Supramolecular Porous Assemblies of Atomically Precise Catalytically Active Cerium-Based Clusters

Megan C. Wasson; Xuan Zhang; Ken Ichi Otake; Andrew S. Rosen; Selim Alayoglu; Matthew D. Krzyaniak; Zhijie Chen; Louis R. Redfern; Lee Robison; Florencia A. Son; Yongwei Chen; Timur Islamoglu; Justin M. Notestein; Randall Q. Snurr; Michael R. Wasielewski; Omar K. Farha

doi:10.1021/acs.chemmater.0c02740

Supramolecular Porous Assemblies of Atomically Precise Catalytically Active Cerium-Based Clusters

Megan C. Wasson, Xuan Zhang, Ken Ichi Otake, Andrew S. Rosen, Selim Alayoglu, Matthew D. Krzyaniak, Zhijie Chen, Louis R. Redfern, Lee Robison, Florencia A. Son, Yongwei Chen, Timur Islamoglu, Justin M. Notestein, Randall Q. Snurr, Michael R. Wasielewski, Omar K. Farha

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

34 Scopus citations

Abstract

Atomically precise metallic clusters offer total structural information lacking in metal oxide and nanoparticle catalysts. However, their use as heterogeneous catalysts requires accessible and robust catalytic sites, yet directing clusters into ordered and porous assemblies through functional control remains elusive. Herein, we report a supramolecular strategy to induce permanent porosity within assemblies of two cerium oxide clusters through the capping ligands used. Single-crystal X-ray crystallography and density functional theory calculations revealed cluster assemblies with accessible channels, while adsorption isotherms showed permanent porosity. The clusters exhibited a bulk modulus >5 GPa in variable pressure diffraction studies. X-ray photoelectron spectroscopy, electron paramagnetic resonance spectroscopy, and Raman spectroscopy demonstrated mixed valency (Ce3+/Ce4+) and oxygen vacancies in the clusters. We benchmarked catalytic activities through the photooxidation of 2-propanol.

Original language	English (US)
Pages (from-to)	8522-8529
Number of pages	8
Journal	Chemistry of Materials
Volume	32
Issue number	19
DOIs	https://doi.org/10.1021/acs.chemmater.0c02740
State	Published - Oct 13 2020
Externally published	Yes

All Science Journal Classification (ASJC) codes

General Chemistry
General Chemical Engineering
Materials Chemistry

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Wasson, M. C., Zhang, X., Otake, K. I., Rosen, A. S., Alayoglu, S., Krzyaniak, M. D., Chen, Z., Redfern, L. R., Robison, L., Son, F. A., Chen, Y., Islamoglu, T., Notestein, J. M., Snurr, R. Q., Wasielewski, M. R., & Farha, O. K. (2020). Supramolecular Porous Assemblies of Atomically Precise Catalytically Active Cerium-Based Clusters. Chemistry of Materials, 32(19), 8522-8529. https://doi.org/10.1021/acs.chemmater.0c02740

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title = "Supramolecular Porous Assemblies of Atomically Precise Catalytically Active Cerium-Based Clusters",

abstract = "Atomically precise metallic clusters offer total structural information lacking in metal oxide and nanoparticle catalysts. However, their use as heterogeneous catalysts requires accessible and robust catalytic sites, yet directing clusters into ordered and porous assemblies through functional control remains elusive. Herein, we report a supramolecular strategy to induce permanent porosity within assemblies of two cerium oxide clusters through the capping ligands used. Single-crystal X-ray crystallography and density functional theory calculations revealed cluster assemblies with accessible channels, while adsorption isotherms showed permanent porosity. The clusters exhibited a bulk modulus >5 GPa in variable pressure diffraction studies. X-ray photoelectron spectroscopy, electron paramagnetic resonance spectroscopy, and Raman spectroscopy demonstrated mixed valency (Ce3+/Ce4+) and oxygen vacancies in the clusters. We benchmarked catalytic activities through the photooxidation of 2-propanol.",

