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The catalytic dechlorination of2,4-dichlorophenol (2,4-DCP) by Ni/Fe bimetallic nanoparticles in the presence of humic acid (HA) was investigated in order to understand their applicability forin situremediation of groundwater.2,4-DCP was catalytically dechlorinated to form the final products – phenol (P) via two intermediates,o-chlorophenol (o-CP) andp-chlorophenol (p-CP). It was demonstrated that the carbon mass balances during the dechlorination were between 84% and 92%, and other carbons were adsorbed on the surface of Ni/Fe bimetallic nanoparticles. The experimental results suggest that HA competed for reaction sites on the Ni/Fe bimetallic nanoparticles with2,4-DCP, and thus reduced the efficiency and rate of the dechlorination of2,4-DCP. The catalytic degradation slowed down as the increase of HA in solution, and when HA's concentrations were 0, 10, 20 and 30 mg L−1, the maximum concentrations ofo-CP were 0.025, 0.041, 0.039 and 0.034 mM in 10, 30, 30 and 30 min, respectively. High Ni content, low initial pH value, high Ni/Fe nanoparticles’ dosage and high temperature favoured the catalytic dechlorination of2,4-DCP. The experimental results show that no other intermediates were generated besides Cl−,o-CP,p-CP and P during the catalytic dechlorination of2,4-DCP. [ABSTRACT FROM PUBLISHER]

Graphical abstract Highlights • 2,4-DCBA was efficiently removed by moveable carbon-supported Pd catalysts. • The catalysts morphologies and chemical structures maintained during the reaction. • Pd/CB exhibited the highest adsorption and dechlorination ability. • The issues of easy loss of Pd and poor long-term performance were addressed. Abstract In the present study, carbon black (CB), multi walled carbon nanotubes (MWCNTs), and granular activated carbon (GAC) were employed to support palladium (Pd) catalyst. The prepared Pd/CB, Pd/MWCNTs and Pd/GAC moveable catalysts were aimed to address the common issues (easy loss of catalyst and poor long-term performance) of normal fixed catalysts. The results of various characterizations (e.g., TEM, XRD, and XPS) clearly show that the Pd nanoparticles were successfully loaded onto the carbon-supports, especially CB and MWCNTs. And more importantly, the morphologies, Pd distribution, and chemical structure of these moveable catalysts were almost not changed after 3 h reaction. The moveable Pd/CB, Pd/MWCNTs, and Pd/GAC catalysts had good reactivity for 2,4-dichlorobenzoic acid (2,4-DCBA) dechlorination, and Pd/CB exhibited the best performance. The Pd/CB also shows the best adsorption capacity of 2,4-DCBA and dechlorination product (benzoic acid, BA), and the adsorption of BA was significantly inhibited in the presence of current due to the repulsion between the both negatively charged compounds and adsorbents. The removal of 2,4-DCBA and the generation rate of BA was improved with a pre-adsorption process, which was a promising strategy with higher dechlorination rate and shortened electrolysis time. Moreover, the loss of Pd catalyst was negligible during the 10 consecutive cycles experiment, and the improved longevity could be expected. These results suggested the good reactivity, stability, and reusability of moveable Pd/CB catalyst. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • Enhanced 2,4-DCBA dechlorination with low intermediate products was achieved. • 2,4-DCBA removal by moveable Pd/AC was 5–194 folds faster than fixed catalysts. • High Pd loading, current, and acidity favored the dechlorination of 2,4-DCBA. • Excessive electrolyte inhibited the dechlorination of 2,4-DCBA. • Good longevity and recyclability of moveable Pd/AC catalyst was confirmed. Abstract In this study, a novel approach was developed for the dechlorination of 2,4-dichlorobenzoic acid (2,4-DCBA) via the combination of the moveable activated carbon (AC) supported palladium (Pd) nanoparticles and nickel (Ni) foam electrode. The morphology and chemical structure of Pd/AC catalyst was investigated by various characterization techniques, including SEM, TEM, EXS-mapping, XRD, and XPS. Pd nanoparticles was successfully loaded and dispersed on the AC, accompanied with the significantly enhanced reactivity. The removal rate of 2,4-DCBA by Ni electrode with moveable Pd/AC catalyst was 222, 25, and 5 folds higher than dispersed AC and Ni electrode system, chemical deposited Pd/Ni electrode, and electrodeposited Pd/Ni electrode, respectively. Compared with the conventional electrocatalytic reductive approach which deposited Pd on the Ni foam electrode, moveable Pd/AC catalyst possesses higher surface area, more atomic H∗ production and more active sites, favored mass transfer, and enhanced reactivity, without the consideration of catalyst loss and deactivation. The effects of Pd:AC mass ratio, constant current, initial solution pH, and electrolyte concentration on the dechlorination of 2,4-DCBA were studied. Generally, high Pd loading, constant current, and acidity favored the dechlorination of 2,4-DCBA, while excessive electrolyte would inhibit the dechlorination of 2,4-DCBA. Good longevity and recyclability of moveable Pd/AC catalyst was confirmed via consecutive experiments. The findings of the present study show that making the catalyst moveable is a promising strategy for electrocatalytic remediation technology. [ABSTRACT FROM AUTHOR]

