ZnO/black phosphorus/C3N4 composite: An effective photocatalyst for Cr (VI) reduction and degradation of rhodamine B.

The utilization of photocatalysts offers a promising approach for the removal of Cr (VI) and rhodamine dyes. Through the generation of reactive species and subsequent degradation reactions, photocatalysis provides an efficient and environmentally friendly method for the remediation of wastewater. In this study, we have synthesized an n-p-n heterojunction of carbon nitride (C3N4), zinc oxide (ZnO), and black phosphorus (BP) through the sonication-stirring method. The photocatalytic ability of this composite was examined for the decomposition rhodamine B (RhB) and detoxification of hexavalent chromium ion (up to 97% during 80 min) under Xenon irradiation. The results of trapper experiments indicated that the active species were hydroxyl radical (˙OH), electron (e-), and superoxide anion radical (˙O2-). Based on the obtained potential of the lowest unoccupied molecular orbitals (LUMO) and the highest occupied molecular orbital (HOMO) for the mentioned semiconductors, through Mutt-Schottky results, the double Z-scheme mechanism was proposed for the studied process. The electrochemical impedance spectroscopy data exhibited good charge transfer for the evaluated composite versus the pure compounds. The impressive separation of holes and electrons along with the low recombination were confirmed by the responses of photocurrent and quenching the photoluminescence (pl) intensity for the composite, respectively. The current density of the composite recorded 66.6%, 87.3%, and 92% higher than those of BP, C3N4, and ZnO, indicating an excellent electron-hole separation for the ternary composite compared to the pure semiconductors. Diffuse reflectance spectra (DRS) data revealed 2.9, 3.17, 1.15, and 2.63 eV as the band gap values for C3N4, ZnO, BP, and composite. The rate constant of the new composite to remove RhB and reduce hexavalent chromium were about 4.79 and 2.64 times higher than that of C3N4, respectively.

Black Phosphorus-based Photocatalysts: Synthesis, Properties, and Applications.

Photocatalysis is considered as an eco-friendly and sustainable strategy, since it uses abundant light for the advancement of the reaction, which is freely accessible and is devoid of environmental pollution. During the last decades, (nano)photocatalysts have gained broad industrial applications in terms of purification and detoxification of water as well as production of green fuels and hydrogen gas due to their special attributes. The degradation or remediation of toxic and hazardous compounds from the environment or changing them into non-toxic entities is a significant endeavor and necessary for the safety of humans, animals, and the environment. Black phosphorus (BP), a two-dimensional single-element material, has a marvelous structure, tunable bandgap, changeable morphology from bulk to nanosheet/quantum dot, and unique physicochemical properties, which makes it attractive material for photocatalytic applications, especially for sustainable development purposes. Since it can serve as a photocatalyst with or without coupling with other semiconductors, various aspects for multidimensional exploitation of BP are deliberated including their preparation via solvothermal, ball milling, calcination, and sonication methods to obtain BP from red phosphorus. The techniques for improving the photocatalytic and stability of BP-based composites are discussed along with their multifaceted applications for environmental remediation, pollution degradation, water splitting, N2 fixation, CO2 reduction, bacterial disinfection, H2 generation, and photodynamic therapy. Herein, most recent advancements pertaining to the photocatalytic applications of BP-based photocatalyst are cogitated, with a focus on their synthesis and properties as well as crucial challenges and future perspectives.

Spectrophotometric-chemometrics study of the effect of solvent composition and temperature on the spectral shape and shift of copper and nickel phthalocyanines in different aqueous-nonaqueous mixed solvents.

Phthalocyanines (Pcs) are green-blue colored aromatic macrocyclic compounds used extensively in the dyeing industry. The assembly phenomenon for dye molecules is directly traceable by most of the spectroscopic methods. In this investigation, the monomer-dimer equilibria of copper and nickel phthalocyanines tetra sulfonic acid tetrasodium salts (CuPcTS, NiPcTS) have been investigated by spectrophotometric and chemometrics methods in binary mixtures of H2O-DMSO and H2O-CH3CN. The dimerization constants, (KD), enthalpies and entropies of CuPcTS and NiPcTS have been calculated by studying the UV-Vis spectra at different concentrations of dyes (10-6 to 10-4molL) and in the temperature range 298-343 K and in some samples up to 353 K by multivariate curve resolution (mcr) methods. By increasing the temperature, the value of KD decreases. The inverse temperature dependence of KD (van't Hoff equation) was used for determination of ΔH 0 and ΔS 0and following that ΔG 0of the dimerization reactions. As a result, upon aggregation, an increase in the intensity of the new shoulder at (~600 nm) and the Q-band at (662-670 nm) and concomitant decrease of the dimer band at (630-624 nm) are observed for all of the samples in different solvents composition. Therefore, the H-dimer type of these pigments was notable, in studied binary solvents. The effect of the solvent composition, concentration dye, and temperature on the spectral responses, the exciton parameters and concentration distribution diagrams of the two pigments were studied and discussed. The density functional theory (DFT) calculations were done in the aqueous and gas phase that they were included the HOMO-LUMO energies and the simulated UV-Vis spectrum. These calculations were beneficial for studying the UV-Vis spectrum of it in the aqueous phase for checking experimental data.