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Manganese dioxide structural effects on its thermal decomposition

机译：二氧化锰的结构对其热分解的影响

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摘要

In this work, the influence of the structure, composition and morphology on the amount of mass lost from γ-MnO2 during heat treatment, and the activation energy for this process (from iso-conversional kinetic analysis), was determined using a statistical approach. It was found that the differential thermogravi-metric (DTG) data for electrolytic manganese dioxide (EMD) samples typically show two regions of mass loss; water bound to surface sites and structural water at or near the surface removed between ~120 and 200°C, and bulk hydroxyl groups lost in the range ~200-400°C. The composition and morphology had the greatest effect on the amount of mass lost; namely, BET surface area and percentage Mn(lll) for the first process (r2 =0.92) and percentage Mn(IV), percentage Mn(III) and cation vacancy fraction for the second (r2 =0.89). The activation energy for the first processes was most affected by BET surface area, c0 and crystallite size in the (2 21) direction (r2 =0.89). Relatively poor correlations were found between the amount of water lost and the activation energy for the second process and the material properties measured in this work. This likely relates to the slow kinetics of the first mass loss which complicates the relationships existing for the second.
机译：在这项工作中，使用统计方法确定了结构，组成和形态对热处理过程中γ-MnO2损失的质量数量的影响以及该过程的活化能（来自等转化动力学分析）。已经发现，电解二氧化锰（EMD）样品的差示热重（DTG）数据通常显示出两个质量损失区域。在约120至200°C之间除去与表面部位结合的水和表面处或附近的结构水，并且在〜200-400°C范围内失去大量羟基。组成和形态对质量损失的影响最大。即，第一个过程的BET表面积和Mn（III）百分比（r2 = 0.92），第二个过程的Mn（IV）百分比，Mn（III）百分比和阳离子空位分数（r2 = 0.89）。第一步的活化能受BET表面积，c0和（2 21）方向上的微晶尺寸的最大影响（r2 = 0.89）。在第二步工艺的失水量和活化能与这项工作中测得的材料性能之间发现了相对较差的相关性。这可能与第一次质量损失的动力学缓慢有关，这使第二次质量损失的关系变得复杂。

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