Elucidating the Copper–Hägg Iron Carbide Synergistic Interactions for Selective CO Hydrogenation to Higher Alcohols
[1];
[5];
[1]
- Department of Agricultural and Biological Engineering, Mississippi State University, Mississippi State, Mississippi 39762, United States
- Key Laboratory of Coal Science and Technology of Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan, Shanxi 030024, People’s Republic of China
- School of Materials Science and Engineering, Southwest Jiaotong University, Chengdu, Sichuan 610031, People’s Republic of China
- Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Science, Beijing 100190, People’s Republic of China
- Department of Chemical and Petroleum Engineering and Department of Chemistry, University of Kansas, Lawrence, Kansas 66045, United States
- X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439, United States
CO hydrogenation to higher alcohols (C2+OH) provides a promising route to convert coal, natural gas, shale gas, and biomass feedstocks into value-added chemicals and transportation fuels. However, the development of nonprecious metal catalysts with satisfactory activity and well-defined selectivity toward C2+OH remains challenging and impedes the commercialization of this process. Here, we show that the synergistic geometric and electronic interactions dictate the activity of Cu-0-chi-Fe5C2 binary catalysts for selective CO hydrogenation to C2+OH, outperforming silica-supported precious Rh-based catalysts, by using a combination of experimental evidence from bulk, surface-sensitive, and imaging techniques collected on real and high-performance Cu-Fe binary catalytic systems coupled with density functional theory calculations. The closer is the d-band center to the Fermi level of Cu-0-chi-Fe5C2(510) surface than those of chi-Fe5C2(510) and Rh(111) surface, and the electron-rich interface of Cu-0-chi-Fe5C2(510) due to the delocalized electron transfer from Cu-0 atoms, facilitates CO activation and CO insertion into alkyl species to C-2-oxygenates at the interface of Cu-0-chi-Fe5C2(510) and thus enhances C2H5OH selectivity. Starting from the CHCO intermediate, the proposed reaction pathway for CO hydrogenation to C2H5OH on Cu-0-chi-Fe5C2(510) is CHCO + (H) -> CH2CO + (H) -> CH3CO + (H) -> CH3CHO + (H) -> CH3CH2O + (H) -> C2H5OH. This study may guide the rational design of high-performance binary catalysts made from earth-abundant metals with synergistic interactions for tuning selectivity.
- Research Organization:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Organization:
- U.S. Department of Agriculture (USDA); National Natural Science Foundation of China (NNSFC); Natural Science Foundation of Shanxi Province; USDOE Office of Science - Office of Basic Energy Sciences - Chemical Sciences, Geosciences, and Biosciences Division; Argonne National Laboratory - Advanced Photon Source
- DOE Contract Number:
- AC02-06CH11357
- OSTI ID:
- 1481734
- Journal Information:
- ACS Catalysis, Vol. 7, Issue 8; ISSN 2155-5435
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
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