Department of Chemistry, University of California, Berkeley, California, 94720, USA.
Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California, 94720, USA.
Nat Commun. 2018 Dec 3;9(1):5133. doi: 10.1038/s41467-018-07458-6.
Over one million tons of CS are produced annually, and emissions of this volatile and toxic liquid, known to generate acid rain, remain poorly controlled. As such, materials capable of reversibly capturing this commodity chemical in an energy-efficient manner are of interest. Recently, we detailed diamine-appended metal-organic frameworks capable of selectively capturing CO through a cooperative insertion mechanism that promotes efficient adsorption-desorption cycling. We therefore sought to explore the ability of these materials to capture CS through a similar mechanism. Employing crystallography, spectroscopy, and gas adsorption analysis, we demonstrate that CS is indeed cooperatively adsorbed in N,N-dimethylethylenediamine-appended M(dobpdc) (M = Mg, Mn, Zn; dobpdc = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate), via the formation of electrostatically paired ammonium dithiocarbamate chains. In the weakly thiophilic Mg congener, chemisorption is cleanly reversible with mild thermal input. This work demonstrates that the cooperative insertion mechanism can be generalized to other high-impact target molecules.
每年生产超过一百万吨的 CS，这种挥发性和有毒液体的排放仍然控制得很差。因此，人们对能够以节能的方式可逆捕获这种商品化学品的材料很感兴趣。最近，我们详细介绍了二胺修饰的金属有机骨架，它们能够通过促进高效吸附-解吸循环的协同插入机制选择性地捕获 CO。因此，我们试图探索这些材料通过类似机制捕获 CS 的能力。通过晶体学、光谱学和气体吸附分析，我们证明 CS 确实通过形成静电配对的铵二硫代氨基甲酸盐链在 N，N-二甲基乙二胺修饰的 M(dobpdc)（M = Mg、Mn、Zn；dobpdc = 4,4'-二氧代联苯-3,3'-二羧酸酯）中协同吸附。在弱硫亲合性的 Mg 同系物中，化学吸附在温和的热输入下可完全可逆。这项工作表明，协同插入机制可以推广到其他高影响目标分子。
