Functional ladder-like heterojunctions of Mo2C layers inside carbon sheaths for efficient CO2 fixation

doi:10.1016/S1872-2067(23)64595-4

Abstract

Abstract:

The development of two-dimensional heterogeneous catalysts with highly exposed active site areas for heterogeneous catalytic systems is highly promising for achieving the green transformation of small molecules. 2D transition metal carbides (TMCs) show great promise for catalysis and carbon capture but suffer from heavy aggregation and autooxidation. Mass transfer barrier is also a standard problem of lamellar TMCs caused by slight aggregation of layers. Here, we successfully developed a method to prepare “ladder-like” heterojunctions of Mo₂C layers confined inside nitrogen-rich carbon sheaths (2D-Mo₂C@NC) via an effective oxygen-diffusion etching strategy, acting as efficient catalysts for CO₂ fixation. The enhanced electron enrichment of the as-integrated 2D-Mo₂C subunits induced by the Schottky barrier could further keep the exposed Mo₂C surface from possible autooxidation and aggregation confronted by conventional 2D TMCs. The experimental results and density functional theory (DFT) calculation further demonstrate that electron-rich Mo₂C could boost the adsorption and activation of CO₂ for universal carbonylation of various diamines, providing a turnover frequency value (TOF) of 10.2 h^-1 to produce benzimidazolone, which is 5.2 times of that of the state-of-the-art catalyst in the literature under even critical conditions.

Key words: Electron-rich 2D-Mo₂C, CO₂ fixation, Schottky heterojunction, Carbonylation, Heterogeneous catalysis

Yu-Shuai Xu, Hong-Hui Wang, Qi-Yuan Li, Shi-Nan Zhang, Si-Yuan Xia, Dong Xu, Wei-Wei Lei, Jie-Sheng Chen, Xin-Hao Li. Functional ladder-like heterojunctions of Mo₂C layers inside carbon sheaths for efficient CO₂ fixation[J]. Chinese Journal of Catalysis, 2024, 58: 138-145.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64595-4

https://www.cjcatal.com/EN/Y2024/V58/I3/138

Figures/Tables 4

Fig. 1. Synthesis and structures of 2D-Mo2C@NC samples. (a) TEM image of the typical 2D-Mo2C@NC sample (N content 7.1 at% and oxidation time 1 h). (b) The thickness of Mo2C nanoflakes in the typical 2D-Mo2C@NC sample. (c) HRTEM image of the typical 2D-Mo2C@NC sample. (d) TEM image of Mo2C/MoO3@NC. (e) XRD patterns of Mo2C@NC (black), Mo2C/MoO3@NC (orange), and the typical 2D-Mo2C@NC (green) samples.

Fig. 2. Catalytic CO2 fixation performance of 2D-Mo2C@NC catalysts for carbonylation of o-phenylenediamine into benzimidazolone. (a) Conversions of o-phenylenediamine (green spheres) and selectivity to benzimidazolone (black spheres) over 2D-Mo2C@NC catalyst at different reaction times. (b) Conversions of o-phenylenediamine to benzimidazolone over NC support, bulk Mo2C, Mo2CTx, Mixture, and 2D-Mo2C@NC catalysts. (c) Scope of substrates catalyzed by optimal 2D-Mo2C@NC catalyst. Reaction conditions for the synthesis of imidazolones: 2 mL N-methylpyrrolidone (NMP), 1 mmol diamine, 0.4 mmol 1,8-diazabicyclo [5.4.0]-7-undecene (DBU), 30 mg catalyst, 140 °C (a), 120 °C (b), 10 bar CO2, 4 h.

Fig. 3. Promoted CO2 fixation on electron-rich 2D-Mo2C in 2D-Mo2C@NC catalysts for benzimidazolone production. (a) Electron density difference stereograms of typical 2D-Mo2C@NC model (Green: electron-rich area, yellow: electron-deficient area). Color code: C, gray; N, blue; Mo, green. (b) Measured work functions (Φ) of bulk Mo2C (dash line) and 2D-Mo2C@NC samples (spheres) with different N contents (Table S2). (c) Calculated adsorption energies (Eads-CO2) of CO2 molecules on the surface of the neutral Mo2C and electron-rich Mo2C (Mo2C+e-) models. Insets: optimized configurations of CO2 on the surface of two Mo2C models. (d) The turnover frequency (TOF) values for carbonylation of o-phenylenediamine with CO2 to benzimidazolone over bulk Mo2C catalyst (dash line) and 2D-Mo2C@NC catalysts (spheres). (e) Mo 3d XPS spectra of 2D-Mo2C@NC (N content 7.1 at%) and bulk Mo2C samples. (f) Reusability of 2D-Mo2C@NC catalyst. Reaction conditions: 1 mL N-methylpyrrolidone (NMP), 1 mmol o-phenylenediamine, 0.4 mmol 1,8-diazabicyclo [5.4.0]-7-undecene (DBU), 10 mg catalyst, 140 °C, 10 bar CO2, 1 h.

Fig. 4. Promoted CO2 fixation on “ladder-like” 2D-Mo2C in 2D-Mo2C@NC catalysts for benzimidazolone production. (a) Schematic model of CO2 adsorption on Mo2C@NC and 2D-Mo2C@NC samples. (b) CO2 TPD results for adsorption capacity of Mo2C@NC and 2D-Mo2C@NC samples. (c) Conversions of o-phenylenediamine to benzimidazolone over Mo2C@NC and 2D-Mo2C@NC catalysts. (d) TOF values of the optimized 2D-Mo2C@NC catalyst (green spheres) and the state-of-the-art catalysts in the literature. Reaction conditions: 1 mL NMP, 1 mmol o-phenylenediamine, 0.4 mmol DBU, 10 mg catalyst, 140 °C (120 °C), 10 bar CO2, 1 h.

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Functional ladder-like heterojunctions of Mo₂C layers inside carbon sheaths for efficient CO₂ fixation

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