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Herein, an efficient one-dimensional (1D) N-doped Co/C nanotube absorber was designed by a cobalt source and solvent ratio comodulation strategy. First, we explored the influences of different cobalt sources (CoCl2, Co-(OAc)2, Co-(NO3)2, and CoSO4) on the morphology and microwave absorption (MA) property, which showed that CoCl2 facilitated the formation of nanotubes with a relatively uniform diameter and length. Notably, the Co/C nanotubes displayed an ultrawide effective absorption bandwidth (EAB) of 6.885 GHz at 2.2 mm when the filling ratio was only 8 wt %. Then, by adjusting the solvent ratio of isopropanol (IPA) and water, Co/C showed a strong absorption of −44.51 dB with an EAB of 5.44 GHz at 2.35 mm. The outstanding MA performance is ascribed to the synergistic effect of dielectric and magnetic components, which is conducive to optimizing the impedance matching, thus broadening the EAB. In addition, the 1D nanostructure is good for constructing three-dimensional (3D) conductive networks and enhancing conductive loss. Since Co nanoparticles are wrapped in carbon nanotubes (CNTs), the confinement effect can effectively prevent the agglomeration of ferromagnetic nanoparticles, adjusting the MA performance. It is worth mentioning that the maximum Radar cross section (RCS) value of Co/C can be reduced by 28.8 dB m2. Furthermore, the RCS values are all lower than −10 dB m2 from −90 to 90° and the minimum RCS value can reach −46.8 dB m2. This work provides a strategy for designing lightweight MA absorbers with strong RL and ultrawide EAB. [ABSTRACT FROM AUTHOR]

The important role of natural organic matter (NOM) -- Fe colloids in influencing contaminant transport, and this role can be influenced by the formation, aggregation, and particle deposition dynamics of NOM-Fe colloids. In this work, NOM-Fe colloids at different C/Fe ratios were prepared by mixing different concentrations of humic acid (HA) with 10 mg/L Fe(11) under duuxlr rUrrtLuons. 1 ne t611ords were characterized by an array of techniques and their aggregation and deposition behaviors were examined under both anoxic and oxic conditions. The colloids are composed of HA-Fe(II) at anoxic conditions, while they are made up of HA-Fe(111) at oxic conditions until the C/Fe molar ratio exceeds I 6 For C/Fe molar ratios above 1.6, the aggregation and deposition kiurli,s of HA-Pe(11) colloids under anoxic conditions are slower than those of HA-Fe(III) colloids under oxic conditions. Further, the aggregation of HA-Fe colloids under both anoxic and oxic conditions decreases with increasing C/Fe molar ratio from 1.6 to 2.3.3. This study highlights the importance of the redox transformation of Fe(ll) to Fe(BI) and the C/Fe ratio for the formation and stability of NOM-Fe colloids that occur in subsurface environments with anoxic -- oxic interfaces. [ABSTRACT FROM AUTHOR]

The practical application of supercapacitors (SCs) has been known to be restricted by low energy density, and zinc ion capacitors (ZICs) with a capacitive cathode and a battery-type anode have emerged as a unique technology that can effectively mitigate the issue. To this end, the design of electrodes with low electrochemical impedance, high specific capacitance, and outstanding reaction stability represents a critical first step. Herein, we report the synthesis of hierarchical Ti 3 C 2 T X @PANI heterostructures by uniform deposition of conductive polyaniline (PANI) polymer nanofibers on the exposed surface of the Ti 3 C 2 T X nanosheets, which are then assembled into a three-dimensional (3D) cross-linking framework by a graphene oxide (GO)-assisted self-convergence hydrothermal strategy. This resulting 3D Ti 3 C 2 T X @PANI-reduced graphene oxide (Ti 3 C 2 T X @PANI-RGO) heterostructure hydrogel shows a large surface area (488.75 F g -1 at 0.5 A g -1 ), outstanding electrical conductivity, and fast reaction kinetics, making it a promising electrode material. Separately, defective RGO (DRGO) hydrogels are prepared by a patterning process, and they exhibit a broad and uniform distribution of mesopores, which is conducive to ion transport with an excellent specific capacitance (223.52 F g -1 at 0.5 A g -1 ). A ZIC is subsequently constructed by utilizing Ti 3 C 2 T X @PANI-RGO as the anode and DRGO as the cathode, which displays an extensive operating voltage (0-3.0 V), prominent energy density (1060.96 Wh kg -1 at 761.32 W kg -1 , 439.87 Wh kg -1 at 9786.86 W kg -1 ), and durable cycle stability (retaining 67.9% of the original capacitance after 4000 cycles at 6 A g -1 ). This study underscores the immense prospect of the Ti 3 C 2 T X -based heterostructure hydrogel and DRGO as a feasible anode and cathode for ZICs, respectively.

