Precise Modulation of CO2 Sorption in Ti8Ce2-Oxo Clusters: Elucidating Lewis Acidity of the Ce Metal Sites and Structural Flexibility

Xingjie Wang; Haomiao Xie; Debabrata Sengupta; Fanrui Sha; Ken Ichi Otake; Yongwei Chen; Karam B. Idrees; Kent O. Kirlikovali; Florencia A. Son; Meng Wang; Junli Ren; Justin M. Notestein; Susumu Kitagawa; Omar K. Farha

doi:10.1021/jacs.4c01092

Precise Modulation of CO₂ Sorption in Ti₈Ce₂-Oxo Clusters: Elucidating Lewis Acidity of the Ce Metal Sites and Structural Flexibility

Xingjie Wang^*, Haomiao Xie, Debabrata Sengupta, Fanrui Sha, Ken Ichi Otake, Yongwei Chen, Karam B. Idrees, Kent O. Kirlikovali, Florencia A. Son, Meng Wang, Junli Ren, Justin M. Notestein, Susumu Kitagawa^*, Omar K. Farha^*

^*Corresponding author for this work

Chemistry

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

4 Scopus citations

Abstract

Investigating the structure-property correlation in porous materials is a fundamental and consistent focus in various scientific domains, especially within sorption research. Metal oxide clusters with capping ligands, characterized by intrinsic cavities formed through specific solid-state packing, demonstrate significant potential as versatile platforms for sorption investigations due to their precisely tunable atomic structures and inherent long-range order. This study presents a series of Ti₈Ce₂-oxo clusters with subtle variations in coordinated linkers and explores their sorption behavior. Notably, Ti₈Ce₂-BA (BA denotes benzoic acid) manifests a distinctive two-step profile during the CO₂ adsorption, accompanied by a hysteresis loop. This observation marks a new instance within the metal oxide cluster field. Of intrigue, the presence of unsaturated Ce(IV) sites was found to be correlated with the stepped sorption property. Moreover, the introduction of an electrophilic fluorine atom, positioned ortho or para to the benzoic acid, facilitated precise control over gate pressure and stepped sorption quantities. Advanced in situ techniques systematically unraveled the underlying mechanism behind this unique sorption behavior. The findings elucidate that robust Lewis base-acid interactions are established between the CO₂ molecules and Ce ions, consequently altering the conformation of coordinated linkers. Conversely, the F atoms primarily contribute to gate pressure variation by influencing the Lewis acidity of the Ce sites. This research advances the understanding in fabricating metal-oxo clusters with structural flexibility and provides profound insights into their host-guest interaction motifs. These insights hold substantial promise across diverse fields and offer valuable guidance for future adsorbent designs grounded in fundamental theories of structure-property relationships.

Original language	English (US)
Pages (from-to)	15130-15142
Number of pages	13
Journal	Journal of the American Chemical Society
Volume	146
Issue number	22
DOIs	https://doi.org/10.1021/jacs.4c01092
State	Published - Jun 5 2024

Funding

This work was supported as part of the Northwestern University Institute for Catalysis in Energy Processes (ICEP), funded by the DOE, Office of Basic Energy Sciences (award number DE-FG02-03ER15457) for the cluster preparation and characterizations performed at Northwestern University. X.W. gratefully acknowledges support from State Key Laboratory of Pulp and Paper Engineering (202303), Guangzhou Municipal Science and Technology Bureau (no. 2024A04J3650). O.K.F. acknowledges research support from NSF (CBET 2119433), U.S. Department of Energy (DOE) Office of Science, Basic Energy Sciences Program for separation studies (DE-FG02-08ER15967) for the sorption study of this work, and the Catalyst Design for Decarbonization Center, an Energy Frontier Research Center also funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award No. DE-SC0023383. F.S. gratefully acknowledges support from the Ryan Fellowship and the International Institute for Nanotechnology at Northwestern University. F.A.S. also acknowledges the Ryan Fellowship and the International Institute for Nanotechnology at Northwestern University along with the Department of Defense (DoD) through the National Defense Science & Engineering Graduate (NDSEG) Fellowship Program. This work made use of the J.B. Cohen X-ray Diffraction Facility supported by the MRSEC program of the National Science Foundation (DMR-1720139) at the Materials Research Center of Northwestern University. This work made use of Keck-II and EPIC facilities of the NUANCE Center at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF NNCI-1542205); the MRSEC program (NSF DMR-1720139) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN. This work made use of the IMSERC at Northwestern University, which has received support from the NSF (CHE-1048773 and DMR-0521267); SHyNE Resource (NSF NNCI-1542205); the State of Illinois and IIN. This work made use of the IMSERC NMR facility at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-2025633), Int. Institute of Nanotechnology, and Northwestern University.

