通过单晶到单晶转化增强金属有机框架中的质子传导

IF 4.7 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR
Cai-Xia Yu, Hao Wu, Zhichao Shao*, Ming-Jun Gao, Xue-Qin Sun and Lei-Lei Liu*, 
{"title":"通过单晶到单晶转化增强金属有机框架中的质子传导","authors":"Cai-Xia Yu,&nbsp;Hao Wu,&nbsp;Zhichao Shao*,&nbsp;Ming-Jun Gao,&nbsp;Xue-Qin Sun and Lei-Lei Liu*,&nbsp;","doi":"10.1021/acs.inorgchem.4c0516910.1021/acs.inorgchem.4c05169","DOIUrl":null,"url":null,"abstract":"<p >In this work, an anionic framework Co-MOF (<b>1</b>) was elaborately constructed, which underwent single-crystal-to-single-crystal (SC-SC) transformation to produce <b>1-Cr</b> and <b>1-Fe</b> after immersion in a CrCl<sub>3</sub> or FeCl<sub>3</sub> solution. Despite the similar crystal structure, the significantly enhanced proton conductivities of <b>1-Cr</b> and <b>1-Fe</b> far exceed that of <b>1</b> at all humidity and temperature conditions. Even at 30 °C and 98% RH, the proton conductivity of <b>1-Cr</b> and <b>1-Fe</b> can reach up to high values of 1.49 × 10<sup>–2</sup> and 6.39 × 10<sup>–3</sup> S cm<sup>–1</sup>, respectively, surpassing that of <b>1</b> by over 5000 times under identical conditions. The partial alteration of the proton-conducting carriers from metal-water cluster [Co(H<sub>2</sub>O)<sub>6</sub>]·6H<sub>2</sub>O] (<b>1</b>) to metal-hydroxyl-water clusters [Cr(OH)<sub>4</sub>(H<sub>2</sub>O)<sub>2</sub>]·6H<sub>2</sub>O] (<b>1-Cr</b>) and [Fe(OH)<sub>4</sub>(H<sub>2</sub>O)<sub>2</sub>]·6H<sub>2</sub>O] (<b>1-Fe</b>) can be attributed for the above-mentioned enhanced performance. The introduction of hydroxyl by SC-SC transformation can establish interconnected proton conduction pathways within the proton channels, which greatly facilitate proton conduction, affording much lower activation energies (0.12 eV for <b>1-Cr</b>, 0.18 eV for <b>1-Fe</b>, and 0.28 eV for <b>1</b>). This research demonstrated that SC-SC transformation not only achieved significantly improved proton conduction but also contributed to a deeper understanding of the structure–property relationships, providing new insights into the design of advanced materials with enhanced proton conductivity.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"64 8","pages":"3908–3916 3908–3916"},"PeriodicalIF":4.7000,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Enhanced Proton Conduction in Metal–Organic Frameworks through Single-Crystal to Single-Crystal Transformation\",\"authors\":\"Cai-Xia Yu,&nbsp;Hao Wu,&nbsp;Zhichao Shao*,&nbsp;Ming-Jun Gao,&nbsp;Xue-Qin Sun and Lei-Lei Liu*,&nbsp;\",\"doi\":\"10.1021/acs.inorgchem.4c0516910.1021/acs.inorgchem.4c05169\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >In this work, an anionic framework Co-MOF (<b>1</b>) was elaborately constructed, which underwent single-crystal-to-single-crystal (SC-SC) transformation to produce <b>1-Cr</b> and <b>1-Fe</b> after immersion in a CrCl<sub>3</sub> or FeCl<sub>3</sub> solution. Despite the similar crystal structure, the significantly enhanced proton conductivities of <b>1-Cr</b> and <b>1-Fe</b> far exceed that of <b>1</b> at all humidity and temperature conditions. Even at 30 °C and 98% RH, the proton conductivity of <b>1-Cr</b> and <b>1-Fe</b> can reach up to high values of 1.49 × 10<sup>–2</sup> and 6.39 × 10<sup>–3</sup> S cm<sup>–1</sup>, respectively, surpassing that of <b>1</b> by over 5000 times under identical conditions. The partial alteration of the proton-conducting carriers from metal-water cluster [Co(H<sub>2</sub>O)<sub>6</sub>]·6H<sub>2</sub>O] (<b>1</b>) to metal-hydroxyl-water clusters [Cr(OH)<sub>4</sub>(H<sub>2</sub>O)<sub>2</sub>]·6H<sub>2</sub>O] (<b>1-Cr</b>) and [Fe(OH)<sub>4</sub>(H<sub>2</sub>O)<sub>2</sub>]·6H<sub>2</sub>O] (<b>1-Fe</b>) can be attributed for the above-mentioned enhanced performance. The introduction of hydroxyl by SC-SC transformation can establish interconnected proton conduction pathways within the proton channels, which greatly facilitate proton conduction, affording much lower activation energies (0.12 eV for <b>1-Cr</b>, 0.18 eV for <b>1-Fe</b>, and 0.28 eV for <b>1</b>). This research demonstrated that SC-SC transformation not only achieved significantly improved proton conduction but also contributed to a deeper understanding of the structure–property relationships, providing new insights into the design of advanced materials with enhanced proton conductivity.</p>\",\"PeriodicalId\":40,\"journal\":{\"name\":\"Inorganic Chemistry\",\"volume\":\"64 8\",\"pages\":\"3908–3916 3908–3916\"},\"PeriodicalIF\":4.7000,\"publicationDate\":\"2025-02-13\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Inorganic Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.inorgchem.4c05169\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Inorganic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.inorgchem.4c05169","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0

