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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]

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: 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]