Modulating charge oriented accumulation via interfacial chemical-bond on In 2 O 3 /Bi 2 MoO 6 heterostructures for photocatalytic nitrogen fixation.

Photocatalytic nitrogen fixation presents an eco-friendly approach to converting atmospheric nitrogen into ammonia (NH3 ), but the process faces challenges due to rapid interface charge recombination. Here, we report an innovative charge transfer and oriented accumulation strategy using an In-O-Mo bond-modulated S-scheme heterostructure composed of In2 O3 /Bi2 MoO6 (In/BMO) synthesized using a simple electrostatic assembly. The unique interfacial arrangement with optimal photocatalyst configuration (3 % In/BMO) enabled enhanced photogenerated electron separation and transfer, leading to a remarkable nitrogen fixation rate of approximately 150.9 μmol·gcat -1 ·h-1 under visible light irradiation. The performance of the photocatalyst was 9-fold and 27-fold higher than that of its pristine components, Bi2 MoO6 and In2 O3 , respectively. The experimental and theoretical evaluation deemed interfacial In-O-Mo bonds crucial for rapid transfer and charge-oriented accumulation. Whereas the generated internal electric field drove the spatial separation and transfer of photo-generated electrons and holes, significantly enhancing the photocatalytic N2 -to-NH3 conversion efficiency. The proposed work lays the foundation for designing S-scheme heterostructures with highly efficient interfacial bonds, offering a promising avenue for substantial improvements in photocatalytic nitrogen fixation.