Unveiling glutamic acid-functionalized LDHs: understanding the Cr(VI) removal mechanism from microscopic and macroscopic view points.

Interlayer functionalization modulation is essential for modifying LDHs and improving their selectivity and adsorption capacity for target pollutants. In this work, Glu@NiFe-LDH was synthesized using a simple one-step hydrothermal method and tested for its ability to remove CrO42- from wastewater. The modification significantly increased the composite material's removal ability by 2-3 times, up to 98.36 mg g-1. The behavior of CrO42- adsorption on Glu@NiFe-LDH was further studied by adjusting the affecting factors (i.e., temperature, pH, contact time, initial concentration, and interfering substance), and the adsorption behavior was confirmed as a spontaneous and chemisorption process. And the result was that Glu@NiFe-LDH demonstrated high capacity, efficiency, stability, and selectivity for the adsorption of CrO42- in a single electrolyte and natural water containing competing anions. Furthermore, molecular dynamics simulations (NVT ensemble) were employed to further reveal the mechanism of glutamic acid modification on LDH at the microscopic scale. Additionally, the IRI analysis method revealed the mechanism of weak interaction between glutamic acid molecules and CrO42-. This study provides a detailed understanding of the intercalation mechanism involved in the amino acid modification of LDHs. It explains the adsorption mechanism of metal oxo-acid radicals by amino acid-modified LDHs from a theoretical perspective. The findings offer experiments and a theoretical basis for designing targeted adsorbents in the future.

3D-Printed river-type thick carbon electrodes for docking possible practical application-level capacitive deionization.

The low carbon mass loading along with serious imbalance between the carbon mass loading and the electrode performance greatly hinders practical applications of capacitive deionization (CDI). Traditional thick bulk-type (BT) carbon electrodes often suffer from extremely limited active sites, thereby being vital to explore a basic strategy to unlock the performance. Herein, 3D-printed thick carbon electrodes were utilized for CDI desalination for the first time. The experimental outcomes revealed that BT electrodes existed a serious salt adsorption capacity (SAC) drop under variable mass loading of 3-30 mg/cm2. In contrary, 3D-printed river-type (RT) electrodes acquired a superior SAC of 10.67 mg/g and achieved 54.1 % SAC rise compared with that of BT electrodes (500 mg/L; 1.0 V; 30 mg/cm2). Meanwhile, RT electrodes took only 12 min to reach the equilibrium SAC of BT electrodes, being 44 min faster. Further, RT electrodes with diverse mass loading of 30-45 mg/cm2 were investigated, and it still kept 7.13 mg/g SAC under ultrahigh mass loading of 45 mg/cm2. This strategy has been successfully extended and carbons with proper micro-meso pore distribution, high specific capacitances and low resistance may be a better selection. Besides, the impact of electrode channel structure on the desalting performance was investigated, and the influence mechanism was revealed via COMSOL simulation. Overall, this work demonstrates the splendid feasibility of utilizing 3D-printed thick carbon electrodes for possible practical application-level CDI desalination.

Investigation of the adsorption performance and mechanism of 2-mercaptoethane sulfonic acid intercalated modified layered double hydroxide on heavy metal ions.

In the adsorption process of functionalized layered double hydroxide (LDH) to target pollutants it, is essential to investigate the role of functional groups. In this work, 2­mercaptoethane sulfonic acid (MS) was used as an intercalation modifier to prepare functionalized NiFe-LDH by solvothermal method. The interfacial interaction between the functional groups and the NiFe-LDH surface was studied via molecular dynamics simulation. During the intercalation process, the more negatively charged sulfonic acid group tends to self-assemble electrostatically with the LDH laminate, while the sulfhydryl group is involved in complexing heavy metal ions. The adsorption experiments showed that the adsorption performance of the adsorbent for the three ions of Cd2+, Mn2+, and Co2+ at 298.15 K was 266.16 mg/g, 175.60 mg/g, and 106.56 mg/g, respectively, which were 10 times, 8.7 times, and 4.9 times higher than that of unmodified NiFe-LDH. Meanwhile, Multiwfn wavefunction analysis combined Visual Molecular Dynamics (VMD) was applied to analyze and visualize the reaction active sites & the interactions between MS and NiFe-LDH, and the complexation of the functional group of MS with metal ions, to insight the role of the functional groups in MS molecule, and to reveal the cause that the adsorption capacity of modified NiFe-LDH for heavy metals greatly improves from the view of atoms.

Investigation of the efficient adsorption performance and adsorption mechanism of 3D composite structure La nanosphere-coated Mn/Fe layered double hydrotalcite on phosphate.

Severe water eutrophication due to large releases of phosphorus has become a worldwide environmental problem. Adsorption active sites is less of traditional adsorbents in the phosphorus removal process resulting in low removal efficiency, so the new high-efficiency phosphorus removal adsorbents become an effective way to solve the problem. In this work, quercetin modified MnFe layered double hydrotalcite three-dimensional composites structures encapsulated by lanthanum (La(III)) nanoparticles (QLa@MnFe-LDH) were successfully prepared by a classical hydrothermal method. The results of the adsorption experiments show that La(III) nanosphere-encapsulated MnFe-LDH provides a more adequate binding site for phosphate adsorption. The adsorption performance of QLa@MnFe-LDH for phosphate was outstanding, the maximum adsorption capacity was 346.5 mg/g at 298.15 K, which was 300 % higher than that of MnFe-LDH. Moreover, QLa@MnFe-LDH retained its high adsorption capacity (>315.5 mg/g) over a wide range of pH (4.0 âˆ¼ 7.0). The active sites of the reactions were predicted by Multiwfn and Visual Molecular Dynamics (VMD), and novel visualization studies of weak interactions were applied to theoretical studies. The modified MnFe-LDH encapsulated by La nanospheres has a strong adsorption capacity for phosphate adsorption. Therefore, the modified QLa@MnFe-LDH was expected to become an effective adsorption material for phosphorus removal.

A modified 'skeleton/skin' strategy for designing CoNiP nanosheets arrayed on graphene foam for on/off switching of NaBH4 hydrolysis.

CoNiP nanosheet array catalysts were successfully prepared on three-dimensional (3D) graphene foam using hydrothermal synthesis. These catalysts were prepared using 3D Ni-graphene foam (Ni/GF), comprising nickel foam as the 'skeleton' and reduced graphene oxide as the 'skin'. This unique continuous modified 'skeleton/skin' structure ensure that the catalysts had a large surface area, excellent conductivity, and sufficient surface functional groups, which promoted in situ CoNiP growth, while also optimizing the hydrolysis of sodium borohydride. The nanosheet arrays were fully characterized and showed excellent catalytic performance, as supported by density functional theory calculations. The hydrogen generation rate and activation energy are 6681.34 mL min-1 g-1 and 31.2 kJ mol-1, respectively, outperforming most reported cobalt-based catalysts and other precious metal catalysts. Furthermore, the stability of mockstrawberry-like CoNiP catalyst was investigated, with 74.9% of the initial hydrogen generation rate remaining after 15 cycles. The catalytic properties, durability, and stability of the catalyst were better than those of other catalysts reported previously.