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

Abstract

Raman spectroscopy was used to establish direct evidence of heterometallic metal centers in a metal–organic framework (MOF). The Cu3(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 Cu3(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.

Authors:
 [1];  [1];  [2];  [1];  [1];  [2];  [1]; ORCiD logo [3];  [4];  [5];  [6];  [2];  [1];  [1];  [1];  [1]
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  1. Univ. of South Carolina, Columbia, SC (United States)
  2. Univ. of Tennessee, Knoxville, TN (United States)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
  4. Stony Brook Univ., NY (United States)
  5. Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., NY (United States)
  6. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1716757
Report Number(s):
BNL-220600-2020-JAAM
Journal ID: ISSN 1948-7185
Grant/Contract Number:  
SC0012704; SC0019360; SC0001004
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 11; Journal Issue: 19; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
02 PETROLEUM; Ions; metal organic frameworks; Raman spectroscopy; electron paramagnetic resonance spectroscopy; quantum mechanics

Citation Formats

Metavarayuth, Kamolrat, Ejegbavwo, Otega, McCarver, Gavin, Myrick, Michael L., Makris, Thomas M., Vogiatzis, Konstantinos D., Manley, Olivia M., Senanayake, Sanjaya D., Ebrahim, Amani M., Frenkel, Anatoly I., Hwang, Sooyeon, Rajeshkumar, Thayalan, Jimenez, Juan D., Chen, Kexun, Shustova, Natalia B., and Chen, Donna A. Direct Identification of Mixed-Metal Centers in Metal–Organic Frameworks: Cu3(BTC)2 Transmetalated with Rh2+ Ions. United States: N. p., 2020. Web. doi:10.1021/acs.jpclett.0c02539.
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Metavarayuth, Kamolrat, Ejegbavwo, Otega, McCarver, Gavin, Myrick, Michael L., Makris, Thomas M., Vogiatzis, Konstantinos D., Manley, Olivia M., Senanayake, Sanjaya D., Ebrahim, Amani M., Frenkel, Anatoly I., Hwang, Sooyeon, Rajeshkumar, Thayalan, Jimenez, Juan D., Chen, Kexun, Shustova, Natalia B., & Chen, Donna A. Direct Identification of Mixed-Metal Centers in Metal–Organic Frameworks: Cu3(BTC)2 Transmetalated with Rh2+ Ions. United States. https://doi.org/10.1021/acs.jpclett.0c02539
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Metavarayuth, Kamolrat, Ejegbavwo, Otega, McCarver, Gavin, Myrick, Michael L., Makris, Thomas M., Vogiatzis, Konstantinos D., Manley, Olivia M., Senanayake, Sanjaya D., Ebrahim, Amani M., Frenkel, Anatoly I., Hwang, Sooyeon, Rajeshkumar, Thayalan, Jimenez, Juan D., Chen, Kexun, Shustova, Natalia B., and Chen, Donna A. Mon . "Direct Identification of Mixed-Metal Centers in Metal–Organic Frameworks: Cu3(BTC)2 Transmetalated with Rh2+ Ions". United States. https://doi.org/10.1021/acs.jpclett.0c02539. https://www.osti.gov/servlets/purl/1716757.
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@article{osti_1716757,
title = {Direct Identification of Mixed-Metal Centers in Metal–Organic Frameworks: Cu3(BTC)2 Transmetalated with Rh2+ Ions},
author = {Metavarayuth, Kamolrat and Ejegbavwo, Otega and McCarver, Gavin and Myrick, Michael L. and Makris, Thomas M. and Vogiatzis, Konstantinos D. and Manley, Olivia M. and Senanayake, Sanjaya D. and Ebrahim, Amani M. and Frenkel, Anatoly I. and Hwang, Sooyeon and Rajeshkumar, Thayalan and Jimenez, Juan D. and Chen, Kexun and Shustova, Natalia B. and Chen, Donna A.},
abstractNote = {Raman spectroscopy was used to establish direct evidence of heterometallic metal centers in a metal–organic framework (MOF). The Cu3(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 Cu3(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.},
doi = {10.1021/acs.jpclett.0c02539},
journal = {Journal of Physical Chemistry Letters},
number = 19,
volume = 11,
place = {United States},
year = {Mon Sep 07 00:00:00 EDT 2020},
month = {Mon Sep 07 00:00:00 EDT 2020}
}
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https://doi.org/10.1021/acs.jpclett.0c02539
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