The role of manganese in CoMnOx catalysts for selective long-chain hydrocarbon production via Fischer-Tropsch synthesis

Chen, Hao; Lian, Zan; Zhao, Xiao; Wan, Jiawei; Pieters, Priscilla F.; Oliver-Meseguer, Judit; Yang, Ji; Pach, Elzbieta; Carenco, Sophie; Treps, Laureline; Liakakos, Nikos; Shan, Yu; Altoe, Virginia; Wong, Ed; Zhuo, Zengqing; Yang, Feipeng; Su, Ji; Guo, Jinghua; Blum, Monika; H. Lapidus, Saul; Hunt, Adrian; Waluyo, Iradwikanari; Ogasawara, Hirohito; Zheng, Haimei; Yang, Peidong; Bell, Alexis T.; López, Núria; Salmeron, Miquel

doi:10.1038/s41467-024-54578-3

Title: The role of manganese in CoMnO_x catalysts for selective long-chain hydrocarbon production via Fischer-Tropsch synthesis

Journal Article · 26 November 2024 · Nature Communications

DOI: https://doi.org/10.1038/s41467-024-54578-3 · OSTI ID:2483531

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Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Barcelona Institute of Science and Technology (BIST), Tarragona (Spain)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); University of California, Berkeley, CA (United States)
University of California, Berkeley, CA (United States)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Cobalt is an efficient catalyst for Fischer–Tropsch synthesis (FTS) of hydrocarbons from syngas (CO + H₂) 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_x 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_x, the key intermediates, increases rapidly on CoMnO_x, while no increase occurs without Mn. DFT simulations reveal that basic O sites in CoMnO_x bind hydrogen atoms resulting from H₂ dissociation on Co⁰ sites, making them less available to react with CH_x intermediates, thus hindering chain termination reactions, which promotes the formation of long-chain hydrocarbons.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Contributing Organization:: Brookhaven National Laboratory (BNL)

Grant/Contract Number:: AC02-05CH11231; AC02-76SF00515; SC0012704

OSTI ID:: 2483531

Report Number(s):: BNL--226432-2024-JAAM

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 15; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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Title: The role of manganese in CoMnO_x catalysts for selective long-chain hydrocarbon production via Fischer-Tropsch synthesis