Ultrastrong Anion Affinity of Anionic Clay Induced by Its Inherent Nanoconfinement.

Layered double hydroxide (LDH), the only anionic clay in the environment, plays a key role in natural ion transportation. The ion retention effect of LDHs was traditionally attributed to ion exchange with low affinity. Here, we demonstrated an ultrastrong interaction between anions and LDHs induced by their inherent nanoconfinement using chromium ore processing residue (COPR) that contained several Cr(VI)-bonded LDHs as a probe. Hydrocalumite (Ca/Al-Cl LDH) was verified as the primary phase for Cr(VI) retention through two types of interactions such as ion exchange and Cr-Ca coordination. More significantly, the confined spacing between two layers of hydrocalumite provided spatial restriction and shielding effects to the intercalated Cr(VI), which enhanced Cr-Ca coordination by shortening the bonding distance and modulating the binding angle to achieve the lowest bonding energy. Such enhancement boosted Cr(VI) affinity up to 3.2 × 105 mL/g, which was 1-3 orders of magnitudes higher than ion exchange. The universality of this mechanism was verified using another Mg/Al-Cl LDH and various anions. This study broke the traditional awareness of low ion affinities of LDHs limited by single ion exchange and disclosed an essential mechanism for unexpected ion retention effects of anionic clays in nature.

Adsorption of low-concentration mercury in water by 3D cyclodextrin/graphene composites: Synergistic effect and enhancement mechanism.

The efficient removal of mercury from aqueous media remains a severe challenge in ensuring environmental safety, especially for low-concentration mercury, which requires adsorbents with high mercury affinity. In this work, we reported a nanocomposite of ß-cyclodextrin and three-dimensional graphene (3D CD@RGO) to enhance the adsorption affinity and capacity for mercury with low concentrations. Characterization of the nanocomposite revealed that cyclodextrin was well dispersed on the 3D graphene support structure to provide highly exposed hydroxyl groups. Adsorption experiments showed that CD@RGO exhibited different adsorption behaviors for mercury within different concentration ranges of 0.2-4.0 mg/L and 4.0-10.0 mg/L, and the adsorption affinity for the former range (KL = 10.05 L/mg) was 1.5 times higher than that for the latter range (KL = 6.69 L/mg). Moreover, CD@RGO had a high adsorption efficiency of 96.6% with a superb adsorption affinity (172.09 L/g) at Ce = 0.01 mg/L, which is 6.70 and 41.25 times higher than that of RGO and RCD (physical mixture of RGO and cyclodextrin), respectively, indicating a synergistic effect of CD@RGO for mercury adsorption. This enhancement can be attributed to the transformation of the adsorption mechanism from the outer-sphere force of electrostatic interaction in RGO to the inner-sphere surface complexation in CD@RGO.