Grain boundary engineering of CeO2 induced electron redistribution for dimethyl carbonate synthesis from CO2

doi:10.1016/S1872-2067(25)64871-6

Abstract

Abstract:

Direct synthesis of dimethyl carbonate (DMC) from CO₂ is critical for achieving carbon neutrality, yet the sluggish formation and conversion of the key *CH₃OCOO intermediate-due to the difficulty of C-O coupling-limit high DMC yields. Herein, we developed a boric acid-assisted recrystallization strategy to fabricate grain-boundary-rich CeO₂ hollow nanospheres, which serve as an efficient catalyst for CO₂ to DMC synthesis. The introduction of grain-boundary (GBs) induced the electron redistribution, which led a decrease in the electron density of bulk Ce ions and created a localized electron-rich region at homogeneous interface. This unique electronic landscape promoted reactive methoxy formation and stronger CO₂ adsorption, thereby enabling more efficient coupling of *CH₃O and *CO₂ to form the *CH₃OCOO. Concurrently, the enhanced CO₂ adsorption facilitated the dissociation of *CH₃OCOO and subsequent DMC formation. As a result, the 4%BCeO₂-GBs achieved an advantageous DMC yield of 19.8 mmol/g. In the assistance of dehydrating agent, the catalyst delivered a remarkable 264.2 mmol/g DMC yield and 7.12% methanol conversion, which was 32 times higher than commercial CeO₂. This study elucidated the intrinsic mechanisms governing *CH₃OCOO intermediate behavior and offers valuable guidance for CO₂ converting into high-value organic chemicals.

Key words: Dimethyl carbonate synthesis, CeO₂ catalyst, Grain boundary engineering, Electron redistribution, Reaction intermediates

Guoqiang Hou, Di Xu, Haifeng Fan, Yangyang Li, Siyi Huang, Mingyue Ding. Grain boundary engineering of CeO₂ induced electron redistribution for dimethyl carbonate synthesis from CO₂[J]. Chinese Journal of Catalysis, 2026, 80: 316-329.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64871-6

https://www.cjcatal.com/EN/Y2026/V80/I1/316

Figures/Tables 8

Scheme 1. Potential role of grain boundary in regulation of electronic structure of CeO2 and reactant adsorption in DMC synthesis from CO2 and methanol.

Fig. 1. The process of formation of CeO2 catalyst by dissolution-recrystallization. (a) TEM images of crystal growth process of Norm-CeO2, 4%BCeO2-GBs and 8%BCeO2 with increasing time from 90 to 200 min at 180 °C. (b) Schematic illustration for fabrication of 4%BCeO2-GBs hollow catalyst.

Fig. 2. Characterization of catalyst. The micro-morphological ofNorm-CeO2 (a), 2%BCeO2-GBs (b), 4%BCeO2-GBs (c), and 8%BCeO2 (d). (e) Rietveld refinement XRD pattern in the range of 5?80 and crystal structure of Norm-CeO2 and 4%BCeO2-GBs. HRTEM images and FFT images of Norm-CeO2 (f) and 4%BCeO2-GBs (g). (h1) Integrated pixel intensities of Norm-CeO2 from the Fig. 2(f). Integrated pixel intensities of GBs taken from the direction of arrow in blue (h2), red (h3), and green (h4). (i) HRTEM images image of 8%B/CeO2. (j) Raman spectra of Norm-CeO2 and 4%BCeO2-GBs at 1% power.

Fig. 3. The catalytic performance of CeO2 catalysts. (a) DMC yield of CeO2 catalysts at 140 °C. (b) DMC yield on 4%BCeO2-GBs at different temperatures. (c) Cycling stability of 4%BCeO2-GBs at 140 and 160 °C. (d) Comparison of the DMC yield with the reported metal oxide catalysts at similar conditions. Reaction conditions: 100 mg catalyst; 11.88 g MeOH; pure CO2; 3.5 MPa; 100?180 °C for 3 h. All data was collected by the average of three times results, the relative error less than 1.8%.

Fig. 4. Structural analysis of CeO2 catalysts. XPS spectra of Ce 3d (a) and O 1s (b) of Norm-CeO2 and 4%BCeO2-GBs and 8%BCeO2. (c) The electron-density distribution CeO2 catalysts containing GBs. (d) ESR spectra of Norm-CeO2 and 4%BCeO2-GBs. CO2-TPD (e) and in-situ DRIFTS of CO2 adsorption (f) of Norm-CeO2 and 4%BCeO2-GBs. (g) The correlation of base density (red line) and IR intensity of bidentate carbonate (blue line) with spin concentration. MeOH-TPD (h) and in-situ DRIFTS of MeOH adsorption (i) of Norm-CeO2 and 4%BCeO2-GBs.

Fig. 5. Reaction mechanism. DRIFTS spectra of pre-adsorbed with MeOH followed by passing CO2 at 140 °C and dynamic relative IR bands intensities of adsorption species for 4%BCeO2-GBs (a,b) and Norm-CeO2 (c,d). DRIFTS spectra of pre-adsorbed with CO2 20 min, Ar was introduced to show the *CO2 adsorption strength, followed by passing MeOH at 140 °C and dynamic relative IR bands intensities of adsorption species for 4%BCeO2-GBs (e,f) and Norm-CeO2 (g,h). The highest IR band intensity of species was defined as 100%.

Fig. 6. Reaction mechanism. DRIFTS spectra of pre-adsorbed with DMC followed by passing Ar at 160 °C and dynamic relative IR bands intensities of decomposed species for 4%BCeO2-GBs (a,b) and Norm-CeO2 (c,d). The highest IR band intensity of species was defined as 100%.

Scheme 2. Potential reaction mechanism for DMC synthesis from CO2 and methanol on 4%BCeO2-GBs.

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Grain boundary engineering of CeO₂ induced electron redistribution for dimethyl carbonate synthesis from CO₂

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