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Crystal engineering of a rectangular sql coordination network to enable xylenes selectivity over ethylbenzene
Chemical Science ( IF 7.6 ) Pub Date : 2020-06-16 , DOI: 10.1039/d0sc02123g
Naveen Kumar 1 , Shi-Qiang Wang 1 , Soumya Mukherjee 1 , Andrey A Bezrukov 1 , Ewa Patyk-Kaźmierczak 1, 2 , Daniel O'Nolan 1 , Amrit Kumar 1 , Mei-Hui Yu 3 , Ze Chang 3 , Xian-He Bu 3 , Michael J Zaworotko 1
Affiliation  

Separation of the C8 aromatic isomers, p-xylene (PX), m-xylene (MX), o-xylene (OX) and ethylbenzene (EB), is relevant thanks to their widespread application as chemical feedstocks but challenging because of their similar boiling points and close molecular dimensions. Physisorptive separation could offer an energy-efficient solution to this challenge but sorbents which exhibit strong selectivity for one of the isomers remain a largely unmet challenge despite recent reports of OX or PX selective sorbents with high uptake capacity. For example, the square lattice, sql, topology coordination network [Co(bipy)2(NCS)2]n (sql-1-Co-NCS) exhibits the rare combination of high OX selectivity and high uptake capacity. Herein we report that a crystal engineering approach enabled isolation of the mixed-linker sql coordination network [Co(bipy)(bptz)(NCS)2]n (sql-1,3-Co-NCS, bipy = 4,4′-bipyridine, bptz = 4,4′-bis(4-pyridyl)tetrazine) and study of its C8 vapour and liquid sorption properties. sql-1,3-Co-NCS was found to exhibit high adsorption capacity from liquid xylenes (∼37 wt%) and is to our knowledge the first sorbent to exhibit high selectivity for each of xylene isomer over EB (SOX/EB, SMX/EB, SPX/EB > 5). Insights into the performance of sql-1,3-Co-NCS are gained from structural studies which reveal stacking interactions between electron-deficient bptz linkers and the respective xylenes. sql-1,3-Co-NCS is the first N-donor mixed-linker sql coordination network studied for its gas/vapour sorption properties and represents a large and diverse class of understudied coordination networks.

中文翻译:


矩形 SQL 配位网络的晶体工程,使二甲苯相对于乙苯具有选择性



C8 芳香族异构体、二甲苯 (PX)、间二甲苯(MX)、二甲苯 (OX) 和乙苯 (EB) 的分离具有重要意义,因为它们广泛用作化学原料,但由于它们的沸点相似,因此具有挑战性点和接近的分子尺寸。物理吸附分离可以为这一挑战提供一种节能的解决方案,但尽管最近有报道称 OX 或 PX 选择性吸附剂具有高吸收能力,但对其中一种异构体表现出强选择性的吸附剂在很大程度上仍然是一个尚未解决的挑战。例如,方格、 sql 、拓扑协调网络[Co(bipy) 2 (NCS) 2 ] n (sql-1-Co-NCS)表现出高 OX 选择性和高吸收容量的罕见组合。在此,我们报告了一种晶体工程方法能够隔离混合链接器sql协调网络[Co(bipy)(bptz)(NCS) 2 ] n ( sql-1,3-Co-NCS , bipy = 4,4′-联吡啶,bptz = 4,4′-双(4-吡啶基)四嗪)及其 C8 蒸气和液体吸附特性的研究。 sql-1,3-Co-NCS被发现对液体二甲苯(∼37 wt%)表现出高吸附能力,并且据我们所知,它是第一种对每种二甲苯异构体比EB( SO OX/EBS MX/EBSP PX/EB > 5)。 对sql-1,3-Co-NCS性能的深入了解来自于结构研究,该研究揭示了缺电子 bptz 连接体与相应二甲苯之间的堆积相互作用。 sql-1,3-Co-NCS是第一个因其气体/蒸汽吸附特性而被研究的 N 供体混合链接器sql协调网络,代表了一类大型且多样化的正在研究的协调网络。
更新日期:2020-07-08
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