Facile reversible hydrogenation of a poly(6‐vinyl‐2,3‐dimethyl‐1,2,3,4‐tetrahydroquinoxaline) gel‐like solid
Facile reversible hydrogenation of a poly(6‐vinyl‐2,3‐dimethyl‐1,2,3,4‐tetrahydroquinoxaline) gel‐like solid
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DOI：
10.1002/pat.5163
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发表时间：
2020-11
影响因子：
3.4
通讯作者：
Yusuke Kaiwa;Kouki Oka;H. Nishide;K. Oyaizu
中科院分区：
文献类型：
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作者：
Yusuke Kaiwa;Kouki Oka;H. Nishide;K. Oyaizu
带有储氢单元的聚合物通过化学键形成来储存氢气，并且具有作为准固体聚合物氢载体的固有优点，例如易于处理和高安全性。最近的一项研究表明，聚（6-乙烯基-1，2，3，4-四氢喹喔啉）凝胶状固体在120°C和空气下脱氢5小时，然后在铱络合物催化剂的存在下，在60°C和环境氢气压力下可逆氢化。本工作旨在通过甲基取代喹喔啉单元中氮原子相邻碳原子上的氢原子来提高脱氢速率。这主要归因于甲基的供电子性质和脱氢态的稳定性。聚（6-乙烯基-2，3-二甲基-1，2，3，4-四氢喹喔啉）凝胶状固体在相同的温和条件下在2小时内快速脱氢。本文为快速脱氢氮杂环化合物的分子设计提供了指导。
Polymers bearing hydrogen storage units store hydrogen gas via chemical bond formation, and have inherent advantages as quasi‐solid polymeric hydrogen carriers, such as handling easiness and high safety. A recent study demonstrated that a poly(6‐vinyl‐1,2,3,4‐tetrahydroquinoxaline) gel‐like solid was dehydrogenated over 5 h under 120°C and air, and then the material was reversibly hydrogenated under 60°C and ambient hydrogen pressure in the presence of an iridium complex catalyst. The present work aimed to improve the dehydrogenation rate via the substitution of methyl groups for hydrogen atoms on carbon atoms adjacent to the nitrogen atoms in the quinoxaline unit. The dramatic improvement was attributed to the electron donating property of methyl group, and stabilization of the dehydrogenated state. The poly(6‐vinyl‐2,3‐dimethyl‐1,2,3,4‐tetrahydroquinoxaline) gel‐like solid was rapidly dehydrogenated within 2 h under the same mild conditions. This article provides a guideline for the molecular design of nitrogen heterocyclic compounds for rapid dehydrogenation.