Nanoscale Insights into the Interaction Mechanism Underlying the Adsorption and Retention of Heavy Metal Ions by Humic Acid.

The mobility and distribution of heavy metal ions (HMs) in aquatic environments are significantly influenced by humic acid (HA), which is ubiquitous. A quantitative understanding of the interaction mechanism underlying the adsorption and retention of HMs by HA is of vital significance but remains elusive. Herein, the interaction mechanism between HA and different types of HMs (i.e., Cd(II), Pb(II), arsenate, and chromate) was quantitatively investigated at the nanoscale. Based on quartz crystal microbalance with dissipation tests, the adsorption capacities of Pb(II), Cd(II), As(V), and Cr(VI) ionic species on the HA surface were measured as ∼0.40, ∼0.25, ∼0.12, and ∼0.02 nmol cm-2, respectively. Atomic force microscopy force results showed that the presence of Pb(II)/Cd(II) cations suppressed the electrostatic double-layer repulsion during the approach of two HA surfaces and the adhesion energy during separation was considerably enhanced from ∼2.18 to ∼5.05/∼4.18 mJ m-2. Such strong adhesion stems from the synergistic metal-HA complexation and cation-π interaction, as evidenced by spectroscopic analysis and theoretical simulation. In contrast, As(V)/Cr(VI) oxo-anions could form only weak hydrogen bonds with HA, resulting in similar adhesion energies for HA-HA (∼2.18 mJ m-2) and HA-As(V)/Cr(VI)-HA systems (∼2.26/∼1.96 mJ m-2). This work provides nanoscale insights into quantitative HM-HA interactions, improving the understanding of HMs biogeochemical cycling.

Design a flower-like magnetic graphite carbon microsphere for enhanced adsorption of 2,4-dichlorophenol.

2,4-Dichlorophenol (2,4-DCP) is a hazardous chlorinated organic chemical, so its removal is an important task to protect the whole ecosystem and human health. During the material preparation, the magnetic graphitic carbon adsorbent (HFMCM) with a sparse sheet-like stacking structure was formed by interlayer assembly of nickel hydroxide nanosheets and hydrothermal glucose carbon. The conditions for optimal performance of the adsorbent are 45 °C and pH 5. The maximum adsorption capacity of HFMCM-180 for 2,4-DCP is 147.06 mg·g-1. Adsorption behavior in accordance with Langmuir isothermal model and pseudo-second-order kinetic models. The adsorbent remains selective for 2,4-DCP in metal ion solutions. More than 75% of the adsorption capacity is maintained after five cycles of adsorption. Electrostatic interaction, hydrogen bonding, and π-π bonding play a major role in the adsorption of 2,4-DCP by HFMCM. The adsorbent was glucose as the carbon source, nickel sulfate as the magnetic source, and hexamethylenetetramine as the precipitant. Its carbonization after pretreatment with different hydrothermal temperatures resulted in the synthesis of flower-like graphitic carbon spheres with magnetic properties. The interconnected pore channels on the adsorbent surface conferred large specific surface area to the material. 2,4-DCP was efficiently adsorbed by π-π stacking, hydrogen bonding, and electrostatic attraction within the pore channels with low spatial potential resistance.