This research focused on the investigation of layered double hydroxide (LDH)/halloysite materials’ adsorption efficiency and mechanisms in reactions with aqueous As(V) and Cr(VI) in a broad pH range. The materials consisting of Mg/Al LDH and halloysite were synthesized using both direct precipitation and physical mixing methods. The XRD, FTIR, DTA, SEM and XPS methods were used to evaluate the quality of the obtained materials and get insight into removal mechanisms. The XRD, FTIR and DTA confirmed LDH formation and showed the dominating presence of intercalated carbonates in the LDH structure. The SEM of the materials revealed characteristic agglomerates of layered LDH particles deposited on halloysite tubular forms. The raw LDH phases showed high removal efficiency of both As(V) and Cr (VI) for initial pH in the range of 3–7. In the studied concentration range the materials containing 25 wt % of LDH exhibited a removal efficiency very similar to the raw LDH. In particular, the halloysite presence in the materials’ mass had a positive effect in the reactions with As(V), which was removed by chemisorption. At a low pH the LDH component underwent partial dissolution, which lowered the adsorption efficiency. Apart from the anion exchange mechanism at a low pH the Cr(VI) was removed via formation of MgCrO₄ with Mg (II) being released from the LDH structure. The XPS spectra for As(V) did not show changes in oxidation state in the reactions. In turn, a partial reduction of Cr(VI) to Cr(III) was observed, especially at a high pH. The use of materials composed of two different minerals is promising due to reduction of costs as well as prevention of adsorbent swelling. This opens the possibility of its use in dynamic adsorption flow through systems.

Industrial wastewaters often contain mobile and toxic anions that cannot be removed by precipitation techniques and most known adsorbents. Layered double hydroxides (LDH) are excellent scavengers of anions; however, their use in real applications is of minor importance owing to their swelling behavior and high cost of production. The performed research shows the possibility of obtaining Mg/Fe LDH using natural magnesite. Moreover, heterostructured LDH/halloysite materials were synthesized. The adsorption efficiency of these materials was very high in both single- and multi-element systems, confirming the LDH selectivity. This was with the exception of wastewaters containing a high concentration of chlorides, which clearly hampered the removal of Cr(VI) and S(VI). The measurements indicated that LDH dissolution took place to a small extent (<10 wt%). The LDH/halloysite materials showed lower efficiency than the raw LDH; however, the clay presence has several benefits in terms of future applications: (i) it significantly reduces the pH, especially in contrast to the calcined LDH, which enables the reuse or safe disposal of purified water; (ii) it reduces swelling of the composite, which opens the possibility for applications in column adsorption; (iii) it induces dual adsorption properties through additional cation adsorption; and (iv) it substantially lowers the price of the adsorbent.

Search for inexpensive and efficient methods of critical raw materials recovery is of great importance across the world due to growing demand for green technologies. Formation and detailed characterization of new Pb- and Light Rare Earth Elements (LREE)-containing phosphates, compared to already described Pb- or LREE-containing phosphates, was described in this work. These phases were precipitated at experimental conditions similar to these used in a newly proposed coprecipitation route for REE recovery from aqueous solutions. The formation of La, Ce, Pr and Sm phosphates from aqueous solutions proceeded differently in the presence of Pb than in its absence. No rhabdophane group minerals, (REE,Ca,Th)(PO ₄ )· n H ₂ O were formed, which were the product of crystallization in the absence of Pb, as evidenced by the PXRD analysis of the control LREE phosphates. Instead, a new, distinct phase was formed, which is neither a ‘phosphoschultenite’, PbHPO ₄ , with La, Ce, Pr or Sm substitution nor a rhabdophane with Pb substitution. This showed that PbHPO ₄ structure did not accept isomorphic substitutions of LREE elements and rhabdophane structures are reluctant to accept Pb substitutions. At the same time, the formation of a hitherto unknown crystalline phase was found to be a mixed (LREE,Pb)-phosphate. A lower pH caused higher crystallinity of phases, as confirmed by SEM and PXRD. FTIR spectroscopy showed the hydrous nature of the obtained phases, which was additionally confirmed by thermal analysis. Decreasing pH of the reaction solution resulted in a higher crystalline water content. Moreover, La-bearing phases contained more chemically bound water than other phases. A combined EDS analysis and ICP-OES led to the chemical composition of new Pb phases with La, Ce, Pr and Sm that can be expressed as La ₂ Pb ₃ (PO ₄ ) ₄ ·3.5H ₂ O, Ce ₂ Pb ₃ (PO ₄ ) ₄ ·3.3H ₂ O, Pr ₂ Pb ₃ (PO ₄ ) ₄ ·3.1H ₂ O and Sm ₂ Pb ₃ (PO ₄ ) ₄ ·3.3H ₂ O, respectively. These results give a better understanding of potential novel recovery pathways of REE from phosphate mineral sources or wastes.