Jiang Yi, Oh Inseon, Joo Se Hun, Seo Yu-Seong, Lee Sun Hwa, Seong Won Kyung, Kim Yu Jin, Hwang Jungseek, Kwak Sang Kyu, Yoo Jung-Woo, Ruoff Rodney S
Center for Multidimensional Carbon Materials (CMCM), Institute for Basic Science (IBS), Ulsan 44919, Republic of Korea.
Department of Physics, Sungkyunkwan University, Suwon, Gyeonggi-do 61419, Republic of Korea.
J Am Chem Soc. 2020 Oct 28;142(43):18346-18354. doi: 10.1021/jacs.0c02389. Epub 2020 Oct 6.
We report the synthesis and characterization of a two-dimensional (2D) MXY-type (M = metal, X, Y = N, S, O, and X ≠ Y) copper 1,3,5-triamino-2,4,6-benzenetriol metal-organic framework (Cu(TABTO)-MOF). The role of oxygen in the synthesis of this MOF was investigated. Copper metal is formed along with the MOF when the synthesis is done in argon as suggested by XRD. When the reaction was exposed to air with vigorous stirring, copper metal was not observed by XRD. However, if there is no stirring, then copper metal is formed, and we learned that this is because oxygen was not allowed to enter the solvent due to the formation of a MOF film at the air/water interface. For the sample synthesized in argon (Cu(TABTO)-Ar), an insulating Cu(TABTO)-Ar pellet (σ < 10 S cm) became a metallic conductor with an electrical conductivity of 0.78 S cm at 300 K after exposure to iodine vapor. This work provides further insights into the role of oxygen in the synthesis of redox-active ligand-based MOFs, expands the family of 2D redox-active ligand-based electrically conductive MOFs, and offers more opportunities in sensing, photocatalytic, electronic, and energy-related applications.
我们报道了一种二维(2D)MXY型(M = 金属,X、Y = N、S、O,且X ≠ Y)铜1,3,5-三氨基-2,4,6-苯三醇金属有机框架(Cu(TABTO)-MOF)的合成与表征。研究了氧在该MOF合成过程中的作用。如X射线衍射(XRD)所示,当在氩气中进行合成时,会生成铜金属和MOF。当反应在剧烈搅拌下暴露于空气中时,XRD未观察到铜金属。然而,如果不进行搅拌,则会生成铜金属,我们了解到这是因为在空气/水界面形成了MOF膜,阻止了氧气进入溶剂。对于在氩气中合成的样品(Cu(TABTO)-Ar),一个绝缘的Cu(TABTO)-Ar小球(σ < 10 S cm)在暴露于碘蒸气后,在300 K时变成了电导率为0.78 S cm的金属导体。这项工作进一步深入了解了氧在基于氧化还原活性配体的MOF合成中的作用,扩展了基于二维氧化还原活性配体的导电MOF家族,并在传感、光催化、电子和能源相关应用中提供了更多机会。