Millions of people worldwide are exposed to excessive concentrations of fluoride (F⁻) from groundwater sources. Ca-Al-CO₃ layered double hydroxides (LDHs) have shown promising defluoridation efficiency; however, defluoridation by Ca-Al-CO₃ LDHs is highly pH sensitive. This study showed that simultaneous acidification by conventional acids, such as HCl and CO₂ substantially increased the performance of Ca-Al-CO₃ LDHs for F- removal at environmentally relevant concentrations (e.g., 10 mg/L) to below the WHO guideline value (1.5 mg/L), while, in comparison to other acids (HNO₃, H₂SO₄, H₃PO₄), the use of HCl and CO₂ does not lead to the introduction of potentially harmful or undesired anions. The addition of HCl and CO₂ to LDHs suspensions did lead to changes to the LDHs structure. Leaching experiments, supported by PHREEQC modelling and characterization (SEM-EDX, XRD and FTIR), strongly suggest that the main mechanism of F- removal by Ca-Al-CO₃ LDHs was F⁻ adsorption or complexation onto/into various rehydrated mixed metal oxides which re-precipitated upon partial LDHs dissolution when acidifying.

Excessive F^- in drinking water due to natural and anthropogenic activities is a serious health hazard affecting humans worldwide. In this study, a comparative assessment was made of eight mineral-based materials with advantageous structural properties for F^- uptake: layered-double-hydroxides (LDHs), geopolymers, softening pellets and struvite. These materials are considered low-cost, for being either a waste or by-product, or can be locally-sourced. It can be concluded that Ca-based materials showed the strongest affinity for F^- (Ca-Al-CO₃ LDHs, slag-based geopolymer, softening pellets). The Langmuir adsorption capacity of Ca-Al-CO₃ LDHs, slag-based geopolymer and softening pellets was observed to be 20.83, 5.23 and 1.20 mg/g, respectively. The main mechanism of F^- uptake on Ca-Al-CO₃ LDHs, Mg-Al-Cl LDHs, slag-based geopolymers and softening pellets was found to be sorption at low initial F^- concentrations (<10 mg/L) whereas precipitation as CaF₂ is proposed to play a major role at higher initial F^- concentrations (>20 mg/L). Although the softening pellets had the highest Ca-content (96-97%; XRF), their dense structure and consequent low BET surface area (2–3 m²/g), resulted in poorer performance than the Ca-based LDHs and slag-based geopolymers. Nevertheless, geopolymers, as well as struvite, were not considered to be of interest for application in water treatment, as they would need modification due to their poor stability and/or F^- leaching.

Sub-nanometer zeolite 13X-supported Ni-ceria catalysts were synthesized for CO₂ methanation. XRD and SEM results show the structure and morphology of 13X zeolite after impregnation and calcination. Ce loading affected the catalysts’ metal dispersion, reducibility, basicity and acidity, and thence their activity and selectivity. STEM-EDX elemental mappings showed that Ce and Ni are predominantly highly dispersed. Ce has a positive effect on the reduction of NiO and leads to a relatively high number of medium basic sites with a low Ce loading. Highly stable 5%Ni2.5%Ce13X had high activity and nearly 100% CH₄ selectivity in CO₂ methanation at 360 °C, which is mainly due to the high dispersion of metals and relatively high amount of medium basic sites. It can be inferred that this catalyst synthesis strategy has great potential for good catalyst dispersion, since metal uptake by the zeolite is selective for the metal citrate complexes in solution.

In this study, F⁻ removal by Ca–Al–CO₃ layered double hydroxides (LDHs) was investigated at environmentally-relevant concentration ranges (2–12 mg/L) to below the WHO guideline, with an emphasis on the effect of LDHs’ modification, as well as the effects of initial F⁻ concentration, adsorbent dose, pH, temperature and co-existing ions. Ca–Al–CO₃ LDHs, either untreated, calcined or microwave treated, showed affinity for the removal of F⁻ from synthetic groundwater with capacities of 6.7–8.4 mg F⁻/g LDHs at groundwater-relevant pH, with a higher F⁻ removal capacity at lower pH (<8) and lower temperature (12 °C, as compared to 25 °C & 35 °C). Since calcination and microwave treatment resulted in only marginal defluorination improvements, using untreated LDHs appears the practically most feasible option. For the untreated LDHs, competition with Cl⁻ and NO₃⁻ was not observed, whereas at higher HCO₃⁻ and SO₄²⁻ concentrations (>250 mg/L) a slight reduction in F⁻ removal was observed. This study indicates the potential of Ca–Al–CO₃ LDHs as a cost-effective F⁻ removal technology, particularly when locally sourced and in combination with low-cost pH correction.