Co+2, Ni+2 and Cu+2 incorporated Bi2O3 nano photocatalysts: Synthesis, DFT analysis of band gap modification, adsorption and photodegradation analysis of rhodamine B and Triclopyr.

This study deals with the fabrication of metal ion (M = Co+2, Ni+2, and Cu+2) doped- Bi2O3 photocatalysts by solution combustion method. All the synthesized materials were characterized and analysed with the help of XRD, FESEM, EDX, HRTEM, UVDRS, Zeta potential, PL, and LCMS techniques for the structural, morphological, surface charge, optical and degradation pathways characteristics. Synthesized compounds were used for the decontamination (adsorption and degradation) of two organic pollutants namely Rhodamine B and Triclopyr. Adsorption aspects of the pollutants were studied in terms of different isotherm, kinetic and thermodynamic models. Adsorption phenomenon was best fitted with the Freundlich (R2 = 0.992) and Langmuir isotherm (R2 = 0.999) models along with pseudo second order model of kinetics for RhB and TC, respectively. Moreover, the thermodynamic parameters indicated exothermic and endothermic adsorption (ΔH ° (-7.19 kJ/mol) for RhB) and (ΔH ° (52.335 kJ/mol) for TC), respectively. Evaluated negative values of ΔG ° indicated spontaneous adsorption with most favourable at 298 K and 318 K for both the pollutants (RhB and TC) respectively. Modification with metal ions significantly improved the removal efficiency of pure Bi2O3 photocatalyst and followed the trend Co+2/Bi2O3 > Ni+2/Bi2O3 > Cu+2/Bi2O3 > Bi2O3. DFT calculations demonstrate that amongst the doped materials, only Co+2/Bi2O3 is characterized by an indirect band gap; which exhibited efficacious photocatalytic activity. Besides, the highest degradation efficiency was obtained in the case of Co+2/Bi2O3 (2 mol %); being 99.80% for RhB in 30 min and 98.50% for TC in 60 min, respectively. The doped nanostructures lead to higher absorption of visible light and more separation of light-induced charged carriers. Effect of pH of the reaction medium and role of reactive oxygen species was also examined. Finally, a probable mechanism of charge transfer and degradation of the pollutants was also presented.

Thermoelectric properties of 1 T monolayer pristine and Janus Pd dichalcogenides.

In this paper, we investigate the stability and thermoelectric properties of 1 T PdSSe, PdSTe and PdSeTe Janus structures using density functional theory (DFT). All three systems are narrow gap semiconductors with indirect bandgaps of 0.94 eV, 0.33 eV and 0.34 eV respectively. Compared to transition metal dichalcogenide (TMD) monolayers, PdS2 and PdSe2 are semiconductors with wider indirect bandgaps of 1.29 eV and 0.69 eV respectively. Phonon dispersion calculations demonstrate that all pristine and Janus structures are mechanically stable despite the presence of negligible negative frequencies around the [Formula: see text] point in PdSTe and PdSeTe. Inspection of the lattice thermal conductivity ([Formula: see text]) shows that these structures are slightly anisotropic in the x and y  directions except for PdSe2 which shows a higher degree of anisotropy. Influenced by the values of [Formula: see text], the thermal electronic conductivity ([Formula: see text]), the electronic conductivity ([Formula: see text]) and the Seebeck effect (S), the figure of merit along the x (ZT xx )and y  (ZT yy ) directions register the largest values in the case of electron doping for the PdSe2 and PdSeTe 2D crystals. Interestingly, the figures of merit of the Janus structures are larger than their corresponding pristine PdX2 (X = S, Se) structures. Once synthesized, such information is crucial for the implementation of the PdXY (Y = Se, Te) structures in industrial applications.