N-Heterocyclic nitreniums (NHNs) have been utilized as Lewis acid catalysts to activate substrates with lone pairs. Alternative to their conventional applications, we have discovered that NHNs can also serve as charge transfer complex catalysts. Herein, we present another potential of NHNs by utilizing a weak interaction between NHNs and CF 3 SO 2 Cl. The method promotes CF 3 SO 2 Cl to undergo photohomolysis, resulting in the CF 3 radical. Mechanistic studies suggested that the weak interaction could be due to the π-hole effect of NHNs.

Oxidation dissolution of arsenopyrite (FeAsS) is one of the important sources of arsenic contamination in soil and groundwater. Biochar, a commonly used soil amendment and environmental remediation agent, is widespread in ecosystems, where it participates in and influences the redox-active geochemical processes of sulfide minerals associated with arsenic and iron. This study investigated the critical role of biochar on the oxidation process of arsenopyrite in simulated alkaline soil solutions by a combination of electrochemical techniques, immersion tests, and solid characterizations. Polarization curves indicated that the elevated temperature (5-45 °C) and biochar concentration (0-1.2 g·L -1 ) accelerated arsenopyrite oxidation. This is further confirmed by electrochemical impedance spectroscopy, which showed that biochar substantially reduced the charge transfer resistance in the double layer, resulting in smaller activation energy ( E a = 37.38-29.56 kJ·mol -1 ) and activation enthalpy (Δ H * = 34.91-27.09 kJ·mol -1 ). These observations are likely attributed to the abundance of aromatic and quinoid groups in biochar, which could reduce Fe(III) and As(V) as well as adsorb or complex with Fe(III). This hinders the formation of passivation films consisting of iron arsenate and iron (oxyhydr)oxide. Further observation found that the presence of biochar exacerbates acidic drainage and arsenic contamination in areas containing arsenopyrite. This study highlighted the possible negative impact of biochar on soil and water, suggesting that the different physicochemical properties of biochar produced from different feedstock and under different pyrolysis conditions should be taken into account before large-scale applications to prevent potential risks to ecology and agriculture.

Constructing catalysts with electronic metal-support interaction (EMSI) is promising for catalytic reactions. Herein, graphene-supported positively charged (Pt 2+ /Pt 4+ ) atomically dispersed Pt catalysts (AD-Pt-G) with Pt x C 3 ( x = 1, 2, and 4)-based EMSI coordination structures are achieved for boosting the catalytic ozonation for odorous CH 3 SH removal. A CH 3 SH removal efficiency of 91.5% can be obtained during catalytic ozonation using optimum 0.5AD-Pt-G within 12 h under a gas hourly space velocity of 60,000 mL h -1 g -1 , whereas that of pure graphene is 40.4%. Proton transfer reaction time-of-flight mass spectrometry, in situ diffuse reflectance infrared Fourier transform spectroscopy/Raman, and electron spin resonance verify that the Pt x C 3 coordination structure with atomic Pt 2+ sites on AD-Pt-G can activate O 2 to generate peroxide species (*O 2 ) for partial oxidation of CH 3 SH during the adsorption period and trigger O 3 into surface atomic oxygen (*O ad ), *O 2 , and superoxide radicals (·O 2 - ) to accomplish a stable, high-efficiency, and deeper oxidation of CH 3 SH during the catalytic ozonation stage. Moreover, the results of XPS and DFT calculation imply the occurrence of Pt 2+ → Pt 4+ → Pt 2+ recirculation on Pt x C 3 for AD-Pt-G to maintain the continuous catalytic ozonation for 12 h, i.e., Pt 2+ species devote electrons in 5d-orbitals to activate O 3 , while Pt 4+ species can be reduced back to Pt 2+ via capturing electrons from CH 3 SH. This study can provide novel insights into the development of atomically dispersed Pt catalysts with a strong EMSI effect to realize excellent catalytic ozonation for air purification.

