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Title: In situ hydrogenation and decarboxylation of oleic acid into heptadecane over a Cu–Ni alloy catalyst using methanol as a hydrogen carrier

In this paper, supported Cu–Ni bimetallic catalysts were synthesized and evaluated for the in situ hydrogenation and decarboxylation of oleic acid using methanol as a hydrogen donor. The supported Cu–Ni alloy exhibited a significant improvement in both activity and selectivity towards the production of heptadecane in comparison with monometallic Cu and Ni based catalysts. The formation of the Cu–Ni alloy is demonstrated by high-angle annular dark-field scanning transmission electron microscopy (HADDF-STEM), energy dispersive X-ray spectroscopy (EDS-mapping), X-ray diffraction (XRD) and temperature programmed reduction (TPR). A partially oxidized Cu in the Cu–Ni alloy is revealed by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) following CO adsorption and X-ray photoelectron spectroscopy (XPS). The temperature programmed desorption of ethylene and propane (ethylene/propane-TPD) suggested that the formation of the Cu–Ni alloy inhibited the cracking of C–C bonds compared to Ni, and remarkably increased the selectivity to heptadecane. The temperature programmed desorption of acetic acid (acetic acid-TPD) indicated that the bimetallic Cu–Ni alloy and Ni catalysts had a stronger adsorption of acetic acid than that of the Cu catalyst. Finally, the formation of the Cu–Ni alloy and a partially oxidized Cu facilitates the decarboxylation reaction and inhibits the cracking reaction of C–C bonds, leading tomore » enhanced catalytic activity and selectivity.« less
Authors:
ORCiD logo [1] ;  [1] ;  [1] ; ORCiD logo [2] ;  [1] ;  [3] ; ORCiD logo [4] ; ORCiD logo [5]
  1. Zhejiang Univ., Hangzhou (China). Key Lab. of Biomass Chemical Engineering of Ministry of Education. College of Chemical and Biological Engineering
  2. Nanjing Tech Univ. (China). State Key Lab. of Materials-Oriented Chemical Engineering. College of Biotechnology and Pharmaceutical Engineering
  3. Zhejiang Univ., Hangzhou (China). Key Lab. of Biomass Chemical Engineering of Ministry of Education. College of Chemical and Biological Engineering; Nanjing Tech Univ. (China). State Key Lab. of Materials-Oriented Chemical Engineering. College of Biotechnology and Pharmaceutical Engineering
  4. Zhejiang Univ., Hangzhou (China). Key Lab. of Biomass Chemical Engineering of Ministry of Education. College of Chemical and Biological Engineering; Columbia Univ., New York, NY (United States). Dept. of Chemical Engineering; Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Dept.
  5. Columbia Univ., New York, NY (United States). Dept. of Chemical Engineering; Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Dept.
Publication Date:
Report Number(s):
BNL-203317-2018-JAAM
Journal ID: ISSN 1463-9262
Grant/Contract Number:
SC0012704; 21436007; 21676243; LR17B060002; LZ14B060002
Type:
Accepted Manuscript
Journal Name:
Green Chemistry
Additional Journal Information:
Journal Volume: 20; Journal Issue: 1; Journal ID: ISSN 1463-9262
Publisher:
Royal Society of Chemistry
Research Org:
Zhejiang Univ., Hangzhou (China); Nanjing Tech Univ. (China); Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org:
USDOE; BNL Laboratory Directed Research and Development (LDRD) Program; National Natural Science Foundation of China (NNSFC); Zhejiang Provincial Natural Science Foundation of China; China Scholarship Council
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1425099

Zhang, Zihao, Yang, Qiwei, Chen, Hao, Chen, Kequan, Lu, Xiuyang, Ouyang, Pingkai, Fu, Jie, and Chen, Jingguang G. In situ hydrogenation and decarboxylation of oleic acid into heptadecane over a Cu–Ni alloy catalyst using methanol as a hydrogen carrier. United States: N. p., Web. doi:10.1039/C7GC02774E.
Zhang, Zihao, Yang, Qiwei, Chen, Hao, Chen, Kequan, Lu, Xiuyang, Ouyang, Pingkai, Fu, Jie, & Chen, Jingguang G. In situ hydrogenation and decarboxylation of oleic acid into heptadecane over a Cu–Ni alloy catalyst using methanol as a hydrogen carrier. United States. doi:10.1039/C7GC02774E.
Zhang, Zihao, Yang, Qiwei, Chen, Hao, Chen, Kequan, Lu, Xiuyang, Ouyang, Pingkai, Fu, Jie, and Chen, Jingguang G. 2017. "In situ hydrogenation and decarboxylation of oleic acid into heptadecane over a Cu–Ni alloy catalyst using methanol as a hydrogen carrier". United States. doi:10.1039/C7GC02774E. https://www.osti.gov/servlets/purl/1425099.
@article{osti_1425099,
title = {In situ hydrogenation and decarboxylation of oleic acid into heptadecane over a Cu–Ni alloy catalyst using methanol as a hydrogen carrier},
author = {Zhang, Zihao and Yang, Qiwei and Chen, Hao and Chen, Kequan and Lu, Xiuyang and Ouyang, Pingkai and Fu, Jie and Chen, Jingguang G.},
abstractNote = {In this paper, supported Cu–Ni bimetallic catalysts were synthesized and evaluated for the in situ hydrogenation and decarboxylation of oleic acid using methanol as a hydrogen donor. The supported Cu–Ni alloy exhibited a significant improvement in both activity and selectivity towards the production of heptadecane in comparison with monometallic Cu and Ni based catalysts. The formation of the Cu–Ni alloy is demonstrated by high-angle annular dark-field scanning transmission electron microscopy (HADDF-STEM), energy dispersive X-ray spectroscopy (EDS-mapping), X-ray diffraction (XRD) and temperature programmed reduction (TPR). A partially oxidized Cu in the Cu–Ni alloy is revealed by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) following CO adsorption and X-ray photoelectron spectroscopy (XPS). The temperature programmed desorption of ethylene and propane (ethylene/propane-TPD) suggested that the formation of the Cu–Ni alloy inhibited the cracking of C–C bonds compared to Ni, and remarkably increased the selectivity to heptadecane. The temperature programmed desorption of acetic acid (acetic acid-TPD) indicated that the bimetallic Cu–Ni alloy and Ni catalysts had a stronger adsorption of acetic acid than that of the Cu catalyst. Finally, the formation of the Cu–Ni alloy and a partially oxidized Cu facilitates the decarboxylation reaction and inhibits the cracking reaction of C–C bonds, leading to enhanced catalytic activity and selectivity.},
doi = {10.1039/C7GC02774E},
journal = {Green Chemistry},
number = 1,
volume = 20,
place = {United States},
year = {2017},
month = {10}
}

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