The thermally induced decarboxylation mechanism of a mixed-oxidation state carboxylate-based iron metal–organic framework
Abstract
Investigations into a thermally generated decarboxylation mechanism for metal site activation and the generation of mesopores in a carboxylate iron-based MOF, PCN-250, have been conducted. PCN-250 exhibits an interesting oxidation state change during thermal treatment under inert atmospheres or vacuum conditions, transitioning from an Fe(III)3 cluster to a Fe(II)Fe(III)2 cluster. To probe this redox event and discern a mechanism of activation, a combination of thermogravimetric analysis, gas sorption, scanning electron microscopy, 57Fe Mössbauer spectroscopy, gas chromatography-mass spectrometry, and X-ray diffraction studies were conducted. The results suggest that the iron-site activation occurs due to ligand decarboxylation above 200 °C. This is also consistent with the generation of a missing cluster mesoporous defect in the framework. The resulting mesoporous PCN-250 maintains high thermal stability, preserving crystallinity after multiple consecutive high-temperature regeneration cycles. Additionally, the thermally reduced PCN-250 shows improvements in the total uptake capacity of methane and CO2.
- Authors:
-
[1];
[1];
[1];
[1];
[1];
[1]
- Texas A & M Univ., College Station, TX (United States)
- Framergy Inc., College Station, TX (United States)
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations Relevant to Clean Energy Technologies (CGS); Texas A & M Univ., College Station, TX (United States)
- Sponsoring Org.:
- USDOE Office of Fossil Energy (FE); National Science Foundation (NSF)
- OSTI Identifier:
- 1767688
- Alternate Identifier(s):
- OSTI ID: 1567713
- Grant/Contract Number:
- SC0001015; FE0026472; AC02-05CH11231; 1632486; NRPR9-377-1-080
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ChemComm
- Additional Journal Information:
- Journal Volume: 55; Journal Issue: 85; Journal ID: ISSN 1359-7345
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; membrane; carbon capture; materials and chemistry by design; synthesis (novel materials); synthesis (self-assembly); synthesis (scalable processing)
Citation Formats
Drake, Hannah F., Day, Gregory S., Vali, Shaik Waseem, Xiao, Zhifeng, Banerjee, Sayan, Li, Jialuo, Joseph, Elizabeth A., Kuszynski, Jason E., Perry, Zachary T., Kirchon, Angelo, Ozdemir, Osman K., Lindahl, Paul A., and Zhou, Hong-Cai. The thermally induced decarboxylation mechanism of a mixed-oxidation state carboxylate-based iron metal–organic framework. United States: N. p., 2019.
Web. doi:10.1039/c9cc04555d.
Drake, Hannah F., Day, Gregory S., Vali, Shaik Waseem, Xiao, Zhifeng, Banerjee, Sayan, Li, Jialuo, Joseph, Elizabeth A., Kuszynski, Jason E., Perry, Zachary T., Kirchon, Angelo, Ozdemir, Osman K., Lindahl, Paul A., & Zhou, Hong-Cai. The thermally induced decarboxylation mechanism of a mixed-oxidation state carboxylate-based iron metal–organic framework. United States. https://doi.org/10.1039/c9cc04555d
Drake, Hannah F., Day, Gregory S., Vali, Shaik Waseem, Xiao, Zhifeng, Banerjee, Sayan, Li, Jialuo, Joseph, Elizabeth A., Kuszynski, Jason E., Perry, Zachary T., Kirchon, Angelo, Ozdemir, Osman K., Lindahl, Paul A., and Zhou, Hong-Cai. Tue .
"The thermally induced decarboxylation mechanism of a mixed-oxidation state carboxylate-based iron metal–organic framework". United States. https://doi.org/10.1039/c9cc04555d. https://www.osti.gov/servlets/purl/1767688.
@article{osti_1767688,
title = {The thermally induced decarboxylation mechanism of a mixed-oxidation state carboxylate-based iron metal–organic framework},
author = {Drake, Hannah F. and Day, Gregory S. and Vali, Shaik Waseem and Xiao, Zhifeng and Banerjee, Sayan and Li, Jialuo and Joseph, Elizabeth A. and Kuszynski, Jason E. and Perry, Zachary T. and Kirchon, Angelo and Ozdemir, Osman K. and Lindahl, Paul A. and Zhou, Hong-Cai},
abstractNote = {Investigations into a thermally generated decarboxylation mechanism for metal site activation and the generation of mesopores in a carboxylate iron-based MOF, PCN-250, have been conducted. PCN-250 exhibits an interesting oxidation state change during thermal treatment under inert atmospheres or vacuum conditions, transitioning from an Fe(III)3 cluster to a Fe(II)Fe(III)2 cluster. To probe this redox event and discern a mechanism of activation, a combination of thermogravimetric analysis, gas sorption, scanning electron microscopy, 57Fe Mössbauer spectroscopy, gas chromatography-mass spectrometry, and X-ray diffraction studies were conducted. The results suggest that the iron-site activation occurs due to ligand decarboxylation above 200 °C. This is also consistent with the generation of a missing cluster mesoporous defect in the framework. The resulting mesoporous PCN-250 maintains high thermal stability, preserving crystallinity after multiple consecutive high-temperature regeneration cycles. Additionally, the thermally reduced PCN-250 shows improvements in the total uptake capacity of methane and CO2.},
doi = {10.1039/c9cc04555d},
journal = {ChemComm},
number = 85,
volume = 55,
place = {United States},
year = {Tue Sep 24 00:00:00 EDT 2019},
month = {Tue Sep 24 00:00:00 EDT 2019}
}
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Works referencing / citing this record:
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