Natural organic matter-iron (NOM-Fe) colloids are ubiquitous at anoxic-oxic interfaces of subsurface environments. Fe(II) or NOM can chemically reduce Cr(VI) to Cr(III), and the formation of Cr(III)-NOM-Fe colloids can control the fate and transport of Cr. We explored the formation and transport of Cr(III)-humic acid (HA)-Fe colloids upon reaction of Cr(VI) with HA-Fe(II) colloids over a range of environmentally relevant conditions. Cr(VI) was completely reduced by HA-Fe(II) complexes under anoxic conditions, and the formation of Cr(III)-HA-Fe colloids depended on HA concentration (or molar C/Fe ratio) and redox conditions. No colloids formed at HA concentrations below 3.5 mg C/L (C/Fe ratio below 1.6), but Cr(III)-HA-Fe colloids formed at higher HA concentrations. In column experiments, Cr(III)-HA-Fe(III) colloids formed under oxic conditions were readily transported through sand-packed porous media. Colloidal stability measurements further suggest that Cr(III)-HA-Fe colloids are highly stable and persist for at least 20 days without substantial change in particle size. This stability is attributed to the enrichment of free HA adsorbed on the Cr(III)-HA-Fe colloid surfaces, intensifying the electrostatic and/or steric repulsion interactions between particles. The new insights provided here are important for evaluating the long-term fate and transport of Cr in organic-rich redox transition zones.

Analysis of complex pore structure of geomaterials is a fundamental issue in geoscience. Here bifunctional nanoparticles with magnetic and fluorescent properties are introduced as novel markers for optical imaging of pore structure in geomaterials. Using the paramagnetic property, powder of the nanoparticle is driven into pores under an external magnetic field, avoiding a tedious sample preparation and eliminating artificial damage of sample preparation in conventional methods. Meanwhile, the fluorescent nanoparticle marker offers a sharp contrast imaging between the rock matrix (black) and pores (bright) under microscopy. Furthermore, fluorescent nanoparticles with different sizes and colors are designed to demonstrate the potential of the method for describing pore throat sizes. Combining the merits of the paramagnetic and fluorescent properties of nanoparticles, a convenient and practical sample preparation is proposed to promote optical imaging analysis of the pore structure in geomaterials.

Sand filters are widely used for well water purification in endemic arsenicosis areas, but arsenic (As) removal is difficult at low intrinsic iron concentrations. This work developed an enhanced sand filter by electrochemically generated Fe(II) from an iron anode. The efficiency of As removal was tested in an arsenic burdened region in the Jianghan Plain, central China. By controlling a current of 0.6 A and a flow rate of about 12 L/h, the filter removed total As in the tube well water from 196 to 472 μg/L to below 10 μg/L, whereas the residual As was about 110 μg/L without electricity. Adsorption and subsequent oxidation on the surface of Fe(III) precipitates are the main processes controlling the removals of As and Fe. During a 30-day intermittent operation, both effluent As concentration and electrical energy consumption decreased progressively. Although filter clogging was observed, it can be alleviated by replacing the top layer of sand. Our findings suggest that dosing Fe(II) by an iron anode is an effective means to enhance As removal in a sand filter.

