Zirconium Modification Promotes Catalytic Activity of a Single-Site Cobalt Heterogeneous Catalyst for Propane Dehydrogenation
Abstract
The effect of Zr modification on the catalytic activity of Co/SiO2 was investigated for nonoxidative propane dehydrogenation. Isolated Zr on SiO2 surface sites were prepared by organometallic synthesis using Zr(OtBu)4 as a precursor. The resulting Zr/SiO2 support was functionalized with Co2+ ions via strong electrostatic adsorption. Spectroscopic (diffuse reflectance infrared Fourier transform spectroscopy, UV-vis, electron paramagnetic resonance) and microscopic characterization (transmission electron microscopy, scanning transition electron microscopy) results are consistent with single-site cobalt that preferentially associates with the mono-dispersed Zr at a variety of loadings and Co/Zr ratios. The oxidation state of Co in the asprepared Co/SiO2 and Co-Zr/SiO2 was both +2 with tetrahedral and octahedral geometries, respectively. In situ X-ray absorption near edge structure and extended Xray absorption fine structure results confirmed that the oxidation state of Co remained as +2 under reaction condition for both Co/SiO2 and Co-Zr/SiO2 samples and both catalysts have tetrahedral Co2+ as the active catalyst. Despite similar Co coordination environments, the catalytic activity and selectivity was significantly improved by the Zr modification of the silica support versus Co/SiO2. This was attributed to the change in oxygen donor ability and Co-O bond strength of the ΞSiO-Zr-O sites of Co-Zr/SiO2 compared with the Ξ-SiO- ligands inmore »
- Authors:
-
;
;
;
[1]
- Department of Chemistry, Illinois Institute of Technology, Chicago, Illinois 60616, United States
- Publication Date:
- Research Org.:
- Illinois Institute of Technology, Chicago, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1470601
- Alternate Identifier(s):
- OSTI ID: 1508627
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Published Article
- Journal Name:
- ACS Omega
- Additional Journal Information:
- Journal Name: ACS Omega Journal Volume: 3 Journal Issue: 9; Journal ID: ISSN 2470-1343
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Zhao, Yiqing, Sohn, Hyuntae, Hu, Bo, Niklas, Jens, Poluektov, Oleg G., Tian, Jun, Delferro, Massimiliano, and Hock, Adam S. Zirconium Modification Promotes Catalytic Activity of a Single-Site Cobalt Heterogeneous Catalyst for Propane Dehydrogenation. United States: N. p., 2018.
Web. doi:10.1021/acsomega.8b00862.
Zhao, Yiqing, Sohn, Hyuntae, Hu, Bo, Niklas, Jens, Poluektov, Oleg G., Tian, Jun, Delferro, Massimiliano, & Hock, Adam S. Zirconium Modification Promotes Catalytic Activity of a Single-Site Cobalt Heterogeneous Catalyst for Propane Dehydrogenation. United States. https://doi.org/10.1021/acsomega.8b00862
Zhao, Yiqing, Sohn, Hyuntae, Hu, Bo, Niklas, Jens, Poluektov, Oleg G., Tian, Jun, Delferro, Massimiliano, and Hock, Adam S. Thu .
"Zirconium Modification Promotes Catalytic Activity of a Single-Site Cobalt Heterogeneous Catalyst for Propane Dehydrogenation". United States. https://doi.org/10.1021/acsomega.8b00862.
@article{osti_1470601,
title = {Zirconium Modification Promotes Catalytic Activity of a Single-Site Cobalt Heterogeneous Catalyst for Propane Dehydrogenation},
author = {Zhao, Yiqing and Sohn, Hyuntae and Hu, Bo and Niklas, Jens and Poluektov, Oleg G. and Tian, Jun and Delferro, Massimiliano and Hock, Adam S.},
abstractNote = {The effect of Zr modification on the catalytic activity of Co/SiO2 was investigated for nonoxidative propane dehydrogenation. Isolated Zr on SiO2 surface sites were prepared by organometallic synthesis using Zr(OtBu)4 as a precursor. The resulting Zr/SiO2 support was functionalized with Co2+ ions via strong electrostatic adsorption. Spectroscopic (diffuse reflectance infrared Fourier transform spectroscopy, UV-vis, electron paramagnetic resonance) and microscopic characterization (transmission electron microscopy, scanning transition electron microscopy) results are consistent with single-site cobalt that preferentially associates with the mono-dispersed Zr at a variety of loadings and Co/Zr ratios. The oxidation state of Co in the asprepared Co/SiO2 and Co-Zr/SiO2 was both +2 with tetrahedral and octahedral geometries, respectively. In situ X-ray absorption near edge structure and extended Xray absorption fine structure results confirmed that the oxidation state of Co remained as +2 under reaction condition for both Co/SiO2 and Co-Zr/SiO2 samples and both catalysts have tetrahedral Co2+ as the active catalyst. Despite similar Co coordination environments, the catalytic activity and selectivity was significantly improved by the Zr modification of the silica support versus Co/SiO2. This was attributed to the change in oxygen donor ability and Co-O bond strength of the ΞSiO-Zr-O sites of Co-Zr/SiO2 compared with the Ξ-SiO- ligands in Co/SiO2. These results show that tuning of the support SiO2 oxygen donation ability by use of an anchoring site (e.g., Ξ-SiO-Zr-O-) can be used to alter both rate and selectivity of propane dehydrogenation with single-site heterogeneous catalysts. These results also show some preference for Co2+ active sites to associate with Ξ-SiO-Zr-O- sites over Ξ-SiO-.},
doi = {10.1021/acsomega.8b00862},
journal = {ACS Omega},
number = 9,
volume = 3,
place = {United States},
year = {Thu Sep 13 00:00:00 EDT 2018},
month = {Thu Sep 13 00:00:00 EDT 2018}
}
https://doi.org/10.1021/acsomega.8b00862
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Works referencing / citing this record:
Cobalt‐Based Catalyst Supported on Different Morphologies of Alumina for Non‐oxidative Propane Dehydrogenation: Effect of Metal Support Interaction and Lewis Acidic Sites
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