Bimetallic Ag–Cu Supported on Graphitic Carbon Nitride Nanotubes for Improved Visible-Light Photocatalytic Hydrogen Production

This work, for the first time, reports visible-light active bare graphitic carbon nitride nanotubes (C₃N₄ NTs) for photocatalytic hydrogen generation, even in the absence of any cocatalyst. Upon uniform dispersion of the cocatalysts, Ag–Cu nanoparticles, on the well-ordered bare C₃N₄ NTs, they exhibit twice the H₂ evolution rate of the bare C₃N₄ NTs. The improved activity is attributed to their unique tubular nanostructure, strong metal–support interaction, and efficient photoinduced electron–hole separation compared to their bare and monometallic counterparts, evidenced by complementary characterization techniques. This work reveals that the H₂ production rates correlate well with the oxidation potentials of the sacrificial reagents used. Triethylamine (TEA) outperforms other sacrificial reagents, including triethanolamine (TEOA) and methanol. Mechanistic studies on the role of various sacrificial reagents in photocatalytic H₂ generation demonstrate that irreversible photodegradation of TEA into diethylamine and acetaldehyde via monoelectronic oxidation contributes to the improved H₂ yield. Similarly, TEOA is oxidized to diethanolamine and glycolaldehyde, whereas methanol is unable to quickly capture the photoinduced holes and remains intact due to the low oxidation potential