Enhancing photocatalytic hydrogen production of carbon nitride: Dominant advantage of crystallinity over mass transfer

Mass transfer enhancement and crystallinity engineering are two prevailing technologies for photocatalyst modification. However, their relative effectiveness in enhancing photocatalytic activity remains unclear due to the lack of rational probing catalysts. In this study, we synthesized two distinct carbon nitride (C3N4) catalysts: one with a high specific surface area (CN-HA) and the other with improved crystallinity (CN-HC). These catalysts served as probes to compare their respective impacts on photocatalytic activities. Comprehensive characterization techniques and density functional theory (DFT) calculation results unveiled that crystallinity played a dominant role in light absorption and charge dynamics, while surface area primarily influenced mass transfer in photocatalysis. Importantly, our findings revealed that crystallinity engineering of photocatalyst achieved a greater impact on photocatalytic hydrogen evolution than that from mass transfer enhancement. Consequently, CN-HC demonstrated a remarkable improvement in photocatalytic performance for hydrogen evolution (6465.4 mu mol h-1 g-1), surpassing both C3N4 and CN-HA by 19.4- and 2.4-fold, respectively, accompanied by a high apparent quantum yield of 23.8 % at 420 nm. This study not only unveils the dominant factor influencing the activity of photocatalysts but also provides a modified approach for robust solar fuel production, shedding light on the path toward efficient and sustainable energy conversion.