

Constructing g-C3N4/Cd1−xZnxS-Based Heterostructures for Efficient Hydrogen Production under Visible Light

Two types of photocatalysts, 1%Pt/Cd1−xZnxS/g-C3N4 (x = 0.2–0.3) and Cd1−xZnxS/1%Pt/g-C3N4 (x = 0.2–0.3), were synthesized by varying the deposition order of platinum, and a solid solution of cadmium and zinc sulfides onto the surface of g-C3N4. The characterization of photocatalysts showed that, for 1%Pt/Cd1−xZnxS/g-C3N4, small platinum particles were deposited onto a solid solution of cadmium and zinc sulfides; in the case of Cd1−xZnxS/1%Pt/g-C3N4, enlarged platinum clusters were located on the surface of graphitic carbon nitride. Based on the structure of the photocatalysts, we assumed that, in the first case, type II heterojunctions and, in the latter case, S-scheme heterojunctions were realized. The activity of the synthesized samples was tested in hydrogen evolution from triethanolamine (TEOA) basic solution under visible light (λ = 450 nm). A remarkable increase in hydrogen evolution rate compared to single-phase platinized 1%Pt/Cd1−xZnxS photocatalysts was observed only in the case of ternary photocatalysts with platinum located on the g-C3N4 surface, Cd1−xZnxS/1%Pt/g-C3N4. Thus, we proved using kinetic experiments and characterization techniques that, for composite photocatalysts based on Cd1−xZnxS and g-C3N4, the formation of the S-scheme mechanism is more favorable than that for type II heterojunction. The highest activity, 2.5 mmol H2 g−1 h−1, with an apparent quantum efficiency equal to 6.0% at a wavelength of 450 nm was achieved by sample 20% Cd0.8Zn0.2S/1% Pt/g-C3N4

Photocatalytic Activity of TiNbC-Modified TiO₂ during Hydrogen Evolution and CO₂ Reduction

Photocatalytic CO2 reduction and the production of hydrogen are urgent tasks of green energy. One of the most studied semiconductor photocatalysts for this purpose is titanium dioxide. However, it has a number of fundamental limitations that do not allow its application for such tasks on an industrial scale. Another class of promising materials, which is being investigated very actively, are two-dimensional materials based on MXenes. In this work, we present the first results on photocatalytic hydrogen evolution and CO2 reduction using TiNbC/TiO2 heterostructures with TiNbC contents of 1, 5, and 10%. The approach to the creation of heterostructures proposed in this work may become a significant breakthrough in the search for new highly efficient systems for carbon dioxide reduction and hydrogen production