已入深夜,您辛苦了!由于当前在线用户较少,发布求助请尽量完整地填写文献信息,科研通机器人24小时在线,伴您度过漫漫科研夜!祝你早点完成任务,早点休息,好梦!

Guest Molecule-Responsive Functional Calcium Phosphonate Frameworks for Tuned Proton Conductivity

化学 单斜晶系 结晶学 水溶液 结构精修 分子 结晶度 膦酸盐 粉末衍射 X射线晶体学 结晶 晶体结构 无机化学 衍射 物理化学 有机化学 物理 光学
作者
Montse Bazaga-García,Rosario M. P. Colodrero,Maria Papadaki,Piotr Garczarek,Jerzy Zoń,Pascual Olivera‐Pastor,Enrique R. Losilla,Laura León‐Reina,Miguel Á. G. Aranda,Duane Choquesillo‐Lazarte,Konstantinos D. Demadis,Aurelio Cabeza
出处
期刊:Journal of the American Chemical Society [American Chemical Society]
卷期号:136 (15): 5731-5739 被引量:208
标识
DOI:10.1021/ja500356z
摘要

We report the synthesis, structural characterization, and functionality (framework interconversions together with proton conductivity) of an open-framework hybrid that combines Ca2+ ions and the rigid polyfunctional ligand 5-(dihydroxyphosphoryl)isophthalic acid (PiPhtA). Ca2[(HO3PC6H3COOH)2]2[(HO3PC6H3(COO)2H)(H2O)2]·5H2O (Ca-PiPhtA-I) is obtained by slow crystallization at ambient conditions from acidic (pH ≈ 3) aqueous solutions. It possesses a high water content (both Ca coordinated and in the lattice), and importantly, it exhibits water-filled 1D channels. At 75 °C, Ca-PiPhtA-I is partially dehydrated and exhibits a crystalline diffraction pattern that can be indexed in a monoclinic cell with parameters close to the pristine phase. Rietveld refinement was carried out for the sample heated at 75 °C, Ca-PiPhtA-II, using synchrotron powder X-ray diffraction data, which revealed the molecular formula Ca2[(HO3PC6H3COOH)2]2[(HO3PC6H3(COO)2H)(H2O)2]. All connectivity modes of the "parent" Ca-PiPhtA-I framework are retained in Ca-PiPhtA-II. Upon Ca-PiPhtA-I exposure to ammonia vapors (28% aqueous NH3) a new derivative is obtained (Ca-PiPhtA-NH3) containing 7 NH3 and 16 H2O molecules according to elemental and thermal analyses. Ca-PiPhtA-NH3 exhibits a complex X-ray diffraction pattern with peaks at 15.3 and 13.0 Å that suggest partial breaking and transformation of the parent pillared structure. Although detailed structural identification of Ca-PiPhtA-NH3 was not possible, due in part to nonequilibrium adsorption conditions and the lack of crystallinity, FT-IR spectra and DTA-TG analysis indicate profound structural changes compared to the pristine Ca-PiPhtA-I. At 98% RH and T = 24 °C, proton conductivity, σ, for Ca-PiPhtA-I is 5.7 × 10–4 S·cm–1. It increases to 1.3 × 10–3 S·cm–1 upon activation by preheating the sample at 40 °C for 2 h followed by water equilibration at room temperature under controlled conditions. Ca-PiPhtA-NH3 exhibits the highest proton conductivity, 6.6 × 10–3 S·cm–1, measured at 98% RH and T = 24 °C. Activation energies (Ea) for proton transfer in the above-mentioned frameworks range between 0.23 and 0.4 eV, typical of a Grothuss mechanism of proton conduction. These results underline the importance of internal H-bonding networks that, in turn, determine conductivity properties of hybrid materials. It is highlighted that new proton transfer pathways may be created by means of cavity "derivatization" with selected guest molecules resulting in improved proton conductivity.

科研通智能强力驱动
Strongly Powered by AbleSci AI
更新
PDF的下载单位、IP信息已删除 (2025-6-4)

科研通是完全免费的文献互助平台,具备全网最快的应助速度,最高的求助完成率。 对每一个文献求助,科研通都将尽心尽力,给求助人一个满意的交代。
实时播报
爆米花应助hyr采纳,获得10
刚刚
刚刚
学不完了完成签到 ,获得积分10
1秒前
充电宝应助一二采纳,获得10
2秒前
BettyNie完成签到 ,获得积分10
3秒前
甜甜圈发布了新的文献求助10
4秒前
yoke完成签到,获得积分10
4秒前
yuan完成签到,获得积分10
5秒前
5秒前
含糊的无声完成签到 ,获得积分10
6秒前
xiaofeiyan发布了新的文献求助40
6秒前
量子星尘发布了新的文献求助10
6秒前
Bin_Liu完成签到,获得积分20
7秒前
8秒前
SciGPT应助想游泳的鹰采纳,获得10
8秒前
悄悄发布了新的文献求助10
9秒前
9秒前
guozizi完成签到,获得积分10
10秒前
11秒前
852应助顺利秋灵采纳,获得10
11秒前
A.y.w完成签到,获得积分10
12秒前
短短急个球完成签到,获得积分10
12秒前
hyr发布了新的文献求助10
12秒前
wwf完成签到,获得积分10
13秒前
甜甜圈完成签到,获得积分10
15秒前
天天快乐应助宁紫涵采纳,获得10
16秒前
tong完成签到 ,获得积分10
20秒前
小邹爱科研完成签到,获得积分20
20秒前
Akim应助organoid elegan采纳,获得10
20秒前
20秒前
搞怪薯片发布了新的文献求助10
21秒前
段盈完成签到,获得积分10
22秒前
风趣的灵枫完成签到 ,获得积分10
23秒前
一二完成签到,获得积分10
23秒前
23秒前
23秒前
gtgyh完成签到 ,获得积分10
24秒前
七七完成签到 ,获得积分10
24秒前
顺利秋灵发布了新的文献求助10
25秒前
明时完成签到,获得积分10
27秒前
高分求助中
A new approach to the extrapolation of accelerated life test data 1000
Picture Books with Same-sex Parented Families: Unintentional Censorship 700
ACSM’s Guidelines for Exercise Testing and Prescription, 12th edition 500
Nucleophilic substitution in azasydnone-modified dinitroanisoles 500
不知道标题是什么 500
Indomethacinのヒトにおける経皮吸収 400
Phylogenetic study of the order Polydesmida (Myriapoda: Diplopoda) 370
热门求助领域 (近24小时)
化学 材料科学 医学 生物 工程类 有机化学 生物化学 物理 内科学 纳米技术 计算机科学 化学工程 复合材料 遗传学 基因 物理化学 催化作用 冶金 细胞生物学 免疫学
热门帖子
关注 科研通微信公众号,转发送积分 3976560
求助须知:如何正确求助?哪些是违规求助? 3520659
关于积分的说明 11204287
捐赠科研通 3257271
什么是DOI,文献DOI怎么找? 1798653
邀请新用户注册赠送积分活动 877835
科研通“疑难数据库(出版商)”最低求助积分说明 806570