Tuning Ag Loading and Particle Size in Ag@g-C₃N₄ Photocatalysts for Selective CO₂ Conversion to CO and CH₄

Elucidating the mechanisms of CO₂ photocatalytic conversion systems is crucial for tackling the challenges of carbon neutrality. In this study, a series of Ag@g-C₃N₄ photocatalysts were constructed with metal particle size modulation as the core strategy to systematically reveal the modulation mechanism of Ag nanoparticles (Ag NPs) size variation on the selectivity of CO₂ photoreduction products. Systematic characterizations revealed that increasing Ag size enhanced visible light absorption, promoted charge separation, and improved CH₄ selectivity. Photocatalytic tests showed Ag_3.0%@CN achieved optimal activity and electron utilization. Energy band analyses indicated that Ag modification preserved favorable conduction band positions while increasing donor capacity. Further density-functional theory (DFT) calculations reveal that Ag NPs size variations significantly affect the adsorption stability and conversion energy barriers of intermediates such as *COOH, CO and CHO, with small-sized Ag₇ NPs favoring the CO pathway, while large-sized Ag NPs stabilize the key intermediates and drive the reaction towards the CH₄ pathway evolution. The experimental and theoretical results corroborate each other and clarify the dominant role of Ag NPs size in regulating the reaction path between CO and CH₄. This study provides mechanistic guidance for the selective regulation of the multi-electron reduction pathway, which is of great significance for the construction of efficient and highly selective CO₂ photocatalytic systems.