Charge transfer mechanism through S-scheme heterojunction in in-situ synthesized TiO2/Fe-doped hydroxyapatite for improved photodegradation of xanthate.

The heterojunction structure of the photocatalyst composite, which necessitates a robust interface and sufficient contact areas, holds the key to obtaining high charge carrier migration efficiency. Here, a novel composite, TiO2 nanoparticles/Fe-doped hydroxyapatite (TONPs/FH_CS), is fabricated using a two-step synthetic technique, in which FH_CS is synthesized from artificial converter slag enriched with Fe and Ca. The unique nanorod@plate structure of FH_CS enables the uniform immobilization of TONPs onto FH_CS. Thereby, an n-n type heterojunction exhibits a highly intimate Ti-O-Fe heterointerface. Kelvin probe testing demonstrates the formation of an interfacial electric field oriented from FH_CS to TONPs, which serves as the driving force for interfacial electron transfer through the Ti-O-Fe channels. The photoacoustic signals provide information on electron trap levels and densities, indicating the formation of the electron transfer channels. •O2- and •OH species are responsible for being the active species in this system. A photoexcited carrier transfer pathway exhibiting an S-scheme mechanism with high separation efficiency significantly enhances the utilization of charge carriers in each phase. Thus, improved xanthate degradation has been achieved using a heterojunction containing a photocatalyst derived from industrial solid waste. This work demonstrates the significant potential of steel-making byproduct utilization in industrial wastewater treatment.

Surface chemistry considerations of gangue dissolved species in the bastnaesite flotation system.

Inefficient flotation of bastnaesite remains a challenge in the production of rare earth elements. This study aimed to investigate the dissolution and adsorption behaviour of species that are commonly released into bastnaesite flotation pulp from Ca/Ba-bearing gangue minerals. The influence and corresponding mechanisms on the bastnaesite mineral surface and collectors, namely sodium oleate (NaOL), were evaluated experimentally based on micro-flotation, zeta potentials, in situ attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), and X-Ray photoelectron spectroscopy (XPS) analyses. The flotation recovery of bastnaesite significantly decreased from ∼95% to ∼25%, ∼15%, ∼80%, ∼25% when exposed to calcite, fluorite, barite, and mixed dissolved species, respectively. The zeta potential of bastnaesite was pH sensitive, indicating that H+ and OH- determine the surface potential of bastnaesite. Solution chemistry analyses revealed that the presence of the dissolved species differed at various pH values. In situ ATR-FTIR demonstrated the different effects of the dissolved species from calcite, fluorite, and barite on collector adsorption. The former two dissolved species mainly depressed the chemisorption of the NaOL monomers (RCOO‒), whereas calcite also affected the physical adsorption of the oleic acid molecular dimer (RCOOH·RCOO‒). Moreover, the barite dissolved species only affected the physical adsorption of the NaOL species. The results of XPS analysis revealed that dissolved species from these three gangues could pre-adsorbed onto bastnaesite and affected the interaction with the collector. Density functional theory calculations were employed to provide further theoretical insights into the interactions between the dissolved species from calcite, fluorite, and barite and NaOL.

In Situ Adsorption of Mixed Anionic/Cationic Collectors in a Spodumene-Feldspar Flotation System: Implications for Collector Design.

Herein, we investigated the effects of mixed collectors with varying alkyl chain lengths and ligand types on the hydrophobicity of the spodumene-feldspar flotation system. Various collector-mineral interactions were compared using in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy with two-dimensional correlation spectroscopy (2D-COS), in situ microcalorimetry, and X-ray photoelectron spectroscopy (XPS). The highest flotation separation performance can be achieved at a molar ratio of 6:1 and pH 8-9. The in situ microcalorimetry results revealed that the difference in the adsorption reaction heat of the mixed collector is larger than that of the single anionic collector. Moreover, the inconformity between the magnitude of adsorption reaction heat and the results observed for flotation recovery indicates that the heat of the reaction presumably involves the adsorption configurations of the collectors and the amounts adsorbed. In in situ ATR-FTIR with 2D-COS, it can be observed that octanohydroxamic acid/dodecylamine (OHA/DDA) is adsorbed much more intensely onto feldspar than onto spodumene due to the availability of more space on feldspar for the subsequent sorption of DDA after the prior bidentate chemisorption of OHA under alkaline conditions, whereas the sodium oleate (NaOL)/DDA adsorption sequence at pH 4-5 was the reverse of that at pH 8-9. Lastly, XPS was employed to provide further supplemental evidence for the bonding between these two minerals and single anionic/mixed collectors at the optimal pH of 8-9. In this study, the powerful in situ detection technologies can establish a new platform for exploring the underlying mechanism of new reagents at the solid-liquid interface. Moreover, the in-depth understanding related to the adsorption behavior of the mixed collector is beneficial for facilitating the selection and design of efficient and environmentally friendly flotation collectors with improved selectivity.

Influence of ultrasound pre-treatment on ilmenite surface chemical properties and collectors' adsorption behaviour.

In this study, we used flotation tests, Fourier transform infrared spectroscopy (FTIR), zeta potential, X-ray photoelectron spectroscopy (XPS), and microcalorimetry measurements to investigate the flotation and possible adsorption mechanisms of the ilmenite surface before and after ultrasonic pre-treatment. Flotation results show that under optimum conditions, the promotion effect of sonication on ilmenite is remarkable. The maximum recovery is 89.54% for ultrasonicated ilmenite at a pH of 4-5. For pH of 8-9, recovery increased again to 66.34%. Microcalorimetry indicates that the adsorption-driven heat release (-Qads) is higher for ultrasonicated ilmenite than for raw one. After pre-treatment, the iso-electric point (IEP) changed from pH 6.2 to pH 4.2. FTIR spectra and zeta potential measurements indicated that metal ions as active sites on the ilmenite surface are probably changed by the ultrasonic treatment. XPS analysis shows that ultrasonic treatment can promotes the oxidation of Fe2+ to Fe3+ and improves the solubilization of Ca2+ and Mg2+ in the pH range of 4-5. Under weakly alkaline condition, ultrasound also can make Ca2+ and Mg2+ re-absorb onto the ilmenite surface as main active sites.