Role of defects and metal coordination on adsorption of acid gases in MOFs and metal oxides: An in situ IR spectroscopic study

William P. Mounfield; Uma Tumuluri; Yang Jiao; Meijun Li; Sheng Dai; Zili Wu; Krista S. Walton

doi:10.1016/j.micromeso.2016.02.023

Role of defects and metal coordination on adsorption of acid gases in MOFs and metal oxides: An in situ IR spectroscopic study

William P. Mounfield, Uma Tumuluri, Yang Jiao, Meijun Li, Sheng Dai, Zili Wu, Krista S. Walton

Research output: Contribution to journal › Article › peer-review

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Abstract

Metal-organic frameworks (MOFs) often display promising performance in ideal, one- or two-component systems; however, industrial adsorption and catalytic applications are almost always in the presence of acid gases that degrade the adsorbent or catalyst. Therefore, it is necessary to understand the interaction of acid gases with MOFs to drive future material design. Acid gas adsorption has been widely investigated on metal oxides, while few fundamental studies exist for MOFs. Therefore, MOF-derived oxides were prepared to give insight into adsorbed species on MOFs by connecting to the understanding that exists for adsorbed species on metal oxides. These MOF-derived oxides retain the overall morphology of the parent MOF, allowing direct comparison of the effect of morphology and the metal coordination environment on adsorbed species and acid gas stability of MOF, MOF-derived oxide, and traditionally synthesized metal oxide. A cerium-based MOF with open-metal sites, CeBTC, and the Ti-based MIL-125 were chosen to prepare MOF-derived oxides. IR studies show that adsorbed species during SO₂ and CO₂ adsorption on the MOF materials could be directly correlated to species observed on the MOF-derived and traditional oxides. In addition, the adsorbed species on the MOF-derived oxides differed from traditional oxides due to their different morphology and retained porosity. SEM and TEM images taken before and after CO₂/SO₂ adsorption experiments revealed degradation of all materials giving visual insight into the degradation mechanism after acid gas exposure. This study advances the understanding of acid gas adsorption on MOFs by correlation of adsorbed species with MOF-derived and traditional metal oxides.

Original language	English
Pages (from-to)	65-75
Number of pages	11
Journal	Microporous and Mesoporous Materials
Volume	227
DOIs	https://doi.org/10.1016/j.micromeso.2016.02.023
State	Published - Jun 2016

Funding

The authors thank Karen Tulig for her help with TEM imaging. This work was supported as part of the Center for Understanding and Control of Acid Gas-Induced Evolution of Materials for Energy (UNCAGE-ME), an Energy Frontier Research Center funded by U.S. Department of Energy , Office of Science, Basic Energy Sciences under Award # DE–SC0012577 . Research at Oak Ridge National Laboratory , including the IR and Raman spectroscopy, was conducted at the Center for Nanophase Materials Sciences, which is a DOE Office of Science User Facility.

Funders	Funder number
U.S. Department of Energy
Office of Science
Basic Energy Sciences	DE–SC0012577

Keywords

Acid gas
Ceria
MOF derived-oxide
Metal-organic framework
Titania

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10.1016/j.micromeso.2016.02.023

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title = "Role of defects and metal coordination on adsorption of acid gases in MOFs and metal oxides: An in situ IR spectroscopic study",

abstract = "Metal-organic frameworks (MOFs) often display promising performance in ideal, one- or two-component systems; however, industrial adsorption and catalytic applications are almost always in the presence of acid gases that degrade the adsorbent or catalyst. Therefore, it is necessary to understand the interaction of acid gases with MOFs to drive future material design. Acid gas adsorption has been widely investigated on metal oxides, while few fundamental studies exist for MOFs. Therefore, MOF-derived oxides were prepared to give insight into adsorbed species on MOFs by connecting to the understanding that exists for adsorbed species on metal oxides. These MOF-derived oxides retain the overall morphology of the parent MOF, allowing direct comparison of the effect of morphology and the metal coordination environment on adsorbed species and acid gas stability of MOF, MOF-derived oxide, and traditionally synthesized metal oxide. A cerium-based MOF with open-metal sites, CeBTC, and the Ti-based MIL-125 were chosen to prepare MOF-derived oxides. IR studies show that adsorbed species during SO2 and CO2 adsorption on the MOF materials could be directly correlated to species observed on the MOF-derived and traditional oxides. In addition, the adsorbed species on the MOF-derived oxides differed from traditional oxides due to their different morphology and retained porosity. SEM and TEM images taken before and after CO2/SO2 adsorption experiments revealed degradation of all materials giving visual insight into the degradation mechanism after acid gas exposure. This study advances the understanding of acid gas adsorption on MOFs by correlation of adsorbed species with MOF-derived and traditional metal oxides.",

keywords = "Acid gas, Ceria, MOF derived-oxide, Metal-organic framework, Titania",

author = "Mounfield, {William P.} and Uma Tumuluri and Yang Jiao and Meijun Li and Sheng Dai and Zili Wu and Walton, {Krista S.}",

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T2 - An in situ IR spectroscopic study

AU - Mounfield, William P.

AU - Tumuluri, Uma

AU - Jiao, Yang

AU - Li, Meijun

AU - Dai, Sheng

AU - Wu, Zili

AU - Walton, Krista S.

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AB - Metal-organic frameworks (MOFs) often display promising performance in ideal, one- or two-component systems; however, industrial adsorption and catalytic applications are almost always in the presence of acid gases that degrade the adsorbent or catalyst. Therefore, it is necessary to understand the interaction of acid gases with MOFs to drive future material design. Acid gas adsorption has been widely investigated on metal oxides, while few fundamental studies exist for MOFs. Therefore, MOF-derived oxides were prepared to give insight into adsorbed species on MOFs by connecting to the understanding that exists for adsorbed species on metal oxides. These MOF-derived oxides retain the overall morphology of the parent MOF, allowing direct comparison of the effect of morphology and the metal coordination environment on adsorbed species and acid gas stability of MOF, MOF-derived oxide, and traditionally synthesized metal oxide. A cerium-based MOF with open-metal sites, CeBTC, and the Ti-based MIL-125 were chosen to prepare MOF-derived oxides. IR studies show that adsorbed species during SO2 and CO2 adsorption on the MOF materials could be directly correlated to species observed on the MOF-derived and traditional oxides. In addition, the adsorbed species on the MOF-derived oxides differed from traditional oxides due to their different morphology and retained porosity. SEM and TEM images taken before and after CO2/SO2 adsorption experiments revealed degradation of all materials giving visual insight into the degradation mechanism after acid gas exposure. This study advances the understanding of acid gas adsorption on MOFs by correlation of adsorbed species with MOF-derived and traditional metal oxides.

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Role of defects and metal coordination on adsorption of acid gases in MOFs and metal oxides: An in situ IR spectroscopic study

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