Direct Identification of Mixed-Metal Centers in Metal-Organic Frameworks: Cu3(BTC)2 Transmetalated with Rh2+ Ions

被引：23

作者：

Metavarayuth, Kamolrat ^{[1
]}

Ejegbavwo, Otega ^{[1
]}

McCarver, Gavin ^{[2
]}

Myrick, Michael L. ^{[1
]}

Makris, Thomas M. ^{[1
]}

Vogiatzis, Konstantinos D. ^{[2
]}

Senanayake, Sanjaya D. ^{[3
]}

Manley, Olivia M. ^{[1
]}

Ebrahim, Amani M. ^{[4
]}

Frenkel, Anatoly, I ^{[3
,4
]}

Hwang, Sooyeon ^{[5
]}

Rajeshkumar, Thayalan ^{[2
]}

Jimenez, Juan D. ^{[6
]}

Chen, Kexun ^{[1
]}

Shustova, Natalia B. ^{[1
]}

Chen, Donna A. ^{[1
]}

机构：

[1] Univ South Carolina, Dept Chem & Biochem, Columbia, SC 29208 USA

[2] Univ Tennessee, Dept Chem, Knoxville, TN 37996 USA

[3] Brookhaven Natl Lab, Chem Div, Upton, NY 11973 USA

[4] SUNY Stony Brook, Dept Mat Sci & Chem Engn, Stony Brook, NY 11794 USA

[5] Brookhaven Natl Lab, Ctr Funct Nanomat, Upton, NY 11973 USA

[6] Univ South Carolina, Dept Chem Engn, Columbia, SC 29208 USA

来源：

JOURNAL OF PHYSICAL CHEMISTRY LETTERS | 2020年 / 11卷 / 19期

关键词：

ELECTRON-PARAMAGNETIC-RESONANCE; HKUST-1; CHEMISTRY; ACTIVATION; CATALYSIS;

D O I：

10.1021/acs.jpclett.0c02539

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：

Raman spectroscopy was used to establish direct evidence of heterometallic metal centers in a metal-organic framework (MOF). The Cu-3(BTC)(2) MOF HKUST-1 (BTC3- = benzenetricarboxylate) was transmetalated by heating it in a solution of RhCl3 to substitute Rh2+ ions for Cu2+ ions in the dinuclear paddlewheel nodes of the framework. In addition to the Cu-Cu and Rh-Rh stretching modes, Raman spectra of (CuxRh1-x)(3)(BTC)(2) show the Cu-Rh stretching mode, indicating that mixed-metal Cu-Rh nodes are formed after transmetalation. Density functional theory studies confirmed the assignment of a Raman peak at 285 cm(-1) to the Cu-Rh stretching vibration. Electron paramagnetic resonance spectroscopy experiments further supported the conclusion that Rh2+ ions are substituted into the paddlewheel nodes of Cu-3(BTC)(2) to form an isostructural heterometallic MOF, and electron microscopy studies showed that Rh and Cu are homogeneously distributed in (CuxRh1-x)(3)(BTC)(2) on the nanoscale.

引用

页码：8138 / 8144

页数：7

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