The concentrations of terrestrially sourced dissolved organic matter (DOM) have expanded throughout aquatic ecosystems in recent decades. Although sorption to minerals in soils is one major pathway to sequestrate soil organic matter, the mechanisms of organic matter−mineral interactions are not thoroughly understood. Here, we investigated the effect of calcium phosphate mineralization on humic acid (HA) fixation in simulated soil solutions, either with or without clay mineral montmorillonite (Mt). We found that Mt in solution promoted nucleation and crystallization of calcium phosphate (CaP) due to amorphous calcium phosphate clustering and coalescence on Mt surface, which contributed to the long-term persistence and accumulation of HA. Organic ligands with specific chemical groups on HA have higher binding energies to CaP−Mt than to CaP/Mt, according to dynamic force spectroscopy observations. Moreover, CaP−Mt formed in solution showed a great capacity for HA adsorption with a maximum adsorption quantity of 156.89 mg/g. Our findings directly support that Mt is crucial for DOM sequestration by facilitating CaP precipitation/transformation. This has an impact on how effectively we understand the long-term turnover of DOM and highlights knowledge gaps that might assist in resolving essential soil C sequestration issues.

Sodium metal is one of the most promising anodes for the prospective low-cost rechargeable batteries. Nevertheless, the commercialization of Na metal anodes remains restricted by sodium dendrite growth. Herein, halloysite nanotubes (HNTs) were chosen as the insulated scaffolds, and Ag nanoparticles were introduced as sodiophilic sites to achieve uniform sodium deposition from bottom to top under the synergistic effect. Density functional theory (DFT) calculation results demonstrated that the presence of Ag greatly increased the binding energy of sodium on HNTs/Ag (−2.85 eV) vs HNTs (−0.85 eV). Meanwhile, thanks to the opposite charges on the inner and outer surfaces of HNTs, faster Na+ transfer kinetics and selective adsorption of SO3CF3 – on the inner surface of HNTs were achieved, thus avoiding the formation of space charge. Accordingly, the coordination between HNTs and Ag afforded a high Coulombic efficiency (about 99.6% at 2 mA cm–2), long lifespan in a symmetric battery (for over 3500 h at 1 mA cm–2), and remarkable cycle stability in Na metal full batteries. This work offers a novel strategy to design a sodiophilic scaffold by nanoclay for dendrite-free Na metal anodes.

In recent decades, the concentration of dissolved organic matter (DOM) in aquatic ecosystems has gradually increased, leading to water pollution problems. Understanding the interfacial chemical processes of DOM on natural minerals is important to the exploration of high-efficiency absorbents. However, studying DOM chemical processes and adsorption mechanisms are still challenging due to the complex DOM structure and environmental system. Hence, we characterized the microstructure changes after the formation of amorphous calcium phosphate (ACP) at the interface of montmorillonite (Mt) minerals in a simulated environment system. Combined with atomic force microscopy and density functional theory (DFT) simulation, the mechanism of interfacial interaction between Mt-ACP and DOM was characterized at the molecular level. Moreover, we further evaluated the adsorption behavior of Mt-ACP as a potential adsorbent for organic matter. The comprehensive investigation of humic acid adsorption, intermolecular force, and DFT simulation is conducive to our understanding of the interfacial interaction mechanism between organic matter and noncrystalline minerals in aquatic environments and provides new perspectives on the application of clay-based mineral materials in pollutant removal under exposure from DOM.

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