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The mineral woodruffite, Zn 2+   x/2  (Mn 4+  1-x  Mn 3+   x )O 2 ·yH 2 O, x ~ 0.4 and y ~ 0.7, is the first known example of a new type of Mn oxide characterized by large tunnels that measure 3 and 4 octahedra (6.9 × 9.2 Å) on a side. These tunnels are rectangular in cross-section and are the largest of any yet reported in natural or synthetic Mn oxides. The thermal stability of woodruffite is comparable to that of todorokite and other large-tunnel Mn oxide phases, breaking down at ~300 °C and eventually transforming to a spinel-type structure. The woodruffite structure may serve as a model for a new class of octahedral molecular sieves with enhanced capabilities as catalysts and selective cationexchange agents.

Woodruffite: A new Mn oxide structure with 3 × 4 tunnels