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

Access to Document

10.1021/jacs.4c01092

Cite this

Wang, X., Xie, H., Sengupta, D., Sha, F., Otake, K. I., Chen, Y., Idrees, K. B., Kirlikovali, K. O., Son, F. A., Wang, M., Ren, J., Notestein, J. M., Kitagawa, S., & Farha, O. K. (2024). Precise Modulation of CO₂ Sorption in Ti₈Ce₂-Oxo Clusters: Elucidating Lewis Acidity of the Ce Metal Sites and Structural Flexibility. Journal of the American Chemical Society, 146(22), 15130-15142. https://doi.org/10.1021/jacs.4c01092

@article{eccf4375c53247de8316bc1d5df14f52,

title = "Precise Modulation of CO2 Sorption in Ti8Ce2-Oxo Clusters: Elucidating Lewis Acidity of the Ce Metal Sites and Structural Flexibility",

abstract = "Investigating the structure-property correlation in porous materials is a fundamental and consistent focus in various scientific domains, especially within sorption research. Metal oxide clusters with capping ligands, characterized by intrinsic cavities formed through specific solid-state packing, demonstrate significant potential as versatile platforms for sorption investigations due to their precisely tunable atomic structures and inherent long-range order. This study presents a series of Ti8Ce2-oxo clusters with subtle variations in coordinated linkers and explores their sorption behavior. Notably, Ti8Ce2-BA (BA denotes benzoic acid) manifests a distinctive two-step profile during the CO2 adsorption, accompanied by a hysteresis loop. This observation marks a new instance within the metal oxide cluster field. Of intrigue, the presence of unsaturated Ce(IV) sites was found to be correlated with the stepped sorption property. Moreover, the introduction of an electrophilic fluorine atom, positioned ortho or para to the benzoic acid, facilitated precise control over gate pressure and stepped sorption quantities. Advanced in situ techniques systematically unraveled the underlying mechanism behind this unique sorption behavior. The findings elucidate that robust Lewis base-acid interactions are established between the CO2 molecules and Ce ions, consequently altering the conformation of coordinated linkers. Conversely, the F atoms primarily contribute to gate pressure variation by influencing the Lewis acidity of the Ce sites. This research advances the understanding in fabricating metal-oxo clusters with structural flexibility and provides profound insights into their host-guest interaction motifs. These insights hold substantial promise across diverse fields and offer valuable guidance for future adsorbent designs grounded in fundamental theories of structure-property relationships.",

author = "Xingjie Wang and Haomiao Xie and Debabrata Sengupta and Fanrui Sha and Otake, {Ken Ichi} and Yongwei Chen and Idrees, {Karam B.} and Kirlikovali, {Kent O.} and Son, {Florencia A.} and Meng Wang and Junli Ren and Notestein, {Justin M.} and Susumu Kitagawa and Farha, {Omar K.}",

note = "Publisher Copyright: {\textcopyright} 2024 American Chemical Society.",

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doi = "10.1021/jacs.4c01092",

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Wang, X, Xie, H, Sengupta, D, Sha, F, Otake, KI, Chen, Y, Idrees, KB, Kirlikovali, KO, Son, FA, Wang, M, Ren, J, Notestein, JM, Kitagawa, S & Farha, OK 2024, 'Precise Modulation of CO₂ Sorption in Ti₈Ce₂-Oxo Clusters: Elucidating Lewis Acidity of the Ce Metal Sites and Structural Flexibility', Journal of the American Chemical Society, vol. 146, no. 22, pp. 15130-15142. https://doi.org/10.1021/jacs.4c01092

TY - JOUR

T1 - Precise Modulation of CO2 Sorption in Ti8Ce2-Oxo Clusters

T2 - Elucidating Lewis Acidity of the Ce Metal Sites and Structural Flexibility

AU - Wang, Xingjie

AU - Xie, Haomiao

AU - Sengupta, Debabrata

AU - Sha, Fanrui

AU - Otake, Ken Ichi

AU - Chen, Yongwei

AU - Idrees, Karam B.

AU - Kirlikovali, Kent O.

