Mechanochemical synthesis of microscale zero-valent iron/N-doped graphene-like biochar composite for degradation of tetracycline via molecular O2 activation.

In this study, we prepared a micron zero-valent iron/N-doped graphene-like biochar (mZVI/NGB) composite using a mechanochemical method for tetracycline (TC) degradation through O2 activation. The mZVI and NGB components formed a strong coupling catalytic system, with mZVI acting as an electron pool and NGB as a catalyst for H2O2 generation. Under circumneutral pH (5.0-6.8), the mZVI/NGB composite exhibited exceptional TC removal efficiency, reaching nearly 100 % under optimal conditions. It also showed good tolerance to co-existing anions, such as Cl-, SO42-, and humic acid. Further studies found that the TC degradation mechanism was mainly ascribed to the non-radical pathway (1O2 and electron transfer), and the Fe2+/Fe3+ redox cycle on the composite's surface also played a crucial role in maintaining catalytic activity. This research contributes to the development of advanced materials for sustainable and effective water treatment, addressing pharmaceutical pollutant contamination in water sources.

Tannic acid modified microscale zero valent iron (TA-mZVI) with enhanced anti-passivation capability for Cr(VI) removal.

The removal of Cr(VI) from aqueous solutions using microscale zerovalent iron (mZVI) shows promising potential. However, the surface passivation of mZVI particles hinders its widespread application. In this study, we prepared tannic acid (TA) modified mZVI composite (TA-mZVI) by a simple sonication method. The introduction of TA allowing TA-mZVI composite to adsorb Cr(VI) rapidly under electrostatic forces attraction, guarantying TA-mZVI exhibited remarkable Cr(VI) removal capacity with a maximum adsorption capacity of 106.1 mg⋅g-1. At an initial pH of 3, it achieved a rapid removal efficiency of 96.2% within just 5 min, which was 7.7 times higher than that of mZVI. Various characterizations, including XPS and CV analysis, indicated that the formation of TA-Fe complexes accelerates electron transfer. In addition, TA endows functional groups to TA-mZVI, raising the dispersion and stability and serves as a protective layer hindering passivation. Further mechanistic analysis revealed that Cr(VI) removal by TA-mZVI followed an adsorption-reduction-precipitation mechanism, with TA mitigating the surface passivation of mZVI and facilitating the reduction of most Cr(VI) to Cr(III). Batch cyclic experiments revealed that TA-mZVI exhibited satisfactory performance, maintaining over 85% Cr(VI) removal even after five cycles and minimally affected by various coexisting ions. With notable advantages in cost-effectiveness, ease-synthesis and recovery, this work provides a great promise for developing efficient reactive adsorbent for addressing Cr(VI) contamination in aqueous solutions.

Sulfidated microscale zero-valent iron/reduced graphene oxide composite (S-mZVI/rGO) for enhanced degradation of trichloroethylene: The role of hydrogen spillover.

Atomic hydrogen (H*) has long been thought to play an important role in the dechlorination of trichloroethylene (TCE) by carbon-supported zero-valent iron (ZVI), which offers an alternative pathway for TCE dechlorination. Herein, we demonstrate that the reductive dechlorination of TCE by sulfidated microscale ZVI (S-mZVI) can be further enhanced by promoting the formation of H* through the introduction of reduced graphene oxide (rGO). The completely degradation of 10 mg/L TCE can be achieved by S-mZVI/rGO within 24 h, which was 3.3 times faster than that of S-mZVI. The change in the distribution of TCE degradation products over time suggests that the introduction of rGO leads to a change in the dechlorination pathway. The percentage of ethane in the final products of TCE degradation by S-mZVI/rGO was 34.3 %, while that of S-mZVI was only 21.9 %. The electrochemical tests confirmed the occurrence of hydrogen spillover in the S-mZVI/rGO composite, which promoted the reductive dechlorination of TCE by H*. Although the S-mZVI/rGO composite had stronger hydrogen evolution propensity than S-mZVI, the S-mZVI/rGO composite still exhibited higher electron utilization efficiency than S-mZVI thanks to the increased utilization of hydrogen.

Strong influence of degree of substitution on carboxymethyl cellulose stabilized sulfidated nanoscale zero-valent iron.

