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有序微孔碳中杂原子对其电化学电容的影响。

Effect of Heteroatoms in Ordered Microporous Carbons on Their Electrochemical Capacitance.

机构信息

Department of Applied Chemistry, Aichi Institute of Technology , Yachigusa 1247, Yakusa-cho, Toyota, 470-0392, Japan.

Institute of Multidisciplinary Research for Advanced Materials, Tohoku University , Sendai 980-8577, Japan.

出版信息

Langmuir. 2016 Nov 22;32(46):11997-12004. doi: 10.1021/acs.langmuir.6b02667. Epub 2016 Nov 7.

Abstract

Micropores play a more important role in enhancing the electrochemical capacitance than mesopores and macropores; therefore, the effect of heteroatom doping into micropores on the electrochemical behavior is interesting. However, heteroatom doping into porous carbon materials would potentially change their pore structures and pore sizes, which also affect their electrochemical capacitive behaviors. To gain insight into the intrinsic effects of heteroatoms on the electrochemical capacitive behaviors, zeolite-templated carbon (ZTC) may be the most suitable candidate. ZTC is an ordered microporous carbon with a uniform micropore size of 1.2 nm, a high surface area, and a large micropore volume. In this work, a series of ZTCs containing oxygen, nitrogen, or boron as heteroatoms, with an ordered pore structure and the same pore size, are prepared. By examining their electrochemical capacitive behaviors in an organic electrolyte, the effect of heteroatom doping can be isolated and discussed without considering the effects of pore structure and pore size. Acid anhydride groups are found to generate pseudocapacitance in two potential ranges, -1.0 to -0.3 V (vs Ag/AgClO) and -0.2 to 0.4 V. B is introduced into the ZTC framework solely as -B(OH), which is found to be an electrochemically inert species. N is introduced as pyridine (3.0%), pyridone/pyrrole (23.8%), quaternary (66.6%), and oxidized N (6.6%), and these species exhibit noticeable pseudocapacitance in the microporous carbon.

摘要

微孔在增强电化学电容方面比介孔和大孔起着更重要的作用;因此,杂原子掺杂到微孔中对电化学行为的影响是很有趣的。然而,杂原子掺杂到多孔碳材料中可能会改变其孔结构和孔径,这也会影响其电化学电容行为。为了深入了解杂原子对电化学电容行为的内在影响,沸石模板碳(ZTC)可能是最合适的候选材料。ZTC 是一种有序的微孔碳,具有均匀的微孔尺寸为 1.2nm、高比表面积和大的微孔体积。在这项工作中,制备了一系列含有氧、氮或硼作为杂原子的 ZTC,它们具有有序的孔结构和相同的孔径。通过在有机溶剂中考察它们的电化学电容行为,可以在不考虑孔结构和孔径影响的情况下,隔离和讨论杂原子掺杂的影响。发现酸酐基团在两个电位范围内产生赝电容,-1.0 到-0.3V(相对于 Ag/AgClO)和-0.2 到 0.4V。B 仅作为-B(OH)被引入到 ZTC 骨架中,被发现是电化学惰性的。N 被引入到 ZTC 中作为吡啶(3.0%)、吡啶酮/吡咯(23.8%)、季铵盐(66.6%)和氧化 N(6.6%),这些物种在微孔碳中表现出明显的赝电容。

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