The role of manganese in CoMnOx catalysts for selective long-chain hydrocarbon production via Fischer-Tropsch synthesis
Cobalt is an efficient catalyst for Fischer-Tropsch synthesis (FTS) of hydrocarbons from syngas (CO + H<sub>2</sub>) with enhanced selectivity for long-chain hydrocarbons when promoted by Manganese. However, the molecular scale origin of the enhancement remains unclear. Here we present an experimental and theoretical study using model catalysts consisting of crystalline CoMnO<sub>x</sub> nanoparticles and thin films, where Co and Mn are mixed at the sub-nm scale. Employing TEM and in-situ X-ray spectroscopies (XRD, APXPS, and XAS), we determine the catalyst's atomic structure, chemical state, reactive species, and their evolution under FTS conditions. We show the concentration of CH<sub>x</sub>, the key intermediates, increases rapidly on CoMnO<sub>x</sub>, while no increase occurs without Mn. DFT simulations reveal that basic O sites in CoMnO<sub>x</sub> bind hydrogen atoms resulting from H<sub>2</sub> dissociation on Co<sup>0</sup> sites, making them less available to react with CH<sub>x</sub> intermediates, thus hindering chain termination reactions, which promotes the formation of long-chain hydrocarbons.
Authors
- Zengqing Zhuo (ORCID: https://orcid.org/0000-0001-6602-760X)
- Feipeng Yang (ORCID: https://orcid.org/0000-0002-5470-3241)
- Zan Lian (ORCID: https://orcid.org/0000-0001-6922-406X)
- Peidong Yang (ORCID: https://orcid.org/0000-0003-4799-1684)
- Saul H. Lapidus (ORCID: https://orcid.org/0000-0002-7486-4325)
- Judit Oliver–Meseguer (ORCID: https://orcid.org/0000-0003-1555-3583)
- Hao Chen (ORCID: https://orcid.org/0000-0003-3759-8352)
- Priscilla F. Pieters (ORCID: https://orcid.org/0000-0001-9000-6657)
- Nikos Liakakos (ORCID: https://orcid.org/0000-0001-5656-8533)
- Ji Su (ORCID: https://orcid.org/0000-0003-2258-162X)
- Monika Blum (ORCID: https://orcid.org/0000-0002-2918-9092)
- Jinghua Guo (ORCID: https://orcid.org/0000-0002-8576-2172)
- Jiawei Wan (ORCID: https://orcid.org/0000-0002-3805-5133)
- Miquel Salmerón (ORCID: https://orcid.org/0000-0002-2887-8128)
- Iradwikanari Waluyo (ORCID: https://orcid.org/0000-0002-4046-9722)
- M. Virginia P. Altoé
- Laureline Treps (ORCID: https://orcid.org/0009-0005-9799-835X)
- Adrian Hunt (ORCID: https://orcid.org/0000-0002-5283-9647)
- Xiao Zhao (ORCID: https://orcid.org/0000-0003-1079-664X)
- Haimei Zheng (ORCID: https://orcid.org/0000-0003-3813-4170)
- Ed Wong
- Hirohito Ogasawara (ORCID: https://orcid.org/0000-0001-5338-1079)
- Elzbieta Pach (ORCID: https://orcid.org/0000-0001-9587-3768)
- Alexis T. Bell (ORCID: https://orcid.org/0000-0002-5738-4645)
- Ji Yang (ORCID: https://orcid.org/0000-0002-3997-385X)
- Sophie Carenco (ORCID: https://orcid.org/0000-0002-6164-2053)
- Shan Yu (ORCID: https://orcid.org/0000-0003-2253-9448)
- Núria López (ORCID: https://orcid.org/0000-0001-9150-5941)
Institutions
- Argonne National Laboratory (US)
- Lawrence Berkeley National Laboratory (US)
- Brookhaven National Laboratory (US)
- SLAC National Accelerator Laboratory (US)
- Institut Català d'Investigació Química (ES)
- University of California, Berkeley (US)
Publication Details
- Journal
- Nature Communications
- Published
- 2024-11-27
- DOI
- https://doi.org/10.1038/s41467-024-54578-3
- Citations
- 15
- Primary Topic
- Catalysts for Methane Reforming
- Type
- article
- Field-Weighted Citation Impact
- 1.60
Funders
- National Science Foundation
- U.S. Department of Energy
- Universidad de Alicante
- European Commission
- Ministerio de Ciencia e Innovación
- Barcelona Supercomputing Center
- Office of Science
- Basic Energy Sciences
- Chemical Sciences, Geosciences, and Biosciences Division
- Brookhaven National Laboratory
- Lawrence Berkeley National Laboratory
- SLAC National Accelerator Laboratory