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Biomimetic O2 adsorption in an iron metal–organic framework for air separation
Chemical Science ( IF 7.6 ) Pub Date : 2020/01/10 , DOI: 10.1039/c9sc06047b
Douglas A. Reed 1, 2, 3, 4 , Dianne J. Xiao 1, 2, 3, 4 , Henry Z. H. Jiang 1, 2, 3, 4 , Khetpakorn Chakarawet 1, 2, 3, 4 , Julia Oktawiec 1, 2, 3, 4 , Jeffrey R. Long 1, 2, 3, 4, 5
Affiliation  

Bio-inspired motifs for gas binding and small molecule activation can be used to design more selective adsorbents for gas separation applications. Here, we report an iron metal–organic framework, Fe-BTTri (Fe3[(Fe4Cl)3(BTTri)8]2·18CH3OH, H3BTTri = 1,3,5-tris(1H-1,2,3-triazol-5-yl)benzene), that binds O2 in a manner similar to hemoglobin and therefore results in highly selective O2 binding. As confirmed by gas adsorption studies and Mössbauer and infrared spectroscopy data, the exposed iron sites in the framework reversibly adsorb substantial amounts of O2 at low temperatures by converting between high-spin, square-pyramidal Fe(II) centers in the activated material to low-spin, octahedral Fe(III)–superoxide sites upon gas binding. This change in both oxidation state and spin state observed in Fe-BTTri leads to selective and readily reversible O2 binding, with the highest reported O2/N2 selectivity for any iron-based framework.

中文翻译:

仿生氧气在铁-金属框架中的空气分离吸附

用于气体结合和小分子活化的生物启发基序可用于设计用于气体分离应用的更具选择性的吸附剂。在这里,我们报告一个铁金属-有机骨架,铁- BTTri(铁3 [(铁4 Cl)的3(BTTri)8 ] 2 ·18CH 3 OH,H 3 BTTri = 1,3,5-三(1 ħ - (1,2,3-三唑-5-基)苯),其以类似于血红蛋白的方式结合O 2,因此导致高度选择性的O 2结合。气体吸附研究以及Mössbauer和红外光谱数据证实,骨架中暴露的铁部位可逆地吸附了大量O 2在低温下,通过在气体结合后将活化材料中的高旋转方锥锥体Fe(II)中心转换为低旋转的八面体Fe(III)-超氧化物位点来实现。在Fe-BTTri中观察到的氧化态和自旋态的这种变化导致选择性和易于逆转的O 2结合,对于任何铁基骨架,报道的O 2 / N 2选择性最高。
更新日期:2020-02-13
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