Bi12O17Cl2 with a Sextuple BiO Layer Composed of Rock‐Salt and Fluorite Units and its Structural Conversion through Fluorination to Enhance Photocatalytic Activity

Abstract Layered bismuth oxyhalides with bilayered (Bi 2 O 2 ) fluorite (FL) slabs are promising visible‐light photocatalysts because of their excellent stability and the ability to adjust band levels depending on the layers combined. It is interesting to manipulate the Bi 2 O 2 slab itself, but only trilayered FL blocks (e.g., Bi 3 O 4 ) are reported so far. Here, a structurally uncharacterized Bi 12 O 17 Cl 2 , which is extensively studied as a photocatalyst for a variety of reactions, has a sextuple Bi 6 O 8.5 block separated by Cl is shown. Unlike double and triple layered cases, the inner region of the Bi 6 O 8.5 block contains 1D rock‐salt (RS) units in the FL matrix along the a ‐axis, causing in‐plane corrugation. A topochemical reaction involving anion‐exchange gives Bi 12 O 17–0.5 x F x Cl 2 ( x ≤ 6) with alternate FL and RS slabs along the c ‐axis. The elimination of the structural corrugation increases higher photo‐conductivity and improves photocatalytic activity against acetic acid decomposition under visible light irradiation. This study paves new opportunities of controlling the properties of layered bismuth oxyhalides by the thickness of Bi–O block, FL/RS configuration, and structural modulation.