Cutting-Edge PCN-ZnO Nanocomposites with Experimental and DFT Insights into Enhanced Hydrogen Evolution Reaction

Polymeric carbon nitride (PCN) and PCN-ZnO nanocomposites are promising candidates for catalysis, particularly for hydrogen evolution reactions (HER). However, their catalytic efficiency requires enhancement to fully realize their potential. This study aims to improve the HER performance of PCN by synthesizing PCN-ZnO nanocomposites using melamine as a precursor. Two synthesis methods were employed: thermal condensation (Method 1) and liquid exfoliation (Method 2). Method 1 resulted in a composite with a 2.44 eV energy gap and reduced particle size, with significantly enhanced performance as a bifunctional electrocatalyst for simultaneous hydrogen and oxygen production. In contrast, Method 2 produced a nanocomposite with an enhanced surface area and a minor alteration in the band gap. In alkaline electrolytes, the PCN-ZnO0.4 nanocomposite synthesized with Method 1 exhibited high HER performance with an overpotential of 281 mV, outperforming pristine PCN (382 mV) and ZnO (302 mV), along with improved oxygen evolution reaction (OER) activity. Further analysis in a two-electrode alkaline electrolyzer using PCN-ZnO0.4 nanocomposite as both the anode and cathode demonstrated its promise as a bifunctional electrocatalyst. Density functional theory (DFT) calculations explained the enhanced catalytic activity of the PCN-ZnO nanocomposite, confirming that hydrogen evolution occurs through the Heyrovsky process, consistent with experimental results. Notably, the solar-to-hydrogen (STH) efficiency of the PCN-ZnO nanocomposite was four times greater, at 21.7% compared to 5.2% for the PCN monolayer, underscoring its potential for efficient solar-driven hydrogen production. This work paves the way for future advancements in the design of high-performance electrocatalysts for sustainable energy applications.