Edge-Enriched Molybdenum Disulfide Ultrathin Nanosheets with a Widened Interlayer Spacing for Highly Efficient Gaseous Elemental Mercury Capture.

Transition metal sulfides have exhibited remarkable advantages in gaseous elemental mercury (Hg0) capture under high SO2 atmosphere, whereas the weak thermal stability significantly inhibits their practical application. Herein, a novel N,N-dimethylformamide (DMF) insertion strategy via crystal growth engineering was developed to successfully enhance the Hg0 capture ability of MoS2 at an elevated temperature for the first time. The DMF-inserted MoS2 possesses an edge-enriched structure and an expanded interlayer spacing (9.8 Å) and can maintain structural stability at a temperature as high as 272 °C. The saturated Hg0 adsorption capacities of the DMF-inserted MoS2 were measured to be 46.91 mg·g-1 at 80 °C and 27.40 mg·g-1 at 160 °C under high SO2 atmosphere. The inserted DMF molecules chemically bond with MoS2, which prevents possible structural collapse at a high temperature. The strong interaction of DMF with MoS2 nanosheets facilitates the growth of abundant defects and edge sites and enhances the formation of Mo5+/Mo6+ and S22- species, thereby improving the Hg0 capture activity at a wide temperature range. Particularly, Mo atoms on the (100) plane represent the strongest active sites for Hg0 oxidation and adsorption. The molecule insertion strategy developed in this work provides new insights into the engineering of advanced environmental materials.

Synthesis of Core-Shell Magnetic Fe3O4@poly(m-Phenylenediamine) Particles for Chromium Reduction and Adsorption.

Magnetic Fe3O4@poly(m-phenylenediamine) particles (Fe3O4@PmPDs) with well-defined core-shell structure were first designed for high performance Cr(VI) removal by taking advantages of the easy separation property of magnetic nanoparticles (MNPs) and the satisfactory adsorption property of polymers. Through controlling the polymerization on MNPs, directly coating was realized without the complicated premodification procedures. The particle property and adsorption mechanism were analyzed in details. Fe3O4@PmPDs exhibited tunable PmPD shell thickness from 10 to 100 nm, high magnetic (∼150 to ∼73 emu g(-1)) and facile separation property by magnet. The coating of PmPD significantly enhanced Cr(VI) adsorption capacity from 46.79 (bare MNPs) to 246.09 mg g(-1) (71.55% PmPD loading proportion), much higher than many reported composite adsorbents. The high Cr(VI) removal performance was attributed to the adsorption of Cr(VI) on protonated imino groups and the efficient reduction of Cr(VI) to Cr(III) by amine, followed by Cr(III) chelated on imino groups, which are spontaneous and endothermic. The Fe3O4@PmPDs have great potential in treating Cr(VI)-contaminated water.

Constructing Heterointerfaces in Dual-Phase High-Entropy Oxides to Boost O2 Activation and SO2 Resistance for Mercury Removal in Flue Gas.

The low O2 activation ability at low temperatures and SO2 poisoning are challenges for metal oxide catalysts in the application of Hg0 removal in flue gas. A novel high-entropy fluorite oxide (MgAlMnCo)CeO2 (Co-HEO) with the second phase of spinel is synthesized by the microwave hydrothermal method for the first time. A high efficiency of Hg0 removal (close to 100%) is achieved by Co-HEO catalytic oxidation at temperatures as low as 100 °C and in the atmosphere of 145 µg m-3 Hg0 at a high GHSV (gas hourly space velocity) of 95,000 h-1. According to O2-TPD and in situ FT-IR, this extremely superior catalytic oxidation performance at low temperatures originates from the activation ability of Co-HEO to transform O2 into superoxide and peroxide, which is promoted by point defects induced from the spinel/fluorite heterointerfaces. Meanwhile, SO2 resistance of Co-HEO for Hg0 removal is also improved up to 2000 ppm due to the high-entropy-stabilized structure, construction of heterointerfaces, and synergistic effect of the multicomponents for inhibiting the oxidation of SO2 to surface sulfate. The design strategy of the dual-phase high-entropy material launches a new route for metal oxides in the application of catalytic oxidation and SO2 resistance.

Low-temperature Hg0 abatement by ionic liquid based on weak interaction.

Low-temperature gaseous elemental mercury (Hg0) abatement is an objective demand in industrial flue gas treatment. In this work, we proposed a new approach for Hg0 capture via weak interaction of ionic liquids. Ionic liquids with varied anions (1-butyl-3-methylimidazolium thioacetate ([Bmim][ThAc]), 1-butyl-3-methylimidazolium diethyldithiocarbamate ([Bmim][DTCR]), and 1-butyl-3-methylimidazolium ethylxanthate ([Bmim][EX])) were designed and synthesized. The interaction energies between ionic liquids and elemental mercury were proved to be positively related to mercury removal efficiency, revealing that the electrostatic interaction derived physical adsorption from anions is the dominant factor affecting mercury removal performance. [Bmim][ThAc] with the largest anionic electrostatic interaction energy showed the best mercury abatement performance, achieving a Hg0 removal efficiency of over 98% and an adsorption capacity of 10.66 mg/g at 50 °C. The influence of temperature and the results of mercury temperature-programmed desorption (Hg-TPD), X-ray photoelectron spectroscopy (XPS) further confirmed that the ionic liquid combines with elemental mercury through physical adsorption. The work provides a new perspective on designing high-efficiency sorbents for mercury removal at low temperature.

"In-situ synthesized" iron-based bimetal promotes efficient removal of Cr(VI) in by zero-valent iron-loaded hydroxyapatite.

Anionic Cr(VI) and cationic heavy metals generally co-exist in industrial effluents and threaten the public health. Zero-valent iron (ZVI) particles tent to passivate rapidly, which results in a gradual drop in its reactivity. In this work, a strategy of "in-situ synthesized" iron-based bimetal was first developed to stimulate the self-activation of passivated ZVI. During this process, ZVI-loaded hydroxyapatite (ZVI/HAP) was prepared to enhance the affinity for co-existing Cu2+, which promoted the in-situ Cu0 deposition on ZVI/HAP to form a Fe-Cu bimetal. The deposited Cu0 significantly decreased the activation energy (Ea) of Cr(VI) reduction by 24.9%, and its corresponding Cr(VI) removal (96.53%) was much higher that of single Cr(VI) system (68.67%) within 9 h. More importantly, the removal of Cr(VI) and Cu2+ were synchronously achieved. Systematical electrochemical characterizations were first introduced to explore the galvanic behaviors of iron-based bimetal. The charge transfer resistance and the negative open circuit potential of ZVI/HAP significantly decreased with the Cu0 deposition, thereby accelerating the electron transfer from Fe0 to Cu2+. The enhanced electron transfer further facilitated the Fe(II) release to promote Cr(VI) reduction. This "in-situ synthesized" iron-based bimetal strategy provides a novel pattern for ZVI activation and exhibits practical application in remediation of combined contaminant.