RESUMO
Polymeric carbon nitride is a promising photoanode material for water-splitting and organic transformation-based photochemical cells. Despite achieving significant progress in performance, these materials still exhibit low photoactivity compared to inorganic photoanodic materials because of a moderate visible light response, poor charge separation, and slow oxidation kinetics. Here, the synthesis of a sodium- and boron-doped carbon nitride layer with excellent activity as a photoanode in a water-splitting photoelectrochemical cell is reported. The new synthesis consists of the direct growth of carbon nitride (CN) monomers from a hot precursor solution, enabling control over the monomer-to-dopant ratio, thus determining the final CN properties. The introduction of Na and B as dopants results in a dense CN layer with a packed morphology, better charge separation thanks to the in situ formation of an electron density gradient, and an extended visible light response up to 550 nm. The optimized photoanode exhibits state-of-the-art performance: photocurrent densities with and without a hole scavenger of about 1.5 and 0.9 mA cm-2 at 1.23 V versus reversible hydrogen electrode (RHE), and maximal external quantum efficiencies of 56% and 24%, respectively, alongside an onset potential of 0.3 V.
RESUMO
Polymeric carbon nitride (CN) has emerged as an attractive material for photocatalysis and photoelectronic devices. However, the synthesis of porous CNs with controlled structural and optical properties remains a challenge, and processable CN precursors are still highly sought after for fabricating homogenous CN layers strongly bound to a given substrate. Here, we report a general method to synthesize highly dispersed porous CN materials that show excellent photocatalytic activity for the hydrogen evolution reaction and good performance as photoanodes in photoelectrochemical cells (PEC): first, supramolecular assemblies of melem and melamine in ethylene glycol and water are prepared using a hydrothermal process. These precursors are then calcined to yield a water-dispersible CN photocatalyst that exhibits beneficial charge separation under illumination, extended visible-light response attributed to carbon doping, and a large number of free amine groups that act as preferential sites for a Pt cocatalyst. The optimized CN exhibits state-of-the-art HER rates up to 23.1 mmol h-1 g-1, with an AQE of 19.2% at 395 nm. This unique synthetic route enables the formation of a homogeneous precursor paste for substrate casting; consequently, the CN photoanode exhibits a low onset potential, a high photocurrent density and good stability after calcination.