摘要

这项研究精心构建了一种阴离子框架 Co-MOF(1),将其浸入氯化铬或氯化铁溶液后,经过单晶到单晶(SC-SC)转变,生成了 1-Cr 和 1-Fe。尽管晶体结构相似,但在所有湿度和温度条件下,1-Cr 和 1-Fe 的质子传导性都显著增强,远远超过了 1。即使在 30 °C 和 98% 相对湿度条件下,1-Cr 和 1-Fe 的质子电导率也能分别达到 1.49 × 10-2 和 6.39 × 10-3 S cm-1 的高值,比相同条件下的 1 高出 5000 多倍。质子传导载体从金属-水簇[Co(H2O)6]-6H2O](1)部分转变为金属-羟基-水簇[Cr(OH)4(H2O)2]-6H2O](1-Cr)和[Fe(OH)4(H2O)2]-6H2O](1-Fe)可归因于上述性能的提高。通过 SC-SC 转化引入羟基,可在质子通道内建立相互连接的质子传导通路,从而大大促进质子传导,使活化能大大降低(1-Cr 为 0.12 eV,1-Fe 为 0.18 eV,1 为 0.28 eV)。这项研究表明,SC-SC 转换不仅显著改善了质子传导,而且有助于加深对结构-性能关系的理解,为设计具有更强质子传导性的先进材料提供了新的见解。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Enhanced Proton Conduction in Metal–Organic Frameworks through Single-Crystal to Single-Crystal Transformation

Enhanced Proton Conduction in Metal–Organic Frameworks through Single-Crystal to Single-Crystal Transformation

In this work, an anionic framework Co-MOF (1) was elaborately constructed, which underwent single-crystal-to-single-crystal (SC-SC) transformation to produce 1-Cr and 1-Fe after immersion in a CrCl3 or FeCl3 solution. Despite the similar crystal structure, the significantly enhanced proton conductivities of 1-Cr and 1-Fe far exceed that of 1 at all humidity and temperature conditions. Even at 30 °C and 98% RH, the proton conductivity of 1-Cr and 1-Fe can reach up to high values of 1.49 × 10–2 and 6.39 × 10–3 S cm–1, respectively, surpassing that of 1 by over 5000 times under identical conditions. The partial alteration of the proton-conducting carriers from metal-water cluster [Co(H2O)6]·6H2O] (1) to metal-hydroxyl-water clusters [Cr(OH)4(H2O)2]·6H2O] (1-Cr) and [Fe(OH)4(H2O)2]·6H2O] (1-Fe) can be attributed for the above-mentioned enhanced performance. The introduction of hydroxyl by SC-SC transformation can establish interconnected proton conduction pathways within the proton channels, which greatly facilitate proton conduction, affording much lower activation energies (0.12 eV for 1-Cr, 0.18 eV for 1-Fe, and 0.28 eV for 1). This research demonstrated that SC-SC transformation not only achieved significantly improved proton conduction but also contributed to a deeper understanding of the structure–property relationships, providing new insights into the design of advanced materials with enhanced proton conductivity.

求助全文
通过发布文献求助,成功后即可免费获取论文全文。 去求助
来源期刊
Inorganic Chemistry
Inorganic Chemistry 化学-无机化学与核化学
CiteScore
7.60
自引率
13.00%
发文量
1960
审稿时长
1.9 months
期刊介绍: Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
确定
请完成安全验证×
copy
已复制链接
快去分享给好友吧!
我知道了
右上角分享
点击右上角分享
0
联系我们:info@booksci.cn Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。 Copyright © 2023 布克学术 All rights reserved.
京ICP备2023020795号-1
ghs 京公网安备 11010802042870号
Book学术文献互助
Book学术文献互助群
群 号:604180095
Book学术官方微信