Carboxymethyl cellulose (CMC) has been widely adopted as stabilizer to enhance the subsurface mobility of nanoscale zerovalent iron (nZVI). However, CMC surface modification also cause severe decrease of the longevity and electron utilization efficiency (εe) of nZVI, which is still not well understood. In this study, we demonstrate the negative influence of CMC on the properties of sulfidated nZVI (S-nZVI) could be reversed by increasing the degree of substitution (D.S.) of CMC. Consistent with previous study, the sample CMC-S-nZVI prepared with commercial CMC with degree of substitution (D.S.) of 0.75 exhibited a considerable low longevity of 33 days with εe of 4.5%, much lower than that of sulfidated nZVI (S-nZVI, 113 days and 13%). In sharp contrast, the sample HCMC-S-nZVI synthesized with CMC with super high D.S. of 1.76 demonstrated significantly enhanced longevity of 139 days and εe of 20%. The enhancement was attributed to compatible molecular structure of CMC with super high D.S. Moreover, the HCMC-S-nZVI also exhibited higher mobility in porous media than CMC-S-nZVI. Our work provides a feasible way to prepare S-nZVI with desired properties including high subsurface transportability, high longevity and high εe.

Ni2P nanocrystals embedded Ni-MOF nanosheets supported on nickel foam as bifunctional electrocatalyst for urea electrolysis.

It's highly desired but challenging to synthesize self-supporting nanohybrid made of conductive nanoparticles with metal organic framework (MOF) materials for the application in the electrochemical field. In this work, we report the preparation of Ni2P embedded Ni-MOF nanosheets supported on nickel foam through partial phosphidation (Ni2P@Ni-MOF/NF). The self-supporting Ni2P@Ni-MOF/NF was directly tested as electrode for urea electrolysis. When served as anode for urea oxidation reaction (UOR), it only demands 1.41 V (vs RHE) to deliver a current of 100 mA cm-2. And the overpotential of Ni2P@Ni-MOF/NF to reach 10 mA cm-2 for hydrogen evolution reaction HER was only 66 mV, remarkably lower than Ni2P/NF (133 mV). The exceptional electrochemical performance was attributed to the unique structure of Ni2P@Ni-MOF and the well exposed surface of Ni2P. Furthermore, the Ni2P@Ni-MOF/NF demonstrated outstanding longevity for both HER and UOR. The electrolyzer constructed with Ni2P@Ni-MOF/NF as bifunctional electrode can attain a current density of 100 mA cm-2 at a cell voltage as low as 1.65 V. Our work provides new insights for prepare MOF based nanohydrid for electrochemical application.

Preparation of palladized carbon nanotubes encapsulated iron composites: highly efficient dechlorination for trichloroethylene and low corrosion of nanoiron.

A method developed based on the capillary effect and capillary condensation theory was used to synthesize an innovative Fe/C/Pd composite in this study. This composite (Fe@CNTs@Pd) consists of carbon nanotubes (CNTs) with nanoscale zerovalent iron (NZVI) on the inner surface and palladium nanoparticles supported on the outer surface of CNTs. This structure successfully addresses the problems of high iron corrosion rate and lower utilization rate of hydrogen in the application of bimetal nanoparticles for trichloroethylene (TCE) removal. TCE degradation experiments and electrochemical tests were conducted to investigate the material properties and reaction mechanisms of the composite. It is found that the prepared composite material contribute a high level of TCE dechlorination rate and substantially reduced hydrogen production during iron corrosion in water compared with the conventional CNTs-supported bimetal materials (Fe/Pd@CNTs). Hydrogen spillover effect helps the reactivity of Fe@CNTs@Pd for TCE degradation and suppressed the galvanic cell effect, which results in a stronger resistance to corrosion. Although the Kobs of Fe@CNTs@Pd was 16.87% lower than that of Fe/Pd@CNTs, the hydrogen production rate of Fe@CNTs@Pd was 10 times slower than that of Fe/Pd@CNTs. Therefore, Fe@CNTs@Pd shows a significant reduction in the corrosion rate at a cost of slightly slower degradation of TCE. In sum, the prepared composites demonstrate important characteristics, including alleviating NZVI agglomeration, maintaining high TCE removal efficiency and reducing the corrosion of NZVI.

Removal of hexavalent chromium in soil and groundwater by supported nano zero-valent iron on silica fume.

Silica fume supported-Fe(0) nanoparticles (SF-Fe(0)) were prepared using commercial silica fume as a support. The feasibility of using this SF-Fe(0) for reductive immobilization of Cr(VI) was investigated through batch tests. Compared with unsupported Fe(0), SF-Fe(0) was significantly more active in Cr(VI) removal especially in 84 wt% silica fume loading. Silica fume had also been found to inhibit the formation of Fe(III)/Cr(III) precipitation on Fe nanoparticles' surface, which was increasing the deactivation resistance of iron. Cr(VI) was removed through physical adsorption of Cr(VI) onto the SF-Fe(0) surface and subsequent reduction of Cr(VI) to Cr(III). The rate of reduction of Cr(VI) could be expressed by pseudo first-order reaction kinetics. The rate constant increased with the increase in iron loading but decreased with the increase in initial Cr(VI) concentration. Furthermore, column tests showed that the SF-Fe(0) could be readily transported in model soil.

