Guided Assembly of Microporous/Mesoporous Manganese Phosphates by Bifunctional Organophosphonic Acid Etching and Templating.

Manganese (Mn)-based compounds are important materials for both energy conversion and energy storage. Unfortunately, it has been a significant challenge to develop highly ordered microporous/mesoporous structures for them to provide more active sites for these applications. In order to do so using the soft-templating method, three conditions have to be met, namely, a strong interaction between the inorganic precursor and the organic templates; eliminating the formation of bulk manganese phosphate; and the preservation of the manganese phosphate framework without it collapsing upon template removal. Herein, a soft-templating approach is reported using an organophosphonic acid (n-hexylphosphonic acid) as both the etching and the templating agent, followed by high-vacuum-assisted annealing. This approach simultaneously satisfies the above conditions. Both microporous and mesoporous manganese phosphates with uniform pore sizes and well-defined pore structures are obtained. The utilization of the organophosphonic acid is shown to be the key in the transformation from bulk manganese oxide into a highly ordered microporous phosphate. A very high surface area of 304.1 m2 g-1 is obtained for the microporous manganese phosphate, which is the highest among the reported values for Mn-based compounds. The ultrafine micropores and high specific surface area of our manganese phosphate promote electrocatalytic activity for the oxygen evolution reaction.