<br>添加二胺的镁-奥沙拉嗪框架中的协同二氧化碳捕获,Journal of the American Chemical Society

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添加二胺的镁-奥沙拉嗪框架中的协同二氧化碳捕获
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2023-07-26 , DOI: 10.1021/jacs.3c03870
Ziting Zhu _{1,

2,

3} , Surya T Parker _{3,

4} , Alexander C Forse _{2,

4} , Jung-Hoon Lee _{5,

6} , Rebecca L Siegelman _{2,

3} , Phillip J Milner _{2,

3} , Hsinhan Tsai _{2,

3} , Mengshan Ye ₂ , Shuoyan Xiong ₂ , Maria V Paley ₂ , Adam A Uliana _{3,

4} , Julia Oktawiec ₂ , Bhavish Dinakar _{3,

4} , Stephanie A Didas ₃ , Katie R Meihaus ₂ , Jeffrey A Reimer ₄ , Jeffrey B Neaton _{5,

6} , Jeffrey R Long _{2,

3,

4}

Affiliation

附加二胺的 Mg ₂ (dobpdc) (dobpdc ^4– = 4,4'-二氧化联苯-3,3'-二羧酸酯)金属有机框架由于其优异的 CO ₂选择性和高分离能力而成为碳捕获的有前途的候选材料和阶梯形吸附曲线，这是由独特的协同吸附机制产生的，导致氨基甲酸铵链的形成。特别是带有具有大体积取代基的伯、仲二胺的材料表现出优异的稳定性和CO ₂吸附性能。然而，这些框架表现出由氨基甲酸铵之间的空间排斥引起的双步吸附行为，最终导致再生能量增加。在此，我们报告了二胺-Mg ₂ (olz) (olz ^4– = ( E )-5,5′-(diazene-1,2-diyl)bis(2-oxydoBenzate)) 类型的框架，其特征在于具有多种二胺体积大的取代基，并在很宽的压力和温度范围内表现出理想的单步CO ₂吸附。 CO ₂吸附数据分析表明，除了空间体积之外，孔内胺的碱度是影响吸附步骤压力的重要因素。此外，发现胺空间体积与CO ₂吸收的协同程度呈负相关。一种材料 ee-2–Mg ₂ (olz)（ee-2 = N , N-二乙基乙二胺）可从模拟煤烟流中吸附 >90% 的_CO2 ，并在广泛的使用过程中表现出出色的热稳定性和氧化稳定性。吸附/解吸循环，使其成为迄今为止从煤烟气中捕获 CO _{2 的}性能最佳的吸附剂之一。光谱表征和范德华校正密度泛函理论计算表明，二胺-Mg ₂ (olz) 材料通过形成氨基甲酸铵链来捕获CO ₂ 。这些结果更广泛地表明了通过明智的设计从根本上改进此类材料的机会。

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Cooperative Carbon Dioxide Capture in Diamine-Appended Magnesium–Olsalazine Frameworks

Diamine-appended Mg₂(dobpdc) (dobpdc^4– = 4,4′-dioxidobiphenyl-3,3′-dicarboxylate) metal–organic frameworks have emerged as promising candidates for carbon capture owing to their exceptional CO₂ selectivities, high separation capacities, and step-shaped adsorption profiles, which arise from a unique cooperative adsorption mechanism resulting in the formation of ammonium carbamate chains. Materials appended with primary,secondary-diamines featuring bulky substituents, in particular, exhibit excellent stabilities and CO₂ adsorption properties. However, these frameworks display double-step adsorption behavior arising from steric repulsion between ammonium carbamates, which ultimately results in increased regeneration energies. Herein, we report frameworks of the type diamine–Mg₂(olz) (olz^4– = (E)-5,5′-(diazene-1,2-diyl)bis(2-oxidobenzoate)) that feature diverse diamines with bulky substituents and display desirable single-step CO₂ adsorption across a wide range of pressures and temperatures. Analysis of CO₂ adsorption data reveals that the basicity of the pore-dwelling amine─in addition to its steric bulk─is an important factor influencing adsorption step pressure; furthermore, the amine steric bulk is found to be inversely correlated with the degree of cooperativity in CO₂ uptake. One material, ee-2–Mg₂(olz) (ee-2 = N,N-diethylethylenediamine), adsorbs >90% of the CO₂ from a simulated coal flue stream and exhibits exceptional thermal and oxidative stability over the course of extensive adsorption/desorption cycling, placing it among top-performing adsorbents to date for CO₂ capture from a coal flue gas. Spectroscopic characterization and van der Waals-corrected density functional theory calculations indicate that diamine–Mg₂(olz) materials capture CO₂ via the formation of ammonium carbamate chains. These results point more broadly to the opportunity for fundamentally advancing materials in this class through judicious design.

更新日期：2023-07-26

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