Catalytic behavior of hexaphenyldisiloxane in the synthesis of pyrite FeS 2
Catalytic behavior of hexaphenyldisiloxane in the synthesis of pyrite FeS 2
复制标题
六苯基二硅氧烷合成黄铁矿 FeS 2 的催化行为
DOI：
10.1039/d0cc03397a
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发表时间：
2020
影响因子：
4.9
通讯作者：
Neilson, James R.
中科院分区：
文献类型：
--
作者：
Todd, Paul K.;Martinolich, Andrew J.;Neilson, James R.
功能性小分子提供了在低温下引导固态无机反应的机会。在这里，我们使用催化量的有机硅分子来影响复分解反应：FeCl2 + Na2S2 → 2NaCl + FeS2。具体而言，六苯基二硅氧烷 ((C6H5)6Si2O) 可提高 150 °C 下进行的复分解反应中的黄铁矿产率。原位同步加速器 X 射线衍射 (SXRD) 与差示扫描量热法 (DSC) 相结合表明，在 (C6H5)6Si2O 的存在下，限制扩散的中间体被规避。对照反应表明观察到的反应途径变化是由 Si-O 官能团引起的。 1H NMR 支持催化行为，因为 (C6H5)6Si2O 事后未发生变化。综上所述，我们假设当 NaCl 和 Na2S4 形成时，极性 Si-O 官能团与氯化铁物质配位，形成一种未知的瞬态中间体。进一步探索这些复分解反应中的目标小分子，为低温控制无机材料合成提供了新策略。
Functional small molecules afford opportunities to direct solid-state inorganic reactions at low temperatures. Here, we use catalytic amounts of organosilicon molecules to influence the metathesis reaction: FeCl2 + Na2S2 → 2NaCl + FeS2. Specifically, hexaphenyldisiloxane ((C6H5)6Si2O) is shown to increase pyrite yields in metathesis reactions performed at 150 °C. In situ synchrotron X-ray diffraction (SXRD) paired with differential scanning calorimetry (DSC) reveals that diffusion-limited intermediates are circumvented in the presence of (C6H5)6Si2O. Control reactions suggest that the observed change in the reaction pathway is imparted by the Si–O functional group. 1H NMR supports catalytic behavior, as (C6H5)6Si2O is unchanged ex post facto. Taken together, we hypothesize that the polar Si–O functional group coordinates to iron chloride species when NaCl and Na2S4 form, forming an unidentified, transient intermediate. Further exploration of targeted small molecules in these metathesis reaction provides new strategies in controlling inorganic materials synthesis at low-temperatures.