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^*

^*Corresponding author for this work

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

18 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

ASJC Scopus subject areas

Chemistry(all)
Chemical Engineering(all)
Materials Chemistry

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10.1021/acs.chemmater.0c02740

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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

@article{fcc471d52f0e45af8f2b3f10bec95408,

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 = "Funding Information: The authors gratefully acknowledge the Northwestern University Institute for Catalysis in Energy Processes (ICEP), funded by the DOE, Office of Basic Energy Sciences (award number DE-FG02-03ER15457). M.C.W. is supported by the NSF Graduate Research Fellowship under grant DGE-1842165. A.S.R. was supported by a fellowship award through the National Defense Science and Engineering Graduate (NDSEG) Fellowship Program and a Ryan Fellowship through the International Institute for Nanotechnology at Northwestern University. A.S.R. and R.Q.S. acknowledge computing support through the Extreme Science and Engineering Discovery Environment (XSEDE) via allocation CTS180057 supported by the National Science Foundation (grant number ACI-1548562). This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract no. DE-AC02-06CH11357. This work made use of the IMSERC X-ray facility at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the State of Illinois, and the International Institute for Nanotechnology (IIN). Also, this work made use of the Keck-II facility of Northwestern University{\textquoteright}s NUANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-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. The REACT Facility of the Northwestern University Center for Catalysis and Surface Science is supported by a grant from the DOE (DE-SC0001329). This work was supported by the DOE, Office of Science, Office of Basic Energy Sciences Award DE-SC0019356 (M.R.W.). Publisher Copyright: Copyright {\textcopyright} 2020 American Chemical Society.",

year = "2020",

month = oct,

day = "13",

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

language = "English (US)",

volume = "32",

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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

TY - JOUR

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.

N1 - Funding Information: The authors gratefully acknowledge the Northwestern University Institute for Catalysis in Energy Processes (ICEP), funded by the DOE, Office of Basic Energy Sciences (award number DE-FG02-03ER15457). M.C.W. is supported by the NSF Graduate Research Fellowship under grant DGE-1842165. A.S.R. was supported by a fellowship award through the National Defense Science and Engineering Graduate (NDSEG) Fellowship Program and a Ryan Fellowship through the International Institute for Nanotechnology at Northwestern University. A.S.R. and R.Q.S. acknowledge computing support through the Extreme Science and Engineering Discovery Environment (XSEDE) via allocation CTS180057 supported by the National Science Foundation (grant number ACI-1548562). This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract no. DE-AC02-06CH11357. This work made use of the IMSERC X-ray facility at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the State of Illinois, and the International Institute for Nanotechnology (IIN). Also, this work made use of the Keck-II facility of Northwestern University’s NUANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-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. The REACT Facility of the Northwestern University Center for Catalysis and Surface Science is supported by a grant from the DOE (DE-SC0001329). This work was supported by the DOE, Office of Science, Office of Basic Energy Sciences Award DE-SC0019356 (M.R.W.). Publisher Copyright: Copyright © 2020 American Chemical Society.

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.

UR - http://www.scopus.com/inward/record.url?scp=85092044844&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85092044844&partnerID=8YFLogxK

U2 - 10.1021/acs.chemmater.0c02740

DO - 10.1021/acs.chemmater.0c02740

M3 - Article

AN - SCOPUS:85092044844

SN - 0897-4756

VL - 32

SP - 8522

EP - 8529

JO - Chemistry of Materials

JF - Chemistry of Materials

IS - 19

ER -

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

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CSD 2003383: Experimental Crystal Structure Determination

CCDC 2000674: Experimental Crystal Structure Determination

CCDC 2179839: Experimental Crystal Structure Determination

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

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ASJC Scopus subject areas

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CSD 2003383: Experimental Crystal Structure Determination

CCDC 2000674: Experimental Crystal Structure Determination

CCDC 2179839: Experimental Crystal Structure Determination

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