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采用 DRIFTS 研究 CoII3[CoIII(CN)6]2 对 CO2 和 SO2 的竞争吸附

Competitive adsorption study of CO2 and SO2 on CoII3[CoIII(CN)6]2 using DRIFTS.

机构信息

Pacific Northwest National Laboratory, P.O. Box 999, Richland, WA 99352, USA.

出版信息

Spectrochim Acta A Mol Biomol Spectrosc. 2010 Sep 15;77(1):287-91. doi: 10.1016/j.saa.2010.05.024. Epub 2010 May 24.

Abstract

Diffuse reflectance infrared Fourier transform spectroscopy was used to study the competitive adsorption of CO(2) and SO(2) on the cobalt Prussian blue analogue Co(II)(3)Co(III)(CN)(6) at 298 K. Characteristic peaks for adsorbed CO(2) and SO(2) species were identified and their relative areas, measured simultaneously as a function of pressure at 298 K, varied in accordance with a Langmuir-Freundlich isotherm fitted to both gases in the low-coverage Henry's Law limit. Evidence for co-adsorption of trace water was also obtained, as well as the apparent formation of an analogous cobalt nitroprusside compound as a reaction product under certain conditions. The several aspects of the adsorption of CO(2) and SO(2) determined in this work point to an important role for real-time diffuse reflectance infrared measurements in adsorption studies, particularly in the case of competitive adsorption where the occurrence and fate of molecular-level markers arising from more than one adsorbed species can be monitored simultaneously. Depending on the application, this may more than offset certain quantitative limitations of the technique that confine measurements to a relatively narrow set of experimental conditions and demand careful consideration of the effects of sample preparation and treatment.

摘要

采用漫反射红外傅里叶变换光谱法研究了在 298 K 下 CO(2)和 SO(2)在钴普鲁士蓝类似物 Co(II)(3)Co(III)(CN)(6)上的竞争吸附。鉴定了吸附态 CO(2)和 SO(2)物种的特征峰,并在 298 K 下同时测量了它们的相对面积随压力的变化,其变化符合在低覆盖度亨利定律极限下两种气体的 Langmuir-Freundlich 等温线拟合。还获得了痕量水共吸附的证据,以及在某些条件下作为反应产物形成类似的钴亚硝基铁氰化物化合物的证据。本工作中确定的 CO(2)和 SO(2)吸附的几个方面表明,实时漫反射红外测量在吸附研究中具有重要作用,特别是在竞争吸附的情况下,因为可以同时监测来自一种以上吸附物种的分子水平标记物的出现和命运。根据应用的不同,这可能会超过该技术的某些定量限制,这些限制将测量限制在相对较窄的一组实验条件内,并需要仔细考虑样品制备和处理的影响。

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