Twisted BiOCl Moiré Superlattices for Photocatalytic Chloride Reforming of Methane.

Abstract

Solar-driven conversion of CH4 into value-added methyl chlorides and H2 with abundant chloride ions offers a sustainable CH4 reforming strategy but suffers from inefficient Cl- activation and severe e--h+ recombination in traditional photocatalysts. Herein, we demonstrate that BiOCl moiré superlattices with a 11.1° twist angle are highly efficient for photocatalytic CH4 reforming into CH3Cl and H2 with NaCl. These moiré superlattices, featuring misalignment-induced tensile strains, destabilize surface Bi-Cl bonds, facilitating a hole-mediated MvK-analogous process to activate lattice Cl into reactive •Cl for CH4 chlorination. Meanwhile, their twisted stacking configurations reinforce interlayer electronic coupling and thus accelerate out-of-plane carrier transfer. Along with surface anchoring of single-atom Pt sites for H2 evolution, the resulting Pt1/BiOCl moiré superlattices deliver a CH3Cl yield of 53.4 μmol g-1 h-1 with an impressive selectivity of 96% under visible light. This study highlights the potential of lattice engineering in two-dimensional photocatalysts to regulate structural strains and carrier dynamics for the decentralized reforming of CH4.