Exploring the Remarkably High Photocatalytic Efficiency of Ultra-Thin Porous Graphitic Carbon Nitride Nanosheets

Graphitic carbon nitride (g-C₃N₄) is a metal-free photocatalyst used for visible-driven hydrogen production, CO₂ reduction, and organic pollutant degradation. In addition to the most attractive feature of visible photoactivity, its other benefits include thermal and photochemical stability, cost-effectiveness, and simple and easy-scale-up synthesis. However, its performance is still limited due to its low absorption at longer wavelengths in the visible range, and high charge recombination. In addition, the exfoliated nanosheets easily aggregate, causing the reduction in specific surface area, and thus its photoactivity. Herein, we propose the use of ultra-thin porous g-C₃N₄ nanosheets to overcome these limitations and improve its photocatalytic performance. Through the optimization of a novel multi-step synthetic protocol, based on an initial thermal treatment, the use of nitric acid (HNO₃), and an ultrasonication step, we were able to obtain very thin and well-tuned material that yielded exceptional photodegradation performance of methyl orange (MO) under visible light irradiation, without the need for any co-catalyst. About 96% of MO was degraded in as short as 30 min, achieving a normalized apparent reaction rate constant (k) of 1.1 × 10^-2 min^-1mg^-1. This represents the highest k value ever reported using C₃N₄-based photocatalysts for MO degradation, based on our thorough literature search. Ultrasonication in acid not only prevents agglomeration of g-C₃N₄ nanosheets but also tunes pore size distribution and plays a key role in this achievement. We also studied their performance in a photocatalytic hydrogen evolution reaction (HER), achieving a production of 1842 µmol h^-1 g^-1. Through a profound analysis of all the samples' structure, morphology, and optical properties, we provide physical insight into the improved performance of our optimized porous g-C₃N₄ sample for both photocatalytic reactions. This research may serve as a guide for improving the photocatalytic activity of porous two-dimensional (2D) semiconductors under visible light irradiation.