Reductive dechlorination of activated carbon-adsorbed trichloroethylene by zero-valent iron: carbon as electron shuttle.

Sequestration of organic contaminants in carbonaceous materials can significantly affect contaminant fate and transport. We investigated the reductive dechlorination of granular-activated carbon (GAC)-adsorbed trichloroethylene (TCE) by nanoscale zero-valent iron (nZVI) to understand the effect of sequestration on abiotic reactivity of organic contaminants. Significant reduction of TCE sequestered in GAC micropores was observed, even though direct contact with nZVI was unlikely. Reduction of sequestered TCE by reactive Fe(II) species or molecular hydrogen was ruled out as the reaction mechanisms. We propose that GAC served as the conductor for the transfer of electrons or atomic hydrogen from nZVI to the micropores, wherein adsorbed TCE molecules were reduced. An important implication for environmental remediation is that carbonaceous adsorbents not only function as a superb sink for organic contaminants but also allow them to be slowly degraded while being trapped.

Effects of nano-scale zero-valent iron particles on a mixed culture dechlorinating trichloroethylene.

Nano-scale zero-valent iron particles (NZVI) are increasingly being used to treat sites contaminated with chlorinated solvents. This study investigated the effect of NZVI on dechlorinating microorganisms that participate in the anaerobic bioremediation of such sites. NZVI can have a biostimulatory effect associated with water-derived cathodic H(2) production during its anaerobic corrosion (730+/-30 micromol H(2) was produced in 166 h in abiotic controls with 1 g/L NZVI) or an inhibitory effect upon contact with cell surfaces (assessed by transmission electron microscopy). Methanogens, which are known to compete for H(2) with dechlorinators, were significantly biostimulated by NZVI and methane production increased relative to NZVI-free controls from 58+/-5 to 275+/-2 micromol. In contrast, bacteria dechlorinating TCE were inhibited by NZVI, and the first-order degradation rate coefficient decreased from 0.115+/-0.005 h(-1) (R(2)=0.99) for controls to 0.053+/-0.003 h(-1) (R(2)=0.98) for treatments with 1 g/L NZVI. Ethene production from TCE was initially inhibited by NZVI, but after 331 h increased to levels observed for an NZVI-free system (7.6+/-0.3 micromol ethene produced in 502 h compared to 11.6+/-0.5 mmol in the NZVI-free system and 3.8+/-0.3 micromol ethene for NZVI alone). Apparently, cathodic H(2) was utilized as electron donor by dechlorinating bacteria, which recovered following the partial oxidation and presumably passivation of the NZVI. Overall, these results suggest that reductive treatment of chlorinated solvent sites with NZVI might be enhanced by the concurrent or subsequent participation of bacteria that exploit cathodic depolarization and reductive dechlorination as metabolic niches.

Reactivity characteristics of poly(methyl methacrylate) coated nanoscale iron particles for trichloroethylene remediation.

The unstable characteristic of nanoscale zerovalent iron (NZVI) has been a drawback in practical application, despite the expectation of an enhanced reactivity. It has been ever-increasing interests to maintain the NZVI stability in air without significant reactivity sacrifice. This study demonstrated a novel method of coating NZVI particles with poly(methyl methacrylate) (PMMA), which protected the core iron nanoparticles from oxidation in air and enhanced their dispersion stability in organic solvents. The reactivity studies on trichloroethene (TCE) reduction showed that the PMMA coated nanoscale zerovalent iron (PNZVI) particles were capable of effectively reducing TCE. The main roles of PMMA on the dechlorination reactions were confirmed to be sorption enhancement, competitive sorption and corrosion inhibition.

Decreasing ammonium generation using hydrogenotrophic bacteria in the process of nitrate reduction by nanoscale zero-valent iron.

An integrated nitrate treatment using nanoscale zero-valent iron (NZVI) and Alcaligenes eutrophus, which is a kind of hydrogenotrophic denitrifying bacteria, was conducted to remove nitrate and decrease ammonium generation. Within 8 days, nitrate was removed completely in the reactors containing NZVI particles plus bacteria while the proportion of ammonium generated was only 33%. That is a lower reduction rate but a smaller proportion of ammonium relative to that in abiotic reactors. It was also found that ammonium generation experienced a biphasic process, involving an increasing period and a stable period. After domestication of the bacteria, the combined NZVI-cell system could remove all nitrate without ammonium released when the refreshed nitrate was introduced. Nitrate reduction and the final product distribution were also studied in batch reactors amended with different initial NZVI contents and biomass concentrations, respectively. Both the nitrate removal rate and the ammonium yield decreased when the initial content of NZVI reduced and the initial biomass concentration increased. However, about 27% of the nitrate was converted to ammonium when excess bacteria (OD(422)=0.026) were used, which was higher than that with appropriate amount of bacteria.

[Microbial reductive dechlorination of TCE with nano iron serving as electron donor].

A trichloroethylene (TCE) dechlorinating enrichment (Dehalococcoides spp.), which was isolated from soil of chlorinated ethene contaminated site, was used to investigate whether nano-scale zero valent iron (NZVI) could serve as electron donor for this consortium via cathodic H2 production during anaerobic corrosion. The results show that in the presence of methanol serving as electron donor, dechlorinating culture of 25 fold dilution [(2.0 +/- 0.44) x 10(5) cell/mL] degraded 20 mg/L TCE completely in 96 h, which was accompanied by the production of 2.706 micromol ethene in 190 h. Methanol-free control caused partial degradation of TCE to primarily cis-DCE in 96 h, with only 0.159 micromol ethene produced in 190 h. This indicates bacteria cannot reduce TCE to ethene without electron donor. But when 4 g/L NZVI was added as sole electron donor, this dechlorinating culture degraded 20 mg/L TCE into ethene and vinyl chloride (VC) in 131 h at a speed higher than that by NZVI alone. Compared to 2.706 micromol ethene produced by Dehalococcoides spp. with methanol added as the electron donor, there was only 1.187 micromol ethene produced by bacteria with NZVI serving as the electron donor, which means NZVI has a potential toxicity on Dehalococcoides spp.. At the meantime, 0.109 micromol acetylene was produced in 190 h, which was relatively lower than 0.161 micromol produced by NZVI alone, indicating bacteria competed with NZVI under electron deficient condition. In conclusion, NZVI could serve as electron donor and support dechlorination activity for Dehalococcoides spp. which could enhance the application of NZVI and usage of dechlorinating culture as a polishing strategy in future ground water remediation.

[Preparation of coated iron nanoparticles for reduction of trichloroethylene].

Nanoscale alpha-Fe particles with size of about 80 nm were prepared with a microemulsion-coated method. The results demonstrated that this kind of iron particles could exist stably in the air for 7 d compared with nanoscale iron particles prepared by liquid-phase and microemulsion methods. The removal rate of trichloroethylene with an initial concentration of 10 mg x L(-1) can reach 90% in 700 h. The reduction kinetics was studied under room temperature, neutral, and anaerobic conditions. Experiments show that the reduction process of TCE by nanoscale iron particles conforms to pseudo first order reaction law. The apparent rate constant (k(obs)) is proportional to concentration of nanoscale iron particles. The k(obs), values 6.49 x 10(-40, 6.64 x 10(-4), 7.10 x 10(-4), 7.43 x 10(-4) min(-1), are corresponding to concentrations of 87.5, 175, 262.5, 350 mg x L(-1) respectively. In the reaction, nanoscale iron particles provides electrons and forms an inner film of Fe3O4, on the surface of which an outer film of Fe2O3 is formed together with water. TCE is degraded by electrons. The principal degradation products were ethene and ethane, and smaller amounts of other chlorinated degradation products were also founded.

Preparation of spherical iron nanoclusters in ethanol-water solution for nitrate removal.

In this study, a higher surface area spherical nanoscale zero valent iron (HNZVI) cluster (80 nm, 54.25 m(2)g(-1)) was synthesized in ethanol-water mixed solvent in the presence of dispersion agent of polyglycol (PEG). At the same time, a lower surface area nanoscale zero valent iron (LNZVI) particle (80 nm, 8.08 m(2)g(-1)) was also prepared with only de-ioned water as reaction media. Their structures, compositions and physical properties were characterized by transmission electron microscope (TEM), X-ray diffractometer (XRD), inductively coupled plasma atomic emission spectrophotometer (ICP-AES), and Brunauer-Emmett-Teller (BET) surface area analyzer and the results obtained for these two kinds of nanoscale iron were compared with each other and also with those reported in the literatures. The HNZVI clusters seemed to be accumulated by smaller iron particles (<10 nm). At the same time, whiskers were formed in the final produce. Reactivity of the HNZVI was affirmed via denitrification of nitrate. The factors controlling the reduction of nitrate, such as pH, dissolved oxygen (DO), iron content as well as the initial nitrate concentration were also discussed. Finally, kinetic analysis revealed that chemical reduction of nitrate by HNZVI could not be described by the first- or pseudo-first-order kinetic model.