A flexible mat of semiconducting polypyrrole nanofibers increases ZnO photocatalytic efficiency through heterojunctions that promote separation of photoinduced charge carriers.

p-Type organic semiconductors are attractive to develop new photo-and photoelectro-catalytic systems, particularly if the conduction band is located at negative redox potentials. An easy synthetic route to produce carbon-doped carbon nitride (C n>3 N 4) with a stable p-type semiconducting character was optimized. The precursors used were melamine and triaminopyrimidine. The p-type C >3 N 4 exhibited a remarkable photoactivity under visible light compared with pristine C 3 N 4 , which is a stable n-type organic semiconductor deeply studied as heterogeneous photocatalyst for many environmental applications. The photoelectrochemical features of the synthesized p-type materials and pristine C 3 N 4 were deeply investigated with chronopotentiometry and cyclic voltammetry, in the dark and under different illumination conditions, and then compared with the photocatalytic activity using 2fluorophenol as substrate and different radiation sources. The p-doping with carbon of C 3 N 4 reduces the band gap, slightly moves the potential of the valence band, and increases the conduction band to more positive potentials, thus precluding the application of these materials when large negative redox potentials are needed.

The direct electrolysis of seawater is greatly inhibited by the oxidation of Cl– to free chlorine, an undesirable, corrosive byproduct. To suppress the parasitic interference of Cl– and any other ion, we developed a freestanding, electrically conducting, 3D macroporous reduced graphene oxide (rGO) scaffold with cobalt oxide particles selectively deposited on the internal walls of its closed pores (with an average diameter of ∼180 μm). The pore walls act as membranes composed of stacked rGO flakes; the nanochannels between rGO layers (size <1 nm) are permeable to water and gases while preventing the diffusion of dissolved ions such as Cl–. Due to this, the catalytic particles are selectively accessible to water molecules but not to ions, allowing electrolysis to occur without chlorine evolution. The electrodes developed exhibit a stable generation of O2 from simulated seawater at pH 14, reaching a specific current density of up to 25 A g–1 during continuous electrolysis with 89–98% Faradaic efficiency, while chlorine generation is below 6 ppm h–1, the sensitivity limit of the detection method employed. The strategy here proposed can be generalized to build electrodes that are inherently selective thanks to their architecture, with catalytically active particles loaded into closed pores with selective ion transport properties.

No abstract