@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",
pages = "8522--8529",
journal = "Chemistry of Materials",
issn = "0897-4756",
publisher = "American Chemical Society",
number = "19",
}