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Silver-functionalized silica aerogel: towards an understanding of aging on iodine sorption performance

机译:银功能化二氧化硅气凝胶:了解老化对碘吸附性能的影响

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The silver-functionalized silica aerogel (Ag ~(0) -aerogel) is being developed for the removal and sequestration of iodine compounds from the off-gas of a nuclear fuel reprocessing plant. This material shows high selectivity and sorption capacity for iodine. However, its sorption performance decreases when exposed to air containing H _(2) O and NO _( x ) at 150 °C for extended periods of time. This phenomenon is referred to as “aging” and simulates exposure of the sorbent during plant idling. This extensive study of unaged and aged samples of Ag ~(0) -aerogel with and without iodine revealed that decreased efficiency of I capture after NO-aging can be attributed to an increase in size of silver nanoparticles and by the formation of free sulfate on their surfaces from oxidized thiol groups. The smaller reactive surface areas of bigger particles and thin sulfate layer on particle surfaces prevented a complete utilization of the silver. By contrast, formation of silver sulfate appears to be the main factor in decreasing the sorption capacity for samples aged in dry or humid air. It is hypothesized that a short period exposure of the Ag ~(0) -aerogel to a reducing gas stream would reduce oxidized silver back to metal and sulfate to sulfide. This may recover the sorption performance of Ag ~(0) -aerogel close to original levels.
机译:银功能化的二氧化硅气凝胶(Ag〜(0)-气凝胶)正在开发中,用于从核燃料后处理厂的废气中去除和螯合碘化合物。该材料显示出对碘的高选择性和吸附能力。但是,当在150°C下长时间暴露于含有H_(2)O和NO_(x)的空气中时,其吸附性能会下降。这种现象称为“老化”,它模拟了植物空转过程中吸附剂的暴露。这项对有或没有碘的Ag〜(0)-气凝胶的未老化和老化样品的广泛研究表明,NO老化后I捕获效率的降低可归因于银纳米颗粒尺寸的增加和在表面上形成游离硫酸盐。它们的表面由氧化的巯基组成。较大颗粒的较小反应表面积和颗粒表面上的薄硫酸盐层阻止了银的完全利用。相反,硫酸银的形成似乎是降低在干燥或潮湿空气中老化的样品的吸附能力的主要因素。假设将Ag〜(0)-气凝胶短时间暴露于还原性气流中将氧化的银还原成金属,将硫酸盐还原成硫化物。这可以恢复接近原始水平的Ag〜(0)-气凝胶的吸附性能。

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