Poly(4-vinyl pyridine) radiografted PVDF track etched membranes as sensors for monitoring trace mercury in water

International audiencePoly-4-vinyl pyridine chains were radiografted inside the etched-tracks of PVDF nanoporous membrane. P4VP grafting was found to be localized on the solid PVDF surface. Coating of these PVDF-g-P4VP membranes with a very thin layer of gold results in an ASV electrochemical sensor. Functionalized ion track-etched PVDF-g-P4VP sensors were found very selective and highly sensitive for mercury LOD 5 ng/L. a b s t r a c t By a radiation-induced grafting technique, we have functionalized track-etched nanoporous polymer membranes with mercury sensitive poly-4-vinyl pyridine (P4VP). Coating of these membranes with a very thin layer of gold results in an electrochemical sensor that is very selective and highly sensitive for mercury LOD 5 ng/L – well below the norms for water (0.015 mg/L potable water and 0.5 mg/L residual waters-French water norms of 27 October 2011). E-beam irradiation permitted optimization of the radiografting synthesis on PVDF thin films prior to ion-track grafting. Synthesis and characterization by EPR, FESEM and FTIR are described in detail. A comparison between FTIR in ATR and transmission modes enabled us to localize the grafting on the surface of the e-beam irradiated PVDF films allowing us to extrapolate what happens on the etched tracks. Using Square Wave Anodic Stripping Voltammetry (SW-ASV), mercury concentrations of 1 mg/L are detected in 2 h and low ng/L concentrations are detected after 24 h of adsorption. The adsorption is passive so sensors do not require instrumentation and the analysis takes only 3–4 min. Also, the P4VP functionalized sensor appears insensitive to pH variations (pHs 3–9), high salt concentrations (up to 1 g/ L) and the presence of other heavy metals in the same solution.

Functionalized Nanoporous Track-Etched b-PVDF Membrane Electrodes for Heavy Metal Determination by Square-Wave Anodic Stripping Voltammetry

Track-etched functionalized nanoporous β-PVDF membrane electrodes, or functionalized membrane electrodes (FMEs), are electrodes made from track-etched, poly(acrylic acid) (PAA) functionalized nanoporous β-poly(vinylidene fluoride) (β-PVDF) membranes with thin porous Au films sputtered on each side as electrodes. To form the β-PVDF nanoporous membranes, β-PVDF films are irradiated by swift heavy ions. After irradiation, radical tracks are stable in the membranes. Chemical etching removes some of the radical tracks revealing nanopores. Radicals, remaining in the pores, initiate radio grafting of PAA from the pore walls of the nanoporous β-PVDF. PAA is a cation exchange polymer that adsorbs metal ions, such as Pb2+, from aqueous solutions thus concentrating the ions into the membrane. After a calibrated time the FME is transferred to an electrochemical cell for square-wave anodic stripping voltammetry analysis

Functionalized Nanoporous Track-Etched B-Pvdf Membrane Electrodes For Heavy Metal Determination By Square-Wave Anodic Stripping Voltammetry

Track-etched functionalized nanoporous beta-PVDF membrane electrodes, or functionalized membrane electrodes (FMEs), are electrodes made from track-etched, poly(acrylic acid) (PAA) functionalized nanoporous beta-poly(vinylidene fluoride) (beta-PVDF) membranes with thin porous Au films sputtered on each side as electrodes. To form the beta-PVDF nanoporous membranes, beta-PVDF films are irradiated by swift heavy ions. After irradiation, radical tracks are stable in the membranes. Chemical etching removes some of the radical tracks revealing nanopores. Radicals, remaining in the pores, initiate radio grafting of PAA from the pore walls of the nanoporous beta-PVDF. PAA is a cation exchange polymer that adsorbs metal ions, such as Pb2+, from aqueous solutions thus concentrating the ions into the membrane. After a calibrated time the FME is transferred to an electrochemical cell for square-wave anodic stripping voltammetry analysis.WoSScopu