Addressing the characterisation challenge to understand catalysis in MOFs: the case of nanoscale Cu supported in NU-1000
Abstract
Here, we explore the dynamic structure and reactivity of Cu species supported on NU-1000. By combining pair distribution function (PDF) analysis and difference envelope density (DED) analysis ofin situsynchrotron-based X-ray scattering data, we simultaneously probe the local structure of supported Cu-species, their distribution within NU-1000 and distortions of the NU-1000 lattice under conditions relevant to catalysis and catalyst activation. Our analyses show that atomic layer deposition (ALD) of Cu in NU-1000 (Cu-AIM) leads to the formation of Cu-oxo clusters within the small pores that connect the triangular and hexagonal channels. Exposure of Cu-AIM to a reducing atmosphere at 200 °C produces metallic Cu0of two distinct particle sizes: ~4 nm nanoparticles and small sub-nanometer clusters. The size of these nanoparticles appears to be constrained by NU-1000 pore dimensions, with evidence of the sub-nanometer clusters being bound within the triangular channels flanked by pyrene rings. This supported Cu0–NU-1000 system is catalytically active for gas-phase ethylene hydrogenation. Exposure of the catalyst to oxidative atmosphere re-oxidises the Cu species to a Cu2O cuprite phase. The dynamic restructuring of the system in different chemical environments underscores the importance of probing these systemsin situ.
- Authors:
-
[2];
[1];
[1]
- Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
- Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry
- Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry; King Abdulaziz Univ., Jeddah (Saudi Arabia). Dept. of Chemistry
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States); Energy Frontier Research Centers (EFRC) (United States). Energy Frontier Research Center for Inorganometallic Catalyst Design (ICDC)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1393892
- Grant/Contract Number:
- AC02-06CH11357; SC0012702
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Faraday Discussions
- Additional Journal Information:
- Journal Volume: 201; Journal ID: ISSN 1359-6640
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Platero-Prats, Ana E., Li, Zhanyong, Gallington, Leighanne C., Peters, Aaron W., Hupp, Joseph T., Farha, Omar K., and Chapman, Karena W. Addressing the characterisation challenge to understand catalysis in MOFs: the case of nanoscale Cu supported in NU-1000. United States: N. p., 2017.
Web. doi:10.1039/c7fd00110j.
Platero-Prats, Ana E., Li, Zhanyong, Gallington, Leighanne C., Peters, Aaron W., Hupp, Joseph T., Farha, Omar K., & Chapman, Karena W. Addressing the characterisation challenge to understand catalysis in MOFs: the case of nanoscale Cu supported in NU-1000. United States. https://doi.org/10.1039/c7fd00110j
Platero-Prats, Ana E., Li, Zhanyong, Gallington, Leighanne C., Peters, Aaron W., Hupp, Joseph T., Farha, Omar K., and Chapman, Karena W. Mon .
"Addressing the characterisation challenge to understand catalysis in MOFs: the case of nanoscale Cu supported in NU-1000". United States. https://doi.org/10.1039/c7fd00110j. https://www.osti.gov/servlets/purl/1393892.
@article{osti_1393892,
title = {Addressing the characterisation challenge to understand catalysis in MOFs: the case of nanoscale Cu supported in NU-1000},
author = {Platero-Prats, Ana E. and Li, Zhanyong and Gallington, Leighanne C. and Peters, Aaron W. and Hupp, Joseph T. and Farha, Omar K. and Chapman, Karena W.},
abstractNote = {Here, we explore the dynamic structure and reactivity of Cu species supported on NU-1000. By combining pair distribution function (PDF) analysis and difference envelope density (DED) analysis ofin situsynchrotron-based X-ray scattering data, we simultaneously probe the local structure of supported Cu-species, their distribution within NU-1000 and distortions of the NU-1000 lattice under conditions relevant to catalysis and catalyst activation. Our analyses show that atomic layer deposition (ALD) of Cu in NU-1000 (Cu-AIM) leads to the formation of Cu-oxo clusters within the small pores that connect the triangular and hexagonal channels. Exposure of Cu-AIM to a reducing atmosphere at 200 °C produces metallic Cu0of two distinct particle sizes: ~4 nm nanoparticles and small sub-nanometer clusters. The size of these nanoparticles appears to be constrained by NU-1000 pore dimensions, with evidence of the sub-nanometer clusters being bound within the triangular channels flanked by pyrene rings. This supported Cu0–NU-1000 system is catalytically active for gas-phase ethylene hydrogenation. Exposure of the catalyst to oxidative atmosphere re-oxidises the Cu species to a Cu2O cuprite phase. The dynamic restructuring of the system in different chemical environments underscores the importance of probing these systemsin situ.},
doi = {10.1039/c7fd00110j},
journal = {Faraday Discussions},
number = ,
volume = 201,
place = {United States},
year = {Mon Apr 03 00:00:00 EDT 2017},
month = {Mon Apr 03 00:00:00 EDT 2017}
}
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