Computational Exploration of the Water Concentration Dependence of the Proton Transport in the Porous UiO-66(Zr)-(CO2H)2 Metal-Organic Framework

被引:42
作者
Borges, Daiane Damasceno [1 ,2 ]
Semino, Rocio [1 ]
Devautour-Vinott, Sabine [1 ]
Jobic, Herve [3 ]
Paesani, Francesco [4 ]
Maurin, Guillaume [1 ]
机构
[1] Univ Montpellier, CNRS, ENSCM, UMR 5253,Inst Charles Gerhardt Montpellier, Pl E Bataillon, R-34095 Montpellier 05, France
[2] Univ Estadual Campinas, Inst Phys Gleb Wataghin, BR-13083970 Campinas, SP, Brazil
[3] Univ Lyon, CNRS, Inst Recherches Catalyse & Environnement Lyon, 2 Av A Einstein, F-69626 Villeurbanne, France
[4] Univ Calif San Diego, Dept Chem & Biochem, La Jolla, CA 92093 USA
基金
巴西圣保罗研究基金会; 美国国家科学基金会;
关键词
ZIRCONIUM TEREPHTHALATE UIO-66(ZR); MOLECULAR-DYNAMICS SIMULATIONS; VALENCE-BOND MODEL; SOLVATION; CONDUCTIVITY; DESIGN; CO2; COMBINATION; MOFS;
D O I
10.1021/acs.chemmater.6b04257
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The UiO-66(Zr)-(CO2H)(2) metal-organic framework been recently revealed as a promising proton conducting material under humidification. Here, aMS-EVB3 molecular dynamics simulations are performed to reveal at the molecular level the structure, thermodynamics, and dynamics of the hydrated proton in three-dimensional (3D)-cages MOF as a function of the water loading. It is found that the most stable proton solvation structure corresponds to a H7O3+ cation and that a transition between this complex and a Zundel cation likely governs the proton transport in this MOF occurring via a Grotthuss-type mechanism. It is further shown that the formation of a H2O hydrogen-bonded bridge that connects the cages occurs only at high water concentration and this creates a path allowing the excess proton to jump from one cage to another. This leads to a faster self-diffusivity of proton at high water concentration, thereby supporting the increase of the proton conductivity with the water loading as experimentally evidenced.
引用
收藏
页码:1569 / 1576
页数:8
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