Agbim Amarachukwu, Banga-Bothy Georgia-Annicette, Samokhvalov Alexander
Department of Chemistry, Morgan State University, Baltimore, Maryland, USA.
Appl Spectrosc. 2024 Jul;78(7):680-691. doi: 10.1177/00037028241248673. Epub 2024 May 8.
Oxidized organosulfur compounds and, in particular, sulfoxides are of interest as solvents in the semiconductor and pharmaceutical industry, environmental contaminants, and simulants in deactivation of chemical warfare agents. An experimental study is reported of the interaction of porphyrin aluminum metal-organic framework Al-MOF-TCPPH (Compound 2) with diethyl sulfoxide (DESO) in pure form and in aqueous solution. First, the suitability of Compound 2 as sorbent in aqueous solution was assessed; namely, its long-term stability (up to 15 days) in liquid water has been investigated at room temperature and under stirring. Here, a novel facile spectroscopic method has been used, a periodic micro-sampling of sorbent from suspension, followed by vacuum mini-filtration and an ex situ time-dependent attenuated total reflection Fourier transform infrared spectroscopy (ATR FT-IR) analysis. Next, the interaction of Compound 2 with pure liquid DESO under ambient conditions was investigated, which yields the stoichiometric adsorption complex (Al-MOF-TCPPH)(DESO) denoted Compound 3. In this adsorption complex, molecules of DESO interact with the OH group and carboxylate group of the sorbent. Then, the removal of DESO from Compound 3 was assessed, using facile treatment with warm water in the micro Soxhlet apparatus followed by the ATR FT-IR analysis. Finally, Compound 2 was tested in sorption of DESO from diluted aqueous solution. In the initial step, the sorption proceeds very quickly (in <1 min the concentration of DESO decreases by about 20%) followed by a much slower step. The maximum amount of adsorbed DESO corresponds to half of the amount adsorbed from pure DESO as found by the high-performance liquid chromatography-ultraviolet detection method. This adsorbed amount corresponds to 1 mol DESO adsorbate per mol of sorbent. Porphyrin aluminum metal-organic framework Compound 2 is promising for the removal of DESO from diluted aqueous solution, and it is of interest for the removal of similar oxidized organosulfur compounds.
氧化有机硫化合物，特别是亚砜，作为半导体和制药行业的溶剂、环境污染物以及化学战剂失活模拟剂受到关注。本文报道了卟啉铝金属有机框架Al-MOF-TCPPH（化合物2）与纯二乙基亚砜（DESO）及水溶液中二乙基亚砜相互作用的实验研究。首先，评估了化合物2作为水溶液中吸附剂的适用性；即在室温下搅拌条件下研究了其在液态水中的长期稳定性（长达15天）。在此，采用了一种新颖便捷的光谱方法，即从悬浮液中定期微量取样吸附剂，随后进行真空微过滤以及非原位随时间变化的衰减全反射傅里叶变换红外光谱（ATR FT-IR）分析。接下来，研究了化合物2在环境条件下与纯液态DESO的相互作用，得到了化学计量吸附络合物（Al-MOF-TCPPH）（DESO），记为化合物3。在该吸附络合物中，DESO分子与吸附剂的OH基团和羧酸根基团相互作用。然后，通过在微型索氏提取器中用温水进行简便处理，随后进行ATR FT-IR分析，评估了从化合物3中去除DESO的情况。最后，测试了化合物2对稀水溶液中DESO的吸附性能。在初始阶段，吸附过程非常迅速（在不到1分钟内DESO浓度降低约20%），随后是一个慢得多的阶段。通过高效液相色谱 - 紫外检测法发现，吸附的DESO最大量相当于从纯DESO中吸附量的一半。该吸附量对应于每摩尔吸附剂吸附1摩尔DESO吸附质。卟啉铝金属有机框架化合物2有望用于从稀水溶液中去除DESO，并且对于去除类似的氧化有机硫化合物也具有研究价值。
