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Two-dimensional molybdenum carbide 2D-Mo₂C as a superior catalyst for CO₂ hydrogenation.

ABSTRACT: Early transitional metal carbides are promising catalysts for hydrogenation of CO₂. Here, a two-dimensional (2D) multilayered 2D-Mo₂C material is prepared from Mo₂CT_x of the MXene family. Surface termination groups T_x (O, OH, and F) are reductively de-functionalized in Mo₂CT_x (500 °C, pure H₂) avoiding the formation of a 3D carbide structure. CO₂ hydrogenation studies show that the activity and product selectivity (CO, CH₄, C₂-C₅ alkanes, methanol, and dimethyl ether) of Mo₂CT_x and 2D-Mo₂C are controlled by the surface coverage of T_x groups that are tunable by the H₂ pretreatment conditions. 2D-Mo₂C contains no T_x groups and outperforms Mo₂CT_x, β-Mo₂C, or the industrial Cu-ZnO-Al₂O₃ catalyst in CO₂ hydrogenation (evaluated by CO weight time yield at 430 °C and 1 bar). We show that the lack of surface termination groups drives the selectivity and activity of Mo-terminated carbidic surfaces in CO₂ hydrogenation.

SUBMITTER: Zhou H

PROVIDER: S-EPMC8448824 | biostudies-literature | 2021 Sep

REPOSITORIES: biostudies-literature

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Two-dimensional molybdenum carbide 2D-Mo2C as a superior catalyst for CO2 hydrogenation.

Zhou Hui H Chen Zixuan Z Kountoupi Evgenia E Tsoukalou Athanasia A Abdala Paula M PM Florian Pierre P Fedorov Alexey A Müller Christoph R CR

Nature communications 20210917 1

Early transitional metal carbides are promising catalysts for hydrogenation of CO2. Here, a two-dimensional (2D) multilayered 2D-Mo2C material is prepared from Mo2CTx of the MXene family. Surface termination groups Tx (O, OH, and F) are reductively de-functionalized in Mo2CTx (500 °C, pure H2) avoiding the formation of a 3D carbide structure. CO2 hydrogenation studies show that the activity and pro ...[more]

PMID: 34535647

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Project description: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 (Tx 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 Tx species and its consequence on CO conversion is highlighted by the observation of a very pronounced activation of Mo2CTx (pretreated in H2 at 400 °C) under FT conditions. This activation process is ascribed to the in situ reductive defunctionalization of Tx 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 α = 0.87, which is ca. twice higher than the α 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 β-Μo2C catalyst that shows no in situ activation under identical FT conditions. The passivating Tx groups of Mo2CTx can be reductively defunctionalized also by using a higher H2 pretreatment temperature of 500 °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.

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Two-dimensional molybdenum carbide 2D-Mo₂C as a superior catalyst for CO₂ hydrogenation.

Publications

Two-dimensional molybdenum carbide 2D-Mo<sub>2</sub>C as a superior catalyst for CO<sub>2</sub> hydrogenation.

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