Amorphizing MnIn2S4 Atomic Layers Create an Asymmetrical InO1S5 Polarization Plane for Photocatalytic Ammonia Synthesis and CO2 Reduction.

ABSTRACT

Building a polarization center is an effective avenue to boost charge separation and molecular activation in photocatalysis. However, a limited number of polarization centers are usually created. Here, a polarization plane based on two-dimensional (2D) atomic layers is designed to maximize the surface polarization centers. The Mn in a 2D crystal lattice is etched from the MnIn2S4 atomic layers to build a consecutive symmetry-breaking structure of isolated InO1S5 sites. More charges aggregate around O, making the isolated InO1S5 sites highly polarized. Due to the formation of the InO1S5 polarization plane, an enormous polarized electric field is formed perpendicular to the 2D atomic layers and the carrier lifetime can be prolonged from 93.2 ps in MnIn2S4 to 1130 ps in amorphous MnxIn2Sy. Meantime, the formed large charge density gradient favors coupling and activation of small molecules. Benefiting from these features, a good NH3 photosynthesis performance (515.8 µmol g-1 h-1) can be realized over amorphous MnxIn2Sy, roughly 2.5 and 48.9 times higher than those of MnIn2S4 atomic layers and bulk MnIn2S4, respectively. The apparent quantum yields reach 5.4 and 3.3% at 380 and 400 nm, respectively. Meanwhile, a greatly improved CO2 reduction activity is also achieved over MnxIn2Sy. This strategy provides an accessible pathway for designing an asymmetrical polarization plane to motivate photocatalysis optimization.