Unveiling the Key Obstacle in Photocatalytic Overall Water Splitting Reaction on Poly (heptazine imide) Semiconductors

Abstract Poly (heptazine imide) (PHI), a classic 2D polymeric photocatalyst, represents a promising organic semiconductor for photocatalytic overall water splitting (POWS). However, since the key bottleneck in POWS of PHI remains unclear, its quantum efficiency of POWS is extremely restrained. To identify the key obstacle in POWS on the PHI, a series of PHI with different stacking modes is synthesized by tuning interlayer cations. The structural characterizations revealed that tuning the interlayer cations of PHI can induce rearrangements in interlayer stacking modes. Additionally, charge carriers dynamics uncover that optimizing the interlayer stacking modes of PHI can promote exciton diffusion and prolong the photoexcited electron lifetimes, thus improving the concentration of surface‐reaching charge. More importantly, this confirms that the POWS activity of PHI is closely correlated with the interlayer stacking modes. This work offers new insight into structural regulation for governing charge‐transport dynamics and the activity of 2D polymeric photocatalysts.