Polychlorinated dibenzo- p -dioxins (PCDDs), as a group of notorious anthropogenic environmental toxicants, are arguably ubiquitous in nature. In this study, we investigated the photocatalytic reductive dechlorination of 2-chlorodibenzo- p -dioxin (2-CDD) over Pd/g-C 3 N 4 catalysts under UV–vis irradiation. The g-C 3 N 4 and a series of Pd/g-C 3 N 4 catalysts were prepared by thermal polymerization and mechanical mixing-illumination method and characterized by XRD, TEM, BET, SEM and UV–vis DRS analyses. Among all the samples, the Pd/g-C 3 N 4 (5 wt%) yielded the optimal dechlorination activity with a total 2-CDD conversion of 54% within 4 h, and 76% of those converted 2-CDD were evolved to dibenzo- p -dioxin (DD). The kinetics of dechlorination could be described as pseudo-first-order decay model (R 2  > 0.84). Corresponding rate constants (k) increased from 0.052 to 0.17 h −1 with Pd contents up to 5 wt% and decreased to 0.13 h −1 with a 10 wt% of Pd. The enhanced activities originated from the surface plasmonic resonance (SPR) effect of Pd nanoparticles and the formation of Schottky barrier between Pd and g-C 3 N 4 , which extend the spectrum responsive range and suppress the charge recombination of g-C 3 N 4 . This is the first report on the photocatalytic reductive removal of PCDDs and may provide a new approach for PCDDs pollution control. [ABSTRACT FROM AUTHOR]

Highlights: [•] Effective electrocatalytic dechlorination of 2,4-D was achieved. [•] Dechlorination efficiency was enhanced by nTiN doped in Pd layer on the electrode. [•] nTiN doping content and Pd loading influenced the dechlorination efficiency. [•] Hydrogen adsorption balance existed between two phases in Pd layer. [•] Active hydrogen atom [H] could be stored in Pd lattice for a period of time. [Copyright &y& Elsevier]

Highlights: [•] Nano-Ni/Fe were synthesized in the presence of ultrasonic irradiation. [•] Ultrasonic irradiation can improve nano-Ni/Fe′ disparity and avoid agglomeration. [•] 2,4-DCP was first adsorbed by nano-Ni/Fe, then was quickly dechlorinated. [•] Factors of reductive dechlorination by nano-Ni/Fe were studied. [ABSTRACT FROM AUTHOR]

Highlights: [•] Pd/Fe-Fe3O4 nanocomposites showed synergy effects on 2,4-DCP dechlorination. [•] Weak acidic condition and high temperature favored 2,4-DCP dechlorination. [•] Common dissolved anions and cations were found to affect 2,4-DCP dechlorination. [•] HA adsorbed on nFe3O4-Pd/Fe would inhibit 2,4-DCP dechlorination. [•] High stabilities and durable reactivity were observed in consecutive experiments. [ABSTRACT FROM AUTHOR]

Highlights: [•] Enhanced catalytic dechlorination of 2,4-dichlorophenoxyacetic acid. [•] Synergistic technology combined nZVI with electrochemistry. [•] Palladium loading and current density had a greater impact on efficiencies. [•] nZVI promoted the generation of electron and enhanced the dechlorination. [Copyright &y& Elsevier]

