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Title: 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:
ORCiD logo [1]; ORCiD logo [2];  [1]; ORCiD logo [1];  [3];  [4]; ORCiD logo [2];  [2]; ORCiD logo [5];  [2]; ORCiD logo [1]
  1. Univ. of Delaware, Newark, DE (United States)
  2. Univ. of Delaware, Newark, DE (United States); Univ. of Pennsylvania, Philadelphia, PA (United States)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
  4. Univ. of Pennsylvania, Philadelphia, PA (United States)
  5. 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) (SC-22)
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. 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., and Vlachos, Dionisios G. Wed . "Spectroscopic characterization of a highly selective NiCu3/C hydrodeoxygenation catalyst". United States. doi: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 = {2018},
month = {10}
}

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Figures / Tables:

Figure 1 Figure 1: (A) Cu K edge and (B) Ni K edge XANES spectra of as-prepared NiCu3/C catalyst.

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