AU - Son, Florencia A.

AU - Wang, Meng

AU - Ren, Junli

AU - Notestein, Justin M.

AU - Kitagawa, Susumu

AU - Farha, Omar K.

PY - 2024/6/5

Y1 - 2024/6/5

N2 - Investigating the structure-property correlation in porous materials is a fundamental and consistent focus in various scientific domains, especially within sorption research. Metal oxide clusters with capping ligands, characterized by intrinsic cavities formed through specific solid-state packing, demonstrate significant potential as versatile platforms for sorption investigations due to their precisely tunable atomic structures and inherent long-range order. This study presents a series of Ti8Ce2-oxo clusters with subtle variations in coordinated linkers and explores their sorption behavior. Notably, Ti8Ce2-BA (BA denotes benzoic acid) manifests a distinctive two-step profile during the CO2 adsorption, accompanied by a hysteresis loop. This observation marks a new instance within the metal oxide cluster field. Of intrigue, the presence of unsaturated Ce(IV) sites was found to be correlated with the stepped sorption property. Moreover, the introduction of an electrophilic fluorine atom, positioned ortho or para to the benzoic acid, facilitated precise control over gate pressure and stepped sorption quantities. Advanced in situ techniques systematically unraveled the underlying mechanism behind this unique sorption behavior. The findings elucidate that robust Lewis base-acid interactions are established between the CO2 molecules and Ce ions, consequently altering the conformation of coordinated linkers. Conversely, the F atoms primarily contribute to gate pressure variation by influencing the Lewis acidity of the Ce sites. This research advances the understanding in fabricating metal-oxo clusters with structural flexibility and provides profound insights into their host-guest interaction motifs. These insights hold substantial promise across diverse fields and offer valuable guidance for future adsorbent designs grounded in fundamental theories of structure-property relationships.

AB - Investigating the structure-property correlation in porous materials is a fundamental and consistent focus in various scientific domains, especially within sorption research. Metal oxide clusters with capping ligands, characterized by intrinsic cavities formed through specific solid-state packing, demonstrate significant potential as versatile platforms for sorption investigations due to their precisely tunable atomic structures and inherent long-range order. This study presents a series of Ti8Ce2-oxo clusters with subtle variations in coordinated linkers and explores their sorption behavior. Notably, Ti8Ce2-BA (BA denotes benzoic acid) manifests a distinctive two-step profile during the CO2 adsorption, accompanied by a hysteresis loop. This observation marks a new instance within the metal oxide cluster field. Of intrigue, the presence of unsaturated Ce(IV) sites was found to be correlated with the stepped sorption property. Moreover, the introduction of an electrophilic fluorine atom, positioned ortho or para to the benzoic acid, facilitated precise control over gate pressure and stepped sorption quantities. Advanced in situ techniques systematically unraveled the underlying mechanism behind this unique sorption behavior. The findings elucidate that robust Lewis base-acid interactions are established between the CO2 molecules and Ce ions, consequently altering the conformation of coordinated linkers. Conversely, the F atoms primarily contribute to gate pressure variation by influencing the Lewis acidity of the Ce sites. This research advances the understanding in fabricating metal-oxo clusters with structural flexibility and provides profound insights into their host-guest interaction motifs. These insights hold substantial promise across diverse fields and offer valuable guidance for future adsorbent designs grounded in fundamental theories of structure-property relationships.

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Precise Modulation of CO₂ Sorption in Ti₈Ce₂-Oxo Clusters: Elucidating Lewis Acidity of the Ce Metal Sites and Structural Flexibility

Abstract

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ASJC Scopus subject areas

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CCDC 2302069: Experimental Crystal Structure Determination

CCDC 2303057: Experimental Crystal Structure Determination

CCDC 2302068: Experimental Crystal Structure Determination

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Precise Modulation of CO2 Sorption in Ti8Ce2-Oxo Clusters: Elucidating Lewis Acidity of the Ce Metal Sites and Structural Flexibility

Abstract

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ASJC Scopus subject areas

Access to Document

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Datasets

CCDC 2302069: Experimental Crystal Structure Determination

CCDC 2303057: Experimental Crystal Structure Determination

CCDC 2302068: Experimental Crystal Structure Determination

Cite this

Precise Modulation of CO₂ Sorption in Ti₈Ce₂-Oxo Clusters: Elucidating Lewis Acidity of the Ce Metal Sites and Structural Flexibility