Abstract: Palladium/Iron (Pd/Fe) nanoparticles were prepared by using ultrasound strengthened liquid phase reductive method to enhance dispersion and avoid agglomeration. The dechlorination of 2,4-dichlorophenol (2,4-DCP) by Pd/Fe nanoparticles was investigated to understand its feasibility for an in situ remediation of contaminated groundwater. Results showed that 2,4-DCP was first adsorbed by Pd/Fe nanoparticles, then quickly reduced to o-chlorophenol (o-CP), p-chlorophenol (p-CP), and finally to phenol (P). The induction of ultrasound during the preparation of Pd/Fe nanoparticles further enhanced the removal efficiency of 2,4-DCP, as a result, the phenol production rates increased from 65% (in the absence of ultrasonic irradiation) to 91% (in the presence of ultrasonic irradiation) within 2h. Our data suggested that the dechlorination rate was dependent on various factors including Pd loading percentage over Fe0, Pd/Fe nanoparticles availability, temperature, mechanical stirring speed, and initial pH values. Up to 99.2% of 2,4-DCP was removed after 300min reaction with these conditions: Pd loading percentage over Fe0 0.3wt.%, initial 2,4-DCP concentration 20mgL−1, Pd/Fe dosage 3gL−1, initial pH value 3.0, and reaction temperature 25°C. The degradation of 2,4-DCP followed pseudo-first-order kinetics reaction and the apparent pseudo-first-order kinetics constant was 0.0468min−1. [Copyright &y& Elsevier]

Abstract: In this study a systematic investigation of two specified MWCNTs-Pd/Fe nanocomposites to remove 2,4-dichlorophenol (2,4-DCP) is presented. Two specified Multi-Walled Carbon Nanotubes (MWCNTs), i.e., 60–100nm and 10–20nm were introduced in nZVI synthesis in order to improve its adsorption–dechlorination efficiency. Both MWCNTs-Pd/Fe nanocomposites showed excellent adsorption efficiencies for phenols and followed the sequential order; 2,4-DCP>p-CP>o-CP>P. Batch sorption experiments including kinetics and isotherm were also intensively investigated. Significantly high 2,4-DCP removal was observed after 1min when it reached to 49.7% and 53.2%, then continuously increased up to 95.2% and 77.7% after 5h at 0.20wt.% Pd loading by 60–100nm and 10–20nm MWCNTs-Pd/Fe nanocomposites, respectively. However, stronger dechlorination and weaker adsorption was found in 60–100nm MWCNTs-Pd/Fe nanocomposites. Moreover, an integrated approach of physical adsorption by 60–100nm MWCNTs and chemical reduction by Pd/Fe nanoparticles to remove 2,4-DCP was successfully achieved. The property of quick adsorption of targeted pollutants and steady release of dechlorination products enhance the applicability of this process for an in situ pollution remediation measures. [Copyright &y& Elsevier]

Abstract: Ni/Fe bimetallic nanoparticles were synthesized for treatment of Aroclor 1242, in order to evaluate their applicability for in situ remediation of groundwater and soil contaminated by polychlorinated biphenyls (PCBs). Our experimental results indicate that the total PCB concentration changed during the reduction of 3,5-dichlorobiphenyl (PCB 14), and biphenyl was produced as the final product. Initially, the concentration of 3-chlorobiphenyl (PCB 2) was increased in the prophase reaction and then slowly decreased, suggesting that Aroclor 1242 was first adsorbed by Ni/Fe nanoparticles, and then, the higher chlorinated congeners were converted gradually to the lower chlorinated congeners, and finally to biphenyl. The dechlorination efficiency of Aroclor 1242 reached approximately 80% at 25°C in just 5h, then 95.6% and 95.8% in 10h and 24h, respectively. The study revealed that high Ni/Fe nanoparticle dosage and high Ni content in Ni/Fe nanoparticles favor the catalytic dechlorination reaction. Moreover, a comparison of different types of catalysts on the dechlorination of Aroclor 1242 indicated that Ni/Mg and Mg powders showed a greater reactivity than Ni/Fe and Fe nanoparticles, respectively. [Copyright &y& Elsevier]