Mackinawite (FeS) nanoparticles have been extensively tested for reducing contaminants under anoxic conditions, while the oxidizing impact induced by FeS under oxic conditions has been largely underestimated. In light of previous findings that hydroxyl radicals (·OH) can be produced from oxygenation of sediment Fe(II), herein we revealed that ·OH can be produced efficiently from FeS oxygenation at circumneutral conditions, yielding 84.7 μmol ·OH per g FeS. Much more ·OH was produced from the oxygenation of FeS compared with siderite, pyrite, and zerovalent iron nanoparticles under the same conditions. The oxidation of FeS was a surface-mediated process, in which O 2 was transformed by the structural Fe(II) on FeS surface to ·OH with the generation of H 2 O 2 intermediate. A small proportion of Fe(II) was regenerated from the reduction of Fe(III) by FeS and S(-II), but this proportion did not significantly contribute to ·OH production. We further validated that the ·OH produced from FeS oxygenation considerably contributed to the oxidation of arsenic. As the change of redox conditions from anoxic to oxic is common in both natural and artificial processes, our findings suggest that the oxidizing impact induced by FeS at oxic conditions should be concerned due to ·OH production.

Transport of colloids in the subsurface is an important environmental process with most research interests centered on the transport in chemically stable conditions. While colloids can be formed under dynamic redox conditions, the impact of redox reactions on their transport is largely overlooked. Taking the redox reactions between ferrihydrite colloids and sulfide as an example, we investigated how and to what extent the redox reactions modulated the transport of ferrihydrite colloids in anoxic sand columns over a range of environmentally relevant conditions. Our results reveal that the presence of sulfide (7.8-46.9 μM) significantly decreased the breakthrough of ferrihydrite colloids in the sand column. The estimated travel distance of ferrihydrite colloids in the absence of sulfide was nearly 7-fold larger than that in the presence of 46.9 μM sulfide. The reduced breakthrough was primarily attributed to the reductive dissolution of ferrihydrite colloids by sulfide in parallel with formation of elemental sulfur (S(0)) particles from sulfide oxidation. Reductive dissolution decreased the total mass of ferrihydrite colloids, while the negatively charged S(0) decreased the overall zeta potential of ferrihydrite colloids by attaching onto their surfaces and thus enhanced their retention in the sand. Our findings provide novel insights into the critical role of redox reactions on the transport of redox-sensitive colloids in saturated porous media.

Mobilization of Arsenic in groundwater is primarily induced by reductive dissolution of As-rich Fe(III) oxyhydroxides under anoxic conditions. Creating a well-controlled artificial environment that favors oxidative precipitation of Fe(II) and subsequent oxidation and uptake of aqueous As can serve as a remediation strategy. We reported a proof of concept study of a novel iron-based dual anode system for As(III) oxidation and removal in synthetic groundwater. An iron anode was used to produce Fe(II) under iron-deficient conditions, and another inert anode was used to generate O2 for oxidative precipitation of Fe(II). For 30 min's treatment, 6.67 μM (500 μg/L) of As(III) was completely oxidized and removed from the solution during the oxidative precipitation process when a total current of 60 mA was equally partitioned between the two anodes. The current on the inert anode determined the rate of O2 generation and was linearly related to the rates of Fe(II) oxidation and of As oxidation and removal, suggesting that the process could be manipulated electrochemically. The composition of Fe precipitates transformed from carbonate green rust to amorphous iron oxyhydroxide as the inert anode current increased. A conceptual model was proposed for the in situ application of the electrochemically induced oxidative precipitation process for As(III) remediation.

