Ultrasonically assisted surface modified CeO2 nanospindle catalysts for conversion of CO2 and methanol to DMC

Kulthananat, Tachatad; Kim-Lohsoontorn, Pattaraporn; Seeharaj, Panpailin

doi:10.1016/j.ultsonch.2022.106164

Cited by 23 publications

(6 citation statements)

References 103 publications

(163 reference statements)

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“…Each spectrum exhibited well-resolved diffraction peaks located at 28.6, 33.1, 47.5, 56.3, 59.1, 69.4, and 77.0°, assigning to the face-centered cubic fluorite structure of CeO 2 crystals. [12] The intensity of diffraction peaks of CeO 2 increased with the increase of calcination temperatures, which implied the crystal growth of CeO 2 . In the meantime, the significantly decreased surface hydroxyl IR signal supported the transformation of Ce(OH) X species to CeO 2 crystal (Figure S2b).…”

Section: Resultsmentioning

confidence: 92%

Dimethyl Carbonate Synthesis from CO₂ over CeO₂ with Electron‐Enriched Lattice Oxygen Species

Hou,

Wang,

et al. 2024

Angewandte Chemie

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The direct synthesis of dimethyl carbonate (DMC) from CO2 has both theoretical and practical value in carbon neutrality, but its efficiency is far from the application requirements due to the lacks of understanding of reaction mechanism and rational design of catalyst. Herein, abundant electron‐enriched lattice oxygen species were introduced into CeO2 catalyst by constructing a large number of point defects and crystal‐terminated phases in the crystal reconstruction process. Benefitting from the modulation of acid‐base properties by electron‐enriched lattice oxygen, a much higher DMC yield of 22.2 mmol g‐1 was achieved on optimized CeO2 catalyst than other reported metal‐oxide‐based catalysts at similar conditions. Mechanistic investigations illustrated that the electron‐enriched lattice oxygen, instead of the oxygen vacancy, not only provided abundant sites for CO2 adsorption and activation, but also significantly induced the weakly absorbed methoxy species formation. Both of which facilitated the coupling of methoxy and CO2 to *CH3OCOO intermediate. In addition, the *CH3OCOO adsorption was obviously weakened on electron‐enriched lattice oxygen, thus shifting the rate‐determining‐step (RDS) from *CH3OCOO formation to *CH3OCOO dissociation and lowing the reaction energy barrier. This work provides insight into the underlying reaction mechanism for DMC synthesis from CO2 and methanol and the design of highly active catalysts.

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Section: Resultsmentioning

confidence: 92%

Dimethyl Carbonate Synthesis from CO₂ over CeO₂ with Electron‐Enriched Lattice Oxygen Species

Hou,

Wang,

et al. 2024

Angewandte Chemie

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“…For the Ce 3d XPS spectra (Figure 2b), the peaks of U, U 0 , U 00 , U 0 00 and V, V 0 , V 00 , V 0 00 are assigned to the spin-orbit multiplets of Ce 3d 3/2 and Ce 3d 5/2 , respectively. [7,25] The characteristic peaks of U 0 and V 0 are attributed to Ce 3þ , while the U, U 00 , U 0 00 and V, V 00 , V 0 00 peaks belong to Ce 4þ state. [20,26] As demonstrated in Table 1, the surface concentration of Ce 3þ of CeO 2 -C is 8.2%, and it increases to 17.5% for CeO 2 -M-5.…”

Section: Characterization Of Lewis Acid-base Sitesmentioning

confidence: 99%

Efficient Visible‐Light‐Assisted Synthesis of Dimethyl Carbonate from CO₂ and Methanol by Ce–Metal Organic Framework‐Derived CeO₂ Nanoparticles

Guan

Zhang

et al. 2023

Solar RRL

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The conversion of carbon dioxide to dimethyl carbonate (DMC) is an attractive process, but thermodynamic limitations of the reaction hinder its further development. In this work, we proposed a simple solution co‐precipitation strategy for the synthesis of a series of Ce‐MOF‐derived CeO2 nanoparticles to rapidly break the thermodynamic equilibrium and achieve highly‐efficient activation of CO2/CH3OH under photo‐thermal system. The CeO2‐M‐5, Ce(NO3)3·6H2O/2‐methylimidazoles molar ratio of 1:5, exhibits the highest DMC yield of 2.52 mmolDMC/g‐1 cat under photo‐thermal system, higher 3.26 times than CeO2‐C (nanoparticle by high‐temperature calcination). Moreover, the DMC yield of CeO2‐M‐5 nanoparticles increases by 10% under the photo‐thermal synergistic system compared to thermocