Highly Cooperative CO2 Adsorption via a Cation Crowding Mechanism on a Cesium-Exchanged Phillipsite Zeolite.

Highly Cooperative CO2 Adsorption via a Cation Crowding Mechanism on a Cesium-Exchanged Phillipsite Zeolite.
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通过铯交换菲利普沸石上的阳离子拥挤机制实现高度协同的 CO2 吸附。

DOI:
10.1002/anie.202305816
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发表时间:
2023
期刊:
Angewandte Chemie (International ed. in English)
影响因子:
--
通讯作者:
Choi HJ
Choi HJ
中科院分区:
--
文献类型:
--
作者:
Choi HJ

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了解CO2在小孔沸石上的吸附机理对于开发更有效的吸附剂用于从N2或CH 4中分离CO2具有实际重要性。在这里,我们报告了在25-75 °C下,在Si/Al比为2.5(Cs-PHI-2.5)的铯交换钙钛矿沸石上的CO2等温线的特征在于直线台阶形状:在低CO2压力(PCO 2)下的有限吸收之后是在临界压力下的高度合作吸收,高于临界压力,吸附迅速接近容量(2.0 mmol g−1)。 结构分析表明,这种等温行为归因于脱水Cs-PHI-2.5中的高浓度和大尺寸的Cs+离子。这导致在Cs+阳离子拥挤和随后的分散在一个临界负载的CO2,这使得PHI框架放松到其宽孔形式,并使其孔填充CO2在一个非常窄的范围内的PCO 2。这种高度协同的现象在其它沸石中还没有观察到。
An understanding of the CO2adsorption mechanisms on small‐pore zeolites is of practical importance in the development of more efficient adsorbents for the separation of CO2from N2or CH4. Here we report that the CO2isotherms at 25–75 °C on cesium‐exchanged phillipsite zeolite with a Si/Al ratio of 2.5 (Cs‐PHI‐2.5) are characterized by a rectilinear step shape: limited uptake at low CO2pressure (PCO2) is followed by highly cooperative uptake at a critical pressure, above which adsorption rapidly approaches capacity (2.0 mmol g−1). Structural analysis reveals that this isotherm behavior is attributed to the high concentration and large size of Cs+ions in dehydrated Cs‐PHI‐2.5. This results in Cs+cation crowding and subsequent dispersal at a critical loading of CO2, which allows the PHI framework to relax to its wide pore form and enables its pores to fill with CO2over a very narrow range of PCO2. Such a highly cooperative phenomenon has not been observed for other zeolites.
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