Photocatalytic oxygen evolution from low-bandgap conjugated microporous polymer nanosheets: a combined first-principles calculation and experimental study.

Nanostructured semiconducting polymers have emerged as a very promising class of metal-free photocatalytic materials for solar water splitting. However, they generally exhibit low efficiency and lack the ability to utilize long-wavelength photons in a photocatalytic oxygen evolution reaction (OER). Here, based on first-principles calculations, we reveal that the two-dimensional (2D) aza-fused conjugated microporous polymer (aza-CMP) with a honeycomb network is a semiconductor with novel layer-dependent electronic properties. The bandgap of the as-synthesized aza-CMP nanosheets is measured to be 1.22 eV, suggesting that they can effectively boost light absorption in the visible and near infrared (NIR) region. More importantly, aza-CMP also possesses a valence band margin suitable for a photocatalytic OER. Taking advantage of the 2D layered nanostructure, we further show that the exfoliated ultrathin aza-CMP nanosheets can exhibit a three-fold enhancement in the photocatalytic OER. After deposition of a Co(OH) cocatalyst, the hybrid Co(OH)/aza-CMP photocatalyst exhibits a markedly improved performance for photocatalytic O evolution. Furthermore, first-principles calculations reveal that the photocatalytic O evolution reaction is energetically feasible for aza-CMP nanosheets under visible light irradiation. Our findings reveal that nanostructured polymers hold great potential for photocatalytic applications with efficient solar energy utilization.