Activated persulfate oxidation is an effective in situ chemical oxidation process for groundwater remediation. However, reactivity of persulfate is difficult to manipulate or control in the subsurface causing activation before reaching the contaminated zone and leading to a loss of chemicals. Furthermore, mobilization of heavy metals by the process is a potential risk. An effective approach using iron electrodes is thus developed to manipulate the reactivity of persulfate in situ for trichloroethylene (TCE) degradation in groundwater and to limit heavy metals mobilization. TCE degradation is quantitatively accelerated or inhibited by adjusting the current applied to the iron electrode, following k1 = 0.00053·Iv + 0.059 (-122 A/m(3) ≤ Iv ≤ 244 A/m(3)) where k1 and Iv are the pseudo first-order rate constant (min(-1)) and volume normalized current (A/m(3)), respectively. Persulfate is mainly decomposed by Fe(2+) produced from the electrochemical and chemical corrosion of iron followed by the regeneration via Fe(3+) reduction on the cathode. SO4(•-) and ·OH cocontribute to TCE degradation, but ·OH contribution is more significant. Groundwater pH and oxidation-reduction potential can be restored to natural levels by the continuation of electrolysis after the disappearance of contaminants and persulfate, thus decreasing adverse impacts such as the mobility of heavy metals in the subsurface.

A novel Pd-based electro-Fenton (E-Fenton) process has recently been developed to transform organic contaminants in groundwater. However, it only produces H2O2 and requires addition of Fe(2+). In this study, an innovative approach is developed to effectively regulate the generation of Fe(2+) from an iron cathode in a three-electrode system in addition to H2O2 production. The Fe(2+) is then used for the Pd-catalytic transformation of methyl tert-butyl ether (MTBE) in groundwater. Results from batch experiments suggest Fe(2+) accumulation follows pseudo-first-order kinetics with rate quantitatively regulated by current and pH, and MTBE can be completely transformed. In a specially configured three-electrode column using iron as the first cathode, the localized acidic conditions develop automatically in the iron cathode and Pd zone by partitioning the current between the two cathodes, leading to controllable generation of Fe(2+) and H2O2. Effects of electrolyte concentrations and types as well as humic acid on MTBE transformation are slight. The stable transformation (~70%) in a long-term study (20 days) suggests this improved Pd-based E-Fenton process is sustainable to produce Fe(2+), H2O2, and appropriate pH conditions simultaneously for transforming organic contaminants. This study presents a new concept of generating Fe(2+) from an iron cathode for the processes requiring Fe(2+).

A novel electro-Fenton process was developed for wastewater treatment using a modified divided electrolytic system in which H2O2 was generated in situ from electro-generated H2 and O2 in the presence of Pd/C catalyst. Appropriate pH conditions were obtained by the excessive H+ produced at the anode. The performance of the novel process was assessed by Rhodamine B (RhB) degradation in an aqueous solution. Experimental results showed that the accumulation of H2O2 occurred when the pH decreased and time elapsed. The maximum concentration of H2O2 reached 53.1 mg/L within 120 min at pH 2 and a current of 100 mA. Upon the formation of the Fenton reagent by the addition of Fe2+, RhB degraded completely within 30 min at pH 2 with a pseudo first order rate constant of 0.109 ± 0.009 min(-1). An insignificant decline in H2O2 generation and RhB degradation was found after six repetitions. RhB degradation was achieved by the chemisorption of H2O2 on the Pd/C surface, which subsequently decomposed into •OH upon catalysis by Pd0 and Fe2+. The catalytic decomposition of H2O2 to •OH by Fe2+ was more powerful than that by Pd0, which was responsible for the high efficiency of this novel electro-Fenton process.

Notoginseng, the root of Panax notoginseng (Burk.) F. H. Chen (Araliaceae), is a Chinese traditional medicine, which is used in both raw and processed forms due to their different pharmacological activities. Detailed chemical investigation on steamed notoginseng led to the isolation of 27 dammarane-type triterpenoids (1-27), including 4 new glycosides, namely, notoginsenosides ST-1-ST-3 and ST-5 (1-4), in addition to 3 other known compounds. Of the new compounds, 1-3 possess new aglycones. Their structures were elucidated on the basis of detailed analyses of their 1D and 2D NMR spectra and chemical reactions. The known compounds, koryoginsenoside-R1 (19), yesanchinoside D (20), 6''-O-acetylginsenoside Rg3 (24), and 3beta,6alpha,12beta-trihydroxydammar-20(21),24-diene ( 25), were isolated from notoginseng for the first time.