Effect of iron substitution in cryptomelane on the heterogeneous reaction with isoprene

Biogenic isoprene is an important pollutant for regional air quality. Being ubiquitously distributed on the earth surface, manganese (hydr)oxides should play a vital role in the transformation of isoprene. Cryptomelane is a typical manganese oxide with isomorphous substitution of Fe for Mn, but less attention has been paid to its heterogeneous reaction with isoprene. When Fe³⁺ replaces Mn³⁺, K⁺ is depleted and Mn³⁺ is oxidized to Mn⁴⁺. In contrast, oxygen vacancies are formed when Fe³⁺ substitutes Mn⁴⁺. Fe substitution creates weak crystallites and abundant mesopores, resulting in the increase of isoprene adsorption. As found by theoretical calculations, the Mn⁴⁺-O^2- bonds at the cross sections of the tunnels is more active than that on the outer wall of the tunnels. After the adsorption of isoprene, bridging carboxylate species and hydrogen-bonding water are produced and the surface octahedra are distorted, i.e., Mn⁴⁺O₆ → Mn³⁺O_6-δ. As the heat facilitates the breakage of Mn⁴⁺-O^2-, the increase of environmental temperature enhances the oxidation of isoprene. The above findings shed light on the effect of Fe substitution in cryptomelane to enhance the oxidation of isoprene, and illustrates that heterogeneous reaction with isoprene impairs the transformation of other environmental substances on cryptomelane.