author = "Wasson, {Megan C.} and Xuan Zhang and Otake, {Ken Ichi} and Rosen, {Andrew S.} and Selim Alayoglu and Krzyaniak, {Matthew D.} and Zhijie Chen and Redfern, {Louis R.} and Lee Robison and Son, {Florencia A.} and Yongwei Chen and Timur Islamoglu and Notestein, {Justin M.} and Snurr, {Randall Q.} and Wasielewski, {Michael R.} and Farha, {Omar K.}",

note = "Publisher Copyright: Copyright {\textcopyright} 2020 American Chemical Society.",

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doi = "10.1021/acs.chemmater.0c02740",

language = "English (US)",

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Wasson, MC, Zhang, X, Otake, KI, Rosen, AS, Alayoglu, S, Krzyaniak, MD, Chen, Z, Redfern, LR, Robison, L, Son, FA, Chen, Y, Islamoglu, T, Notestein, JM, Snurr, RQ, Wasielewski, MR & Farha, OK 2020, 'Supramolecular Porous Assemblies of Atomically Precise Catalytically Active Cerium-Based Clusters', Chemistry of Materials, vol. 32, no. 19, pp. 8522-8529. https://doi.org/10.1021/acs.chemmater.0c02740

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T1 - Supramolecular Porous Assemblies of Atomically Precise Catalytically Active Cerium-Based Clusters

AU - Wasson, Megan C.

AU - Zhang, Xuan

AU - Otake, Ken Ichi

AU - Rosen, Andrew S.

AU - Alayoglu, Selim

AU - Krzyaniak, Matthew D.

AU - Chen, Zhijie

AU - Redfern, Louis R.

AU - Robison, Lee

AU - Son, Florencia A.

AU - Chen, Yongwei

AU - Islamoglu, Timur

AU - Notestein, Justin M.

AU - Snurr, Randall Q.

AU - Wasielewski, Michael R.

AU - Farha, Omar K.

PY - 2020/10/13

Y1 - 2020/10/13

N2 - Atomically precise metallic clusters offer total structural information lacking in metal oxide and nanoparticle catalysts. However, their use as heterogeneous catalysts requires accessible and robust catalytic sites, yet directing clusters into ordered and porous assemblies through functional control remains elusive. Herein, we report a supramolecular strategy to induce permanent porosity within assemblies of two cerium oxide clusters through the capping ligands used. Single-crystal X-ray crystallography and density functional theory calculations revealed cluster assemblies with accessible channels, while adsorption isotherms showed permanent porosity. The clusters exhibited a bulk modulus >5 GPa in variable pressure diffraction studies. X-ray photoelectron spectroscopy, electron paramagnetic resonance spectroscopy, and Raman spectroscopy demonstrated mixed valency (Ce3+/Ce4+) and oxygen vacancies in the clusters. We benchmarked catalytic activities through the photooxidation of 2-propanol.

AB - Atomically precise metallic clusters offer total structural information lacking in metal oxide and nanoparticle catalysts. However, their use as heterogeneous catalysts requires accessible and robust catalytic sites, yet directing clusters into ordered and porous assemblies through functional control remains elusive. Herein, we report a supramolecular strategy to induce permanent porosity within assemblies of two cerium oxide clusters through the capping ligands used. Single-crystal X-ray crystallography and density functional theory calculations revealed cluster assemblies with accessible channels, while adsorption isotherms showed permanent porosity. The clusters exhibited a bulk modulus >5 GPa in variable pressure diffraction studies. X-ray photoelectron spectroscopy, electron paramagnetic resonance spectroscopy, and Raman spectroscopy demonstrated mixed valency (Ce3+/Ce4+) and oxygen vacancies in the clusters. We benchmarked catalytic activities through the photooxidation of 2-propanol.

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ER -

Supramolecular Porous Assemblies of Atomically Precise Catalytically Active Cerium-Based Clusters

Abstract

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