Layered double hydroxides as efficient photocatalysts for visible-light degradation of Rhodamine B.

A series of Zn/M-NO3-LDHs (M=Al, Fe, Ti, and Fe/Ti) have been synthesized by two different methods, and their activities for visible-light photocatalytic degradation on Rhodamine B (RB) were tested. Solids were analyzed by XRD, FT-IR, and ICP characterization, confirming the formation of pure LDH phase with good crystal structure. It was observed that the band gap of these nitrate LDH materials was following this order: Zn/Fe-NO3-LDHs (2.55 eV)>Zn/Fe/Ti-NO3-LDHs (2.88 eV)>Zn/Ti-NO3-LDHs (3.0 3eV)>Zn/Al-NO3-LDHs (3.23 eV); however, the degradation performance of RB by four materials followed the order: Zn/Ti-NO3-LDHs (98%)>Zn/Al-NO3-LDHs (96%)>Zn/Fe/Ti-NO3-LDHs (88%)>Zn/Fe-NO3-LDHs (72%). In addition, a possible mechanism for photocatalytic degradation on RB has also been presumed. Moreover, after three regeneration cycles, the percentage of RB degradation rate was still close to 90%.

Treatment of methyl orange by calcined layered double hydroxides in aqueous solution: adsorption property and kinetic studies.

Adsorption of a weak acid dye, methyl orange (MO) by calcined layered double hydroxides (LDO) with Zn/Al molar ratio of 3:1 was investigated. In the light of so called "memory effect," LDO was found to recover their original layered structure in the presence of appropriate anions, after adsorption part of MO(-) and CO(2-)(3) (come from air) intercalated into the interlayer of LDH which had been supported by XRD and ICP. The results of adsorption experiments indicate that the maximum capacity of MO at equilibrium (Q(e)) and percentage of adsorption (eta%) with a fixed adsorbent dose of 0.5 g L(-1) were found to be 181.9 mg g(-1) and 90.95%, respectively, when MO concentration, temperature, pH and equilibrium time were 100 mg L(-1), 298 K, 6.0 and 120 min, respectively. The isotherms showed that the adsorption of MO by Zn/Al-LDO was both consistent with Langmuir and Freundlich equations. The adsorption process was spontaneous and endothermic in nature and followed pseudo-second-order kinetic model. The calculated value of E(a) was found to be 77.1 kJ mol(-1), which suggests that the process of adsorption of methyl orange is controlled by the rate of reaction rather than diffusion. The possible mechanism for MO adsorption has also been presumed. In addition, the competitive anions on adsorption and the regeneration of Zn/Al-LDO have also been investigated.

Selective quantification of trace palladium in road dusts and roadside soils by displacement solid-phase extraction online coupled with electrothermal atomic absorption spectrometry.

There is a growing concern about the effect of palladium on human health because of the toxicity and increasing occurrence of palladium as a result of its extensive use in automotive catalytic converters. Development of reliable analytical methodologies for the determination of palladium in environmental materials is of great importance for critical evaluation of the possible risks for human health. In this work, a displacement solid-phase extraction technique was developed and online coupled to electrothermal atomic absorption spectrometry (ETAAS) for selective and sensitive determination of trace palladium in environmental samples without need of any special selective complexing agents, selective sorbents, and masking agents. The developed methodology involved the online formation of copper pyrrolidine dithiocarbamate (Cu-PDC), and the resultant Cu-PDC was extracted onto a microcolumn packed with the sorbent from a cigarette filter. Trace Pd(II) was selectively preconcentrated through loading the sample solution onto the microcolumn by online displacement reaction between Pd(II) and the extracted Cu-PDC on the microcolumn. The retained analyte was subsequently eluted with 40 microL of ethanol for online ETAAS determination. Interferences from coexisting heavy metal ions with lower stability of their PDC complexes relative to Cu-PDC were minimized. The tolerable concentrations of Cd-(II), Fe(III), Co(II), Mn(II), Cr(III), and Zn(II) were up to 2, 6, 40, 2, 1.5, and at least 100 mg L(-1), respectively. Compared with conventional solid-phase extraction methodology, the developed displacement solid-phase extraction protocol gave 2-4 orders of magnitude improvement in the maximum tolerable concentrations of coexisting heavy metal ions. With the consumption of only 2.8 mL of sample solution, an enhancement factor of 52 and a detection limit (3sigma) of 18 ng L(-1) were achieved at a sample throughput of 30 samples h(-1). The precision (RSD, n = 13) was 2.5% at the 1 microg L(-1) level. The present methodology was successfully applied to selective determination of trace palladium in local road dusts and roadside soils.

Determination of trace mercury in environmental and foods samples by online coupling of flow injection displacement sorption preconcentration to electrothermal atomic absorption spectrometry.

The toxic effects of mercury are well-known. To establish sources of mercury contamination and to evaluate levels of mercury pollution, sensitive, selective, and accurate analytical methods with excellent reproducibility are required. We have developed a novel methodology for the determination of trace mercury in environmental and foods samples by online coupling of flow injection (FI) displacement sorption preconcentration in a knotted reactor (KR) to electrothermal atomic absorption spectrometry (ETAAS). The developed methodology involved the online formation of copper pyrrolidine dithiocarbamate (Cu-PDC), presorption of the resulting Cu-PDC onto the inner walls of the KR, and selective retention of the analyte Hg(ll) onto the inner walls of the KR through online displacement reaction between Hg(ll) and the presorbed Cu-PDC. The retained analyte was subsequently eluted by 50 microL of ethanol and online detected by ETAAS. Interferences from coexisting heavy metal ions with lower stability of their APDC complexes relative to Cu- PDC were minimized without the need of any masking reagents. The tolerable concentrations of Cu(II), Cd(II), Fe(III), Ni(III), and Zn(II) were up to 12, 20, 16, 20, and 60 mg L(-1), respectively. No additional chemical modifiers for the stabilization of mercury were required in the present system owing to the stability of Hg-PDC at the drying stage, and no pyrolysis stage was necessary due to the effective removal of the matrices. With consumption of 2.5 mL of sample solution, an enhancement factor of 91 was obtained in comparison with direct injection of 50 microL of aqueous solution. The relative detection limit (3s) was 6.2 ng L(-1), corresponding to an absolute detection limit of 15.5 pg. The precision (RSD, n = 13) was 1.1% at the 2 microg L(-1) level. The method was successfully applied to the determination of mercury in several certified environmental and foods reference materials and locally collected water samples.