A thermodynamic analysis using quantum chemical methods was carried out to identify optimal functional group candidates that can be included in metal–organic frameworks and activated carbons for the selective capture of toxic industrial chemicals (TICs) in humid air. We calculated the binding energies of 14 critical TICs plus water with a series of 10 functional groups attached to a naphthalene ring model. Using vibrational calculations, the free energies of adsorption were calculated in addition to the binding energies. Our results show that, in these systems, the binding energies and free energies follow similar trends. We identified copper(I) carboxylate as the optimal functional group (among those studied) for the selective binding of the majority of the TICs in humid air, and this functional group exhibits especially strong binding for sulfuric acid. Further thermodynamic analysis shows that the presence of water weakens the binding strength of sulfuric acid with the copper carboxylate group. Our calculations predict that functionalization of aromatic rings would be detrimental to selective capture of COCl₂, CO₂, and Cl₂ under humid conditions. Finally, we found that forming an ionic complex, H₃O⁺HSO₄⁻, between H₂SO₄ and H₂O via proton transfer is not favorable on copper carboxylate.

中文翻译：

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官能团的计算筛选，用于捕获多孔材料中的有毒工业化学品

进行了使用量子化学方法的热力学分析，以确定可以包含在金属有机框架和活性炭中的最佳官能团候选物，以选择性地捕获潮湿空气中的有毒工业化学品（TIC）。我们计算了14个关键TICs加水的结合能，以及与萘环模型连接的一系列10个官能团的水。使用振动计算，除了结合能之外，还计算了吸附的自由能。我们的结果表明，在这些系统中，结合能和自由能遵循相似的趋势。我们发现铜（我）羧酸盐作为最佳的官能团（在研究的那些当中），是大多数TIC在潮湿空气中的选择性结合，并且该官能团对硫酸表现出特别强的结合力。进一步的热力学分析表明，水的存在会削弱硫酸与羧酸铜基团的结合强度。我们的计算预测，芳香环的官能化将不利于潮湿条件下选择性捕获COCl ₂，CO ₂和Cl ₂。最后，我们发现，形成离子复合物，H ₃ ö ⁺ HSO ₄ ^-，H之间₂ SO ₄和H ₂ ö通过质子转移对羧酸铜不利。