Spectroscopic characterization of a highly selective NiCu3/C hydrodeoxygenation catalyst
Abstract
Here, the design of selective and active heterogeneous catalysts for the hydrodeoxygenation (HDO) of biomass-derived platform molecules requires understanding of the catalyst structure under reaction conditions. In this work, we design, build and qualify an operando X-ray absorption (XAS) cell to characterize a highly selective NiCu3 catalyst under HDO conditions. We complement XAS measurements with X-ray photoelectron spectroscopy (XPS) studies and theoretical calculations to show that in bimetallic NiCu catalysts, Ni and Cu are segregated. The as-made catalysts are mixed oxides, with a NiO shell over a NiCuOx core. The core becomes a partially reduced metal alloy after treatment with hydrogen at temperatures below 473 K, while the shell becomes fully reduced at higher treatment temperatures. As a result, the liquid-phase reaction results in gradual reoxidation of the catalyst to a core–shell mixed oxide, in which the Cu in the core is predominately Cu(I) and the Ni shell is predominately Ni(II).
- Authors:
-
[1];
[2];
[1];
[2];
[5];
[1]
- Univ. of Delaware, Newark, DE (United States)
- Univ. of Delaware, Newark, DE (United States); Univ. of Pennsylvania, Philadelphia, PA (United States)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Univ. of Pennsylvania, Philadelphia, PA (United States)
- Univ. of Delaware, Newark, DE (United States); Brookhaven National Lab. (BNL), Upton, NY (United States); Columbia Univ., New York, NY (United States)
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Catalysis Center for Energy Innovation (CCEI); Brookhaven National Lab. (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1487252
- Report Number(s):
- BNL-209752-2018-JAAM
Journal ID: ISSN 2044-4753; CSTAGD
- Grant/Contract Number:
- SC0012704
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Catalysis Science and Technology
- Additional Journal Information:
- Journal Volume: 8; Journal Issue: 23; Journal ID: ISSN 2044-4753
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
Citation Formats
Goulas, Konstantinos A., Lee, Jennifer D., Zheng, Weiqing, Lym, Jonathan, Yao, Siyu, Oh, Deborah S., Wang, Cong, Gorte, Raymond J., Chen, Jingguang G., Murray, Christopher B., and Vlachos, Dionisios G. Spectroscopic characterization of a highly selective NiCu3/C hydrodeoxygenation catalyst. United States: N. p., 2018.
Web. doi:10.1039/C8CY01280F.
Goulas, Konstantinos A., Lee, Jennifer D., Zheng, Weiqing, Lym, Jonathan, Yao, Siyu, Oh, Deborah S., Wang, Cong, Gorte, Raymond J., Chen, Jingguang G., Murray, Christopher B., & Vlachos, Dionisios G. Spectroscopic characterization of a highly selective NiCu3/C hydrodeoxygenation catalyst. United States. https://doi.org/10.1039/C8CY01280F
Goulas, Konstantinos A., Lee, Jennifer D., Zheng, Weiqing, Lym, Jonathan, Yao, Siyu, Oh, Deborah S., Wang, Cong, Gorte, Raymond J., Chen, Jingguang G., Murray, Christopher B., and Vlachos, Dionisios G. Wed .
"Spectroscopic characterization of a highly selective NiCu3/C hydrodeoxygenation catalyst". United States. https://doi.org/10.1039/C8CY01280F. https://www.osti.gov/servlets/purl/1487252.
@article{osti_1487252,
title = {Spectroscopic characterization of a highly selective NiCu3/C hydrodeoxygenation catalyst},
author = {Goulas, Konstantinos A. and Lee, Jennifer D. and Zheng, Weiqing and Lym, Jonathan and Yao, Siyu and Oh, Deborah S. and Wang, Cong and Gorte, Raymond J. and Chen, Jingguang G. and Murray, Christopher B. and Vlachos, Dionisios G.},
abstractNote = {Here, the design of selective and active heterogeneous catalysts for the hydrodeoxygenation (HDO) of biomass-derived platform molecules requires understanding of the catalyst structure under reaction conditions. In this work, we design, build and qualify an operando X-ray absorption (XAS) cell to characterize a highly selective NiCu3 catalyst under HDO conditions. We complement XAS measurements with X-ray photoelectron spectroscopy (XPS) studies and theoretical calculations to show that in bimetallic NiCu catalysts, Ni and Cu are segregated. The as-made catalysts are mixed oxides, with a NiO shell over a NiCuOx core. The core becomes a partially reduced metal alloy after treatment with hydrogen at temperatures below 473 K, while the shell becomes fully reduced at higher treatment temperatures. As a result, the liquid-phase reaction results in gradual reoxidation of the catalyst to a core–shell mixed oxide, in which the Cu in the core is predominately Cu(I) and the Ni shell is predominately Ni(II).},
doi = {10.1039/C8CY01280F},
journal = {Catalysis Science and Technology},
number = 23,
volume = 8,
place = {United States},
year = {Wed Oct 24 00:00:00 EDT 2018},
month = {Wed Oct 24 00:00:00 EDT 2018}
}
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Cited by: 9 works
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Figures / Tables:
Figure 1: (A) Cu K edge and (B) Ni K edge XANES spectra of as-prepared NiCu3/C catalyst.
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