10.1002/anie.201814611
Angewandte Chemie International Edition
COMMUNICATION
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interface, where they undergo insertion reactions with alkyl
species to form CmHyCHO* species,[4a] as shown in Scheme 1
(Path ②)). So the oxygenates are selectively produced by the
step-wise hydrogenation of the as-obtained intermediates. The
CO* or CHxO* insertion into CHy is recognized as the rate-
determining step to produce C2+ oxygenates, and CHxO*
insertion may occur preferentially than that of CO* over the
studied interface.[4a,11] Compared with the sole CoMn catalyst,
the multifunctional catalyst with the appropriate proximity
provides complementary insertion species, resulting in
increasing ratio of adsorbed molecular CHxO* to alkyl species,
thus leading to higher selectivity to oxygenates. A definitive
proof is still required in future work through extensive operando
spectroscopic and microscopic investigation to further elucidate
the reaction network and catalytic mechanism for HAS.
In conclusion, we have succeeded in designing
a
multifunctional catalyst composed of CoMn oxides and
CuZnAlZr oxides that can greatly raise the oxygenates
selectivity to 58.1 wt%, where more than 92.0 wt% are C2+OH in
the oxygenates fraction. The total selectivity to value-added
chemicals including oxygenates and olefins reaches 80.6 wt% at
CO conversion of 29.0 %. The C1 slates are greatly suppressed,
and the weight fraction of C2+OH in the oxygenates distribution is
as high as 98.9 wt% for catalyst with granule stacking, which is
superior than the other interaction manners. For the
multifunctional catalyst, the CoMn oxides provide the required
dual active sites such as Co/Co2C for higher oxygenates
formation, while the CuZnAlZr oxides could effectively tailor the
reaction network and selectively boost the insertion reactions by
hydrogenating aldehydes to the corresponding alcohols as well
as providing supplementary CHxO* as adsorption species for
insertion. The selective promotion of the reaction network via the
synergistic effect of the different components is responsible for
suppressing C1 products and enhancing the selectivity to higher
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Acknowledgements
We are grateful for financial support from the National Key R&D
Program of China (2017YFB0602202, 2017YFB0602203,
2018YFB0604700), Natural Science Foundation of China
(21573271, 91545112, 21776296 and 21703278), Key Research
Program of Frontier Sciences, CAS (Grant No. QYZDB-SSW-
SLH035), the “Transformational Technologies for Clean Energy
and Demonstration”, Strategic Priority Research Program of the
Chinese Academy of Sciences (Grant No. XDA21020600), the
Youth Innovation Promotion Association of CAS and SARI
Interdisciplinary Youth Innovation Research funding (171001).
Keywords: higher oxygenates • syngas conversion • cobalt
carbide • olefins • synergetic effect
[11] Y. -H. Zhao, K. Sun, X. Ma, J. Liu, D. Sun, H. -Y. Su, W. -X.
Li, Angew. Chem. Int. Ed. 2011, 50, 5335-5338.
Conflict of interest
The authors declare no conflict of interest.
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