Abstract: Nanoscale Pd/Fe particles were combined with multi-walled carbon nanotubes (MWNTs) to prepare supported particles (MWNT-stabilized Pd/Fe), which were used to remove 2,4-dichlorophenol (2,4-DCP). The adsorption capacity of MWNTs was found to be increased with the increasing amount of chlorine atoms, and the removal rates of phenol (P), 2-chlorophenol (2-CP), 4-chlorophenol (4-CP) and 2,4-DCP reached 19.7%, 60.5%, 72.0% and 95.1% respectively, in 1min by MWNTs due to π–π interaction. The adsorption kinetics and adsorption isotherm were also discussed. MWNTs as a supporter, was effective for avoiding the agglomeration of nZVI. Furthermore, the speedy removal efficiency of the initial substances (2,4-DCP) reached about 50% in 1min, and over the time continued to rise to 100%, remaining low concentrations (<1mgL−1) of the intermediate substances (o-CP, p-CP), and gradual release of the final substance (P) from MWNT-stabilized Pd/Fe composites during the whole process, proposed a novel method for in situ remediation technology. [Copyright &y& Elsevier]

Abstract: The electrochemical reductive dechlorination of 2,4-dichlorophenoxyacetic acid (2,4-D) in an aqueous solution was investigated at ambient temperature using a palladium/nickel foam (Pd/Ni foam) electrode in batch mode experiments. The catalytic electrode prepared using the standard chemical deposition method was further characterized using X-ray diffraction and scanning electron microscopy. It was observed that the reaction followed a pseudo-first-order kinetics model, the magnetic agitator-supported system could achieve 87% removal of 2,4-D within 4h, which is 16% higher than the efficiency obtained under a nitrogen atmosphere. No organic intermediates other than phenoxyacetic (PA), o-chlorophenoxyacetic acid (o-CPA) and p-chlorophenoxyacetic acid (p-CPA) were observed to be generated during the reaction. The dechlorination efficiency depended on several factors including the current density, the palladium loading and the initial concentrations of the supporting NaCl electrolyte and the 2,4-D. The palladium loading and the NaCl concentration had a greater effect on the dechlorination kinetics of 2,4-D. Furthermore, the efficiencies of dechlorination and PA formation could be improved by optimizing the reaction system by modifying the ventilation conditions. [Copyright &y& Elsevier]

Abstract: This paper describes the synthesis of sodium carboxymethyl cellulose (CMC)-stabilized Pd/Fe nanoparticles and their applications to the dechlorination of 2,4-dichlorophenoxyacetic acid (2,4-D) under controlled laboratorial conditions. For this purpose batch mode experiments were conducted to understand the effects of CMC on the surface characteristics of Pd/Fe nanoparticles, optimum removal of 2,4-D and other surface interactions mechanism. Our experimental results demonstrated considerable enhancements in particle stability and chemical reactivity with the addition of CMC to Pd/Fe nanoparticles. Transmission electron microscopy (TEM) analysis indicated that CMC-stabilized Pd/Fe nanoparticles were well dispersed, and nanoparticles remained in suspension for days compared to non-stabilized Pd/Fe nanoparticles precipitated within minutes. The isoelectric point (IEP) of the nanoparticles shifted from pH 6.5 to 2.5, suggesting that CMC-stabilized Pd/Fe nanoparticles were negatively charged over a wider pH range. Our batch experiments demonstrated that CMC-stabilized Pd/Fe nanoparticles (0.6gFeL−1) were able to remove much higher levels of 2,4-D with only one intermediate 2-chlorophenoxyacetic acid (2-CPA) and the final organic product phenoxyacetic acid (PA), than non-stabilized Pd/Fe nanoparticles or microsized Pd/Fe particles. The removal percentage of 2,4-D increased from 10% to nearly 100% as the reaction pH decreased from 11.5 to 2.5. The optimal CMC/Fe mass ratio for the dechlorination of 2,4-D was determined to be 5/1, and the removal of 2,4-D was evidently hindered by an overdose of CMC. [Copyright &y& Elsevier]