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Design and synthesis of spherical-platelike ternary copper-cobalt-manganese catalysts for direct conversion of syngas to ethanol and higher alcohols

Author:
Sun, Kai, Tan, Minghui, Bai, Yunxing, Gao, Xiaofeng, Wang, Peng, Gong, Nana, Zhang, Tao, Yang, Guohui, Tan, Yisheng
Source:
Journal of catalysis 2019 v.378 pp. 1-16
ISSN:
0021-9517
Subject:
X-ray diffraction, X-ray photoelectron spectroscopy, active sites, adsorption, carbon monoxide, catalysts, catalytic activity, cobalt, copper, coprecipitation, ethanol, geometry, hydrogenation, manganese, nanosheets, probability, synergism, synthesis gas
Abstract:
Novel CuCoMn ternary catalyst with a “spherical-platelike” (CuMn-Co) nanosized particles structure was designed and successfully performed in ethanol and higher alcohols (HA) production via heterogeneous CO hydrogenation. The “spherical-platelike” CuCoMn catalyst, achieved through a simple co-precipitation (CP) route followed by a calcination-reduction process, contained a CuMn-rich sphere structure and a Co-dominated nanosheet. The catalyst demonstrated a total alcohols selectivity of 46.2%, and the fraction of ethanol reached up to 45.4% among the total alcohols products, which is superior to the classical modified CuCo-based catalysts. The outstanding catalytic performance was attributed to the unique “spherical-platelike” structure, which altered the surface Cu+/Cu0 distribution and the dispersion of Co species. As revealed by in situ XRD, H2-TPR, in situ XPS, HAADF-STEM and in situ DRIFT spectra techniques, a strong electronic and geometric interaction between Cu and Mn species in optimized CuCoMn catalyst modified the chemical states of Cu species to present a higher proportion of surface Cu+/(Cu0 + Cu+) and, especially, enhanced the linear CO adsorption on Cu+ active sites, which provided a higher probability of CO insertion, and eventually contributed to promotion of catalytic performance. In addition, a higher probability of bridge CO adsorption on metallic Co was also observed over the CuCoMn catalyst, which was beneficial for the formation of CHx intermediates. It is concluded that a synergistic effect between Cu+ and Co species, promoted by the presence of manganese species, was responsible for CO hydrogenation to produce ethanol.
Agid:
6592773