TS-1 zeolite and a series of Zr-modified samples (TS-1/xZr) were synthesized and systematically characterized to investigate the influence of zirconium incorporation on structural, textural, and photocatalytic properties. The structural and textural properties of the samples were examined by XRD and nitrogen adsorption isotherms. Elemental analysis (EDXRF, SEM/EDS) and FTIR confirmed successful incorporation of Zr into the TS-1 framework. Photocatalytic tests under white light irradiation using crystal violet (CV), methylene blue (MB), rhodamine B (RhB) and methyl orange (MO) dyes revealed enhanced degradation efficiency for the Zr-containing samples, particularly TS-1/10Zr. Kinetic modeling using pseudo-first-order (PFO) and pseudo-second-order (PSO) approaches indicated that dye degradation followed mainly PSO kinetics. Reusability studies demonstrated sustained stability and recyclability of the catalysts. The improved photocatalytic performance is attributed to synergistic electronic effects between Ti and Zr species, which enhance charge separation and light absorption.
The present study focuses on the adsorption of Pb(II) by the H-form of titanosilicates (ETS-4, GTS-1) and clinoptilolite. The H-forms were prepared by first exchanging the extra-framework cations—Na+, K+, Ca2+, etc.—with NH4+, and by subsequent thermal treatment for obtaining H-forms. The purity and thermal behaviour of the initial, NH4+, and H-forms of ETS-4, GTS-1, and clinoptilolite were analysed by powder XRD, while the morphology and size of the particles were determined by SEM. The chemical composition of the solids and the solutions was obtained by WDXRF and ICP-OES, respectively. The kinetics research of the Pb(II) adsorption processes was based on WDXRF and ICP-OES. The H-forms of the materials displayed favourable properties for the adsorption of Pb(II). The best behaviour in this respect was demonstrated by GTS-1 when compared to ETS-4 and clinoptilolite.
The present work focuses on the removal of dyes from polluted water, and, more precisely, the targets are crystal violet (CV) and methylene blue (MB). For this purpose, a series of Zr-modified catalysts based on microporous Engelhard Titanium Silicate 10 (ETS-10) were developed and synthesized. Aiming at improvement in the photodegradation efficiency and stability of ETS-10, Zr centers replacing part of Ti ones were introduced during the synthesis procedure. The obtained Na-K-ETS-10/xZr catalysts were characterized by X-ray powder diffraction (XRD), wavelength dispersive X-ray fluorescence (WDXRF), N2 physisorption and Fourier transform infrared spectroscopy (FTIR). The photocatalytic properties of Na-K-ETS-10/xZr- (x = 5, 10, 15 and 20 wt% Zr) catalysts were studied in terms of water purification from crystal violet and methylene blue. The Na-K-ETS-10/xZr wt% x = 6 catalyst appeared to be the most efficient in the photodegradation of CV and MB, removing nearly 100% of the dyes. Kinetic studies showed that the removal of CV and MB is a rapid process and one, which obeys the non-linear pseudo-second-order model.
In this study, the photocatalytic performance of natural clinoptilolite was enhanced through copper modification, achieved via ion exchange followed by KOH-induced precipitation, leading to materials with different copper speciation. Physicochemical characterization using WDXRF, PXRD, FTIR and N2 physisorption revealed a transition from exchanged Cu2+ species at low loading to the formation of copper-bearing phases such as brochantite, Cu(OH)2 and CuO at higher alkalinity. The Cu-modified samples were evaluated for the photocatalytic degradation of Congo red under UV irradiation. Among them, sample NZ-Cu3 exhibited the highest activity, achieving approximately 91% dye degradation within 30–40 min. Kinetic analysis demonstrated that the degradation process is better described by the pseudo-second-order model, indicating that chemisorption plays a dominant role. Radical scavenger experiments revealed that photogenerated holes (h⁺) are the primary reactive species responsible for dye degradation, while hydroxyl radicals contribute to a lesser extent. The enhanced photocatalytic performance is attributed to the synergistic effect of photocatalytic degradation, improved charge separation and the presence of surface copper species, highlighting Cu-modified clinoptilolite as a promising low-cost photocatalyst for wastewater treatment.
1 December 2023 in Review of the Bulgarian Geological Society
The natural zeolites were ultrasonically treated and impregnated with silver nanoparticles. The surface stabilized silver nanoparticles dispersion was obtained using an effective electrochemical reduction method. The phase and elemental composition, structure of the Ag-impregnated zeolites (clinoptilolite and mordenite) was studied by various methods such as powder X-ray diffraction, X-ray fluorescence analyses and Fourier-transform infrared spectroscopy. The Ag-impregnated clinoptilolite and mordenite natural zeolite materials with 1.20 wt %, 0.97 wt %, 0.83 wt % and 1.18 wt % silver content were established by XRF analysis. As initial materials were used three types clinoptilolite from Beli Plast, Most, Golobradovo (Kardzhali, Bulgaria) deposits and mordenite from Lyaskovets deposit in Eastern Rhodopes, Bulgaria. The catalytic ability of Ag-mordenite and Ag-clinoptilolites was investigated in the ecologically important reaction of ozone decomposition. The Ag-loaded mordenite demonstrates the higher conversion degree of ozone more than 40% in comparison with Ag-clinoptilolite materials at room temperature.
FAU-type zeolite NaX was successfully prepared using hydrothermal synthesis at 90 °C for 6 h. The Mn- and Cu-ion-exchanged NaX zeolites were obtained. After the ion exchange, the zeolite powders were thermally treated at 300 °C. As well as Ag-ion-exchanged zeolite, NaX and zeolite were impregnated with two types of Ag nanoparticle dispersions: citrate surface-stabilized (Cit@Ag NPs) and polymer-stabilized (PVP@Ag) nanoparticles. Silver nanoparticles were synthesized using the electrochemical reduction method. The changes in the phase and chemical composition and structure of the obtained zeolite powders before and after ion exchange or impregnation were investigated by PXRD analysis, FTIR spectroscopy, and XRF analysis. The results show that Mn, Cu-exchanged NaX, and that impregnated with Ag demonstrated catalytic abilities towards ozone decomposition in comparison with pure zeolite (non-catalytic activity).