Engineering Nitrogen-Doped Carbon Quantum Dots: Tailoring Optical and Chemical Properties through Selection of Nitrogen Precursors

The process of N-doping is frequently employed to enhance the properties of carbon quantum dots. However, the precise requirements for nitrogen precursors in producing high-quality N-doped carbon quantum dots (NCQDs) remain undefined. This research systematically examines the influence of various nitrogen dopants on the morphology, optical features, and band structure of NCQDs. The dots are synthesized using an efficient, eco- friendly, and rapid continuous hydrothermal flow technique. This method offers unparalleled control over synthesis and doping, while also eliminating convention-related issues. Citric acid is used as the carbon source, and urea, trizma base, beta-alanine, L-arginine, and EDTA are used as nitrogen sources. Notably, urea and trizma produced NCQDs with excitation-independent fluorescence, high quantum yields (up to 40%), and uniform dots with narrow particle size distributions. Density functional theory (DFT) and time-dependent DFT modelling established that defects and substituents within the graphitic structure have a more significant impact on the NCQDs’ electronic structure than nitrogen-containing functional groups. Importantly, for the first time, this work demonstrates that the conventional approach of modelling single-layer structures is insufficient, but two layers suffice for replicating experimental data. This study, therefore, provides essential guidance on the selection of nitrogen precursors for NCQD customization for diverse applications

3D printed SrNbO₂N photocatalyst for degradation of organic pollutants in water

Organic pollutants in water are a major concern for the environment and human health, and require urgent attention. Here, we developed for the first time monolithic structures by 3D printing of perovskite metal oxynitride, SrNbO2N, for photocatalytic degradation of organic pollutant in water. Advanced, synchrotron-based XRD-CT measurements were employed to gain structural insight into photocatalyst formulation and assess the fidelity of design in terms of both the chemical and physical form of the photocatalysts to be imaged. Our 3D printed material showed excellent photocatalytic activity, degrading 100% of methylene blue (MB) as well as good stability for three cycle operations. This is due to high adsorption of the 3D printed oxynitride towards MB which enhanced its photoredox reactivity. It is also evident from the excellent charge transfer demonstrating a charge transfer rate of (1.5 ± 0.2) × 108 s−1. We performed Time-Dependent Density Functional Theory (TD-DFT) calculations to understand the photocatalyst structure and degradation pathways. Our calculated band gap (at Γ) of 1.88 eV is in good agreement with the experimental values. We found that the highest valence bands were contributed by N p orbitals and the lowest conduction bands corresponded to Nb d orbitals offering avenues for fine-tuning the band gap. Hence, the ability to tailor photocatalyst monoliths by 3D printing renders their water treatment application more facile compared to their powder suspension counterparts

Effect of substituents in hydroxyl radical-mediated degradation of azo pyridone dyes: Theoretical approaches on the reaction mechanism

Understanding the degradation behavior of azo dyes in photocatalytic wastewater treatment is of fundamental and practical importance for their application in textile-processing and other coloration industries. In this study, quantum chemistry, as density functional theory, was used to elucidate different degradation pathways of azo pyridone dyes in a hydroxyl radical (HO•) initiated photocatalytic system. A series of substituted azo pyridone dyes were synthesized by changing the substituent group in the para position of the benzene moiety, ranging from strong electron-donating to strong electron-withdrawing groups. The effect of dye molecular structure on the photocatalytic degradation reaction mechanism was analyzed and quantification of substituent effects on the thermodynamic and kinetics parameters was performed. Potential energy surface analysis revealed the most susceptible reaction site for the HO• attack. The calculated reaction barriers are found to be strongly affected by the nature of substituent group with a good correlation using Hammett σp constants and experimentally determined reaction rates. The stability of pre-reaction complexes and transition state complexes were analyzed applying the distortion-interaction model. The increased stability of the transition state complexes with the distancing from the substituent group has been established

3D printed SrNbO2N photocatalyst for degradation of organic pollutants in water

Organic pollutants in water are a major concern for the environment and human health, and require urgent attention. Here, we developed for the first time monolithic structures by 3D printing of perovskite metal oxynitride, SrNbO2N, for photocatalytic degradation of organic pollutant in water. Advanced, synchrotron-based XRD-CT measurements were employed to gain structural insight into photocatalyst formulation and assess the fidelity of design in terms of both the chemical and physical form of the photocatalysts to be imaged. Our 3D printed material showed excellent photocatalytic activity, degrading 100% of methylene blue (MB) as well as good stability for three cycle operations. This is due to high adsorption of the 3D printed oxynitride towards MB which enhanced its photoredox reactivity. It is also evident from the excellent charge transfer demonstrating a charge transfer rate of (1.5 ± 0.2) × 108 s−1. We performed Time-Dependent Density Functional Theory (TD-DFT) calculations to understand the photocatalyst structure and degradation pathways. Our calculated band gap (at Γ) of 1.88 eV is in good agreement with the experimental values. We found that the highest valence bands were contributed by N p orbitals and the lowest conduction bands corresponded to Nb d orbitals offering avenues for fine-tuning the band gap. Hence, the ability to tailor photocatalyst monoliths by 3D printing renders their water treatment application more facile compared to their powder suspension counterparts