Abstract
The development of visible-light responsive photocatalysts would permit more efficient use of solar energy, and thus would bring sustainable solutions to many environmental issues. Conductive polymers appear as a new class of very active photocatalysts under visible light. Among them poly(3,4-ethylenedioxythiophene) (PEDOT) is one of the most promising conjugated polymer with a wide range of applications. PEDOT nanostructures synthesized in soft templates via chemical oxidative polymerization demonstrate unprecedented photocatalytic activities for water treatment without the assistance of sacrificial reagents or noble metal co-catalysts and turn out to be better than TiO2 as benchmark catalyst. The PEDOT nanostructures exhibit a narrow band gap (E = 1.69 eV) and are characterized by excellent ability to absorb light in visible and near infrared region. The novel PEDOT-based photocatalysts are very stable with cycling and can be reused without appreciable loss of activity. Interestingly, hollow micrometric vesicular structures of PEDOT are not effective photocatalysts as compared to nanometric spindles suggesting size and shape dependent photocatalytic properties. The visible-light active photocatalytic properties of the polymer nanostructures present promising applications in solar light harvesting and broader fields.
Highlights
In the last few years, polymer nanostructures have attracted a lot of attention for energy conversion and storage applications[18]
We show that conducting PEDOT polymer nanostructures exhibit exceptionally high and shape dependent-photocatalytic activities both under UV and visible light, which is higher than that of plasmonic Ag nanoparticle modified TiO2 (Ag-TiO2) and of poly(diphenylbutadiyne) (PDPB) nanofibers recently published[18]
TiO2 and Ag-TiO2, PDPB nanofibers and the synthesized PEDOT vesicles and PEDOT nanospindles under UV (a,c) and visible light (> 450 nm) (b,d) irradiation
Summary
Reagents. 3,4-ethylenedioxythiophene (EDOT), iron (III) chloride, cetyltrimethylammonium bromide (CTAB) (≥ 98%), sodium chloride, toluene (> 99%), pentanol (≥ 99%), silver perchlorate AgClO4 (> 98%), phenol (C6H5OH) and methyl orange were purchased from Sigma-Aldrich. The hexagonal mesophases were made of a mixture of cetyltrimethylammonium bromide (CTAB) as surfactant, salted water (NaCl), toluene as oil and pentanol as cosurfactant. The cosurfactant (20 μ L of pentanol) was added to the mixture which was strongly vortexed for a few minutes This led to a perfectly translucent, birefringent and stable gel consisting in a hexagonal mesophase for PEDOT vesicles structures. EDOT and/or FeCl3 were dissolved separately in toluene and added to the viscous micellar solution during mesophases preparation. Hantzsch method for the determination of formaldehyde In this method, 1.5 mL of reactant solution was extracted after photo irradiation of organic pollutants in the presence of PEDOT spindles, TiO2 (P25TiO2), Ag nanoparticle modified TiO2 (Ag-TiO2) diluted in 1 mL of 0.2 M acetoacetanilide in ethanol and 2.5 mL of 4 M ammonium acetate. TOC was measured by IR after complete oxidation by catalytic combustion at 680 °C on exclusive platinum catalyst, the inorganic carbon being removed by a previous acidification and air purging
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