The Impact of Oxygen Surface Coverage and Carbidic Carbon on the Activity and Selectivity of Two-Dimensional Molybdenum Carbide (2D-Mo2C) in Fischer–Tropsch Synthesis
Abstract
Transformations of oxygenates (CO2, CO, H2O, etc.) via Mo2C-based catalysts are facilitated by the high oxophilicity of the material; however, this can lead to the formation of oxycarbides and complicate the identification of the (most) active catalyst state and active sites. In this context, the two-dimensional (2D) MXene molybdenum carbide Mo2CTx (T-x are passivating surface groups) contains only surface Mo sites and is therefore a highly suitable model catalyst for structure-activity studies. Here, we report that the catalytic activity of Mo2CTx in Fischer-Tropsch (FT) synthesis increases with a decreasing coverage of surface passivating groups (mostly O*). The in situ removal of T-x species and its consequence on CO conversion is highlighted by the observation of a very pronounced activation of Mo2CTx (pretreated in H-2 at 400 degrees C) under FT conditions. This activation process is ascribed to the in situ reductive defunctionalization of T-x groups reaching a catalyst state that is close to 2D-Mo2C (i.e., a material containing no passivating surface groups). Under steady-state FT conditions, 2D-Mo2C yields higher hydrocarbons (C5+ alkanes) with 55% selectivity. Alkanes up to the kerosine range form, with value of alpha = 0.87, which is ca. twice higher than the alpha value reported for 3D-Mo2C catalysts. The steady-state productivity of 2D-Mo2C to C5+ hydrocarbons is ca. 2 orders of magnitude higher relative to a reference beta-Mu o(2)C catalyst that shows no in situ activation under identical FT conditions. The passivating T-x groups of Mo2CTx can be reductively defunctionalized also by using a higher H-2 pretreatment temperature of 500 degrees C. Yet, this approach leads to a removal of carbidic carbon (as methane), resulting in a 2D-Mo2C1-x catalyst that converts CO to CH4 with 61% selectivity in preference to C5+ hydrocarbons that are formed with only 2% selectivity. Density functional theory (DFT) results attribute the observed selectivity of 2D-Mo2C to C5+ alkanes to a higher energy barrier for the hydrogenation of surface alkyl species relative to the energy barriers for C-C coupling. The removal of O* is the rate-determining step in the FT reaction over 2D-Mo2C, and O* is favorably removed in the form of CO2 relative to H2O, consistent with the observation of a high CO2 selectivity (ca. 50%). The absence of other carbon oxygenates is explained by the energetic favoring of the direct over the hydrogen-assisted dissociative adsorption of CO. Show more
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https://doi.org/10.3929/ethz-b-000659841Publication status
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Journal / series
ACS CatalysisVolume
Pages / Article No.
Publisher
American Chemical SocietySubject
carbide catalysts; defunctionalization of MXenes; Fischer-Tropsch synthesis; two-dimensional (2D)materials; oxygen coverage; molybdenum carbide; DFT calculationsFunding
ETH-40 19-2 - Understanding Selectivity and Active Sites in Carbide-Based Catalysts for the Fischer-Tropsch Process via Fischer-Tropsch Process of Model 2D Carbides (MXenes) with Isolated Dopant Single Sites (ETHZ)
ETH-40 17-2 - Advanced materials by atomic layer deposition (ALD): from controlling porosity of ALD-grown overcoats to the molecular understanding of silica-aluminas (ETHZ)
180544 - NCCR Catalysis (phase I) (SNF)
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