Structural dynamics of Ni/Mo2CTx MXene catalysts under reaction modulate CO2 reduction performance

doi:10.1016/S1872-2067(25)64681-X

Abstract

Abstract:

The catalyst's structural dynamics under reaction conditions critically determine their performance. We proved this indication by studying Ni nanoparticles supported on Mo₂CT_x MXene, where the average size during CO₂ hydrogenation changed from 12.9 to 3.1 nm. A parallel increase of CO selectivity from 21.1% to 92.6% at 400 °C was observed, while the CO₂ conversion rate remained at about 84.0 mmol·g_cat^-1·h^-1. This transformation involved partial removal of Mo₂CT_x terminal groups, allowing direct interaction between Ni and Mo atoms instead of indirect coupling through -O terminations. The shift from a Ni-O-Mo to a Ni-Mo interaction enhanced electron transfer from Ni to Mo₂CT_x, strengthening the metal-support interaction and driving Ni nanoparticle dispersion. In-situ mechanistic analysis and kinetic isotope studies revealed that Ni dispersion suppresses the formate and carboxyl pathway, promotes direct CO₂ dissociation, and inhibits CO hydrogenation, shifting the primary product from CH₄ to CO. These findings provide a strategy for designing highly selective and stable MXene-based catalysts through engineered metal-support interactions.

Key words: Mo₂CT_x MXene, CO₂ hydrogenation, Metal-support interactions, Catalytic selectivity, Structure evolution

Jun Ma, Bing Xu, Shuo Cao, Shiyan Li, Wei Chu, Siglinda Perathoner, Gabriele Centi, Yuefeng Liu. Structural dynamics of Ni/Mo₂CT_x MXene catalysts under reaction modulate CO₂ reduction performance[J]. Chinese Journal of Catalysis, 2025, 72: 243-253.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64681-X

https://www.cjcatal.com/EN/Y2025/V72/I5/243

Figures/Tables 7

Fig. 1. (a) Schematic showing the synthesis of 2D Mo2CTx MXene and Ni/Mo2CTx catalyst. XRD patterns (b), XPS survey spectra (c) and Raman spectra (d) of Mo2Ga2C, Mo2CTx and Ni/Mo2CTx.

Fig. 2. (a) CO2 conversion and CO selectivity as a function of reaction temperature in three cycles. (b) CO2 conversion rate and product selectivity of Ni/Mo2CTx after reduction and after treatment on CO2 hydrogenation conditions at different temperatures for 2 h. (c) CO2 reaction rate and selectivity of Ni/Mo2CTx-R at 500 °C. (d) Stability test of Ni/Mo2CTx-T500 at 500 °C. Reaction conditions: mcat. = 50.0 mg, WHSV = 60000 mL·gcat-1·h-1, H2/CO2 = 4.

Fig. 3. BF-STEM image (a) and EELS image and corresponding EELS mapping (b) of Ni/Mo2CTx-R, EELS spectra in area (i) (c) and (ii) (d). (e) TEM image of Ni/Mo2CTx-R. (f) HR-TEM images of Ni/Mo2CTx with [001] and [100] axis view. (j) HR-TEM image of Ni/Mo2CTx-T500. HR-TEM images of Ni/Mo2CTx-T500 with [001] (k) and [100] (m) axis view. (g, i, l, n) is a schematic structural corresponding to the HR-TEM image on the left.

Fig. 4. (a) XRD patterns of Ni/Mo2CTx-R, Ni/Mo2CTx-T400, Ni/Mo2CTx-T500 and Mo2CTx-R500. (b) Raman spectra of Ni/Mo2CTx-R, Ni/Mo2CTx-T400 and Ni/Mo2CTx-T500.

Fig. 5. Mo 3d (a) andNi 2p3/2 (b) XPS spectra of Ni/Mo2CTx-R, Ni/Mo2CTx-T400 and Ni/Mo2CTx-T500 catalysts. (c) Mo-C/Mo and Ni0/Ni contents of samples calculated from XPS spectra.

Fig. 6. (a) Temperature-programmed CO2 + H2-DRIFTS ramping from 50 to 400 °C over Ni/Mo2CTx-R (a) and Ni/Mo2CTx-T500 (b). Relative intensity of carboxyl (c) and formate (d) intermediates in in-situ DRFIT spectra. (e) Scheme of Carboxyl (i), Formate (ii) and Bidentate carbonate (iii) intermediates.

Fig. 7. Kinetic D2 isotope effects experiments of CO2 hydrogenation (a) and CO hydrogenation (b). Reaction conditions: T = 220 °C, 50 mg catalyst, WHSV = 60000 mL·gcat.-1·h?1. (c) Schematic representation of the origin of the inverse kinetic isotope effect and thermodynamic isotope effect in the CO2 hydrogenation reaction. (d) The scheme of the catalytic pathway for the CO2 hydrogenation over Ni/Mo2CTx-R and Ni/Mo2CTx-T500.

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Structural dynamics of Ni/Mo₂CT_x MXene catalysts under reaction modulate CO₂ reduction performance

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