Guided Assembly of Microporous/Mesoporous Manganese Phosphates by Bifunctional Organophosphonic Acid Etching and Templating
Guided Assembly of Microporous/Mesoporous Manganese Phosphates by Bifunctional Organophosphonic Acid Etching and Templating
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DOI：
10.1002/adma.201901124
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发表时间：
2019-05
影响因子：
29.4
通讯作者：
Yating Hu;Yu Zhang;Changjian Li;Ling Wang;Yonghua Du;G. Mo;Xu Li;A. Cheetham;John Wang
中科院分区：
文献类型：
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作者：
Yating Hu;Yu Zhang;Changjian Li;Ling Wang;Yonghua Du;G. Mo;Xu Li;A. Cheetham;John Wang
锰（Mn）基化合物是能量转换和能量储存的重要材料。不幸的是，这一直是一个重大的挑战，开发高度有序的微孔/介孔结构，为他们提供更多的活性位点，这些应用。为了使用软模板方法这样做，必须满足三个条件，即无机前体和有机模板之间的强相互作用;消除块状磷酸锰的形成;以及保留磷酸锰骨架而不会在模板去除时坍塌。在本文中，报道了使用有机膦酸（正己基膦酸）作为蚀刻剂和模板剂两者，然后进行高真空辅助退火的软模板方法。该方法同时满足上述条件。获得具有均匀孔径和明确孔结构的微孔和介孔磷酸锰。有机膦酸的利用被证明是从块状氧化锰转化为高度有序的微孔磷酸盐的关键。微孔磷酸锰的表面积高达304.1 m2 g−1，是Mn基化合物中最高的。我们的磷酸锰的超细微孔和高比表面积提高了析氧反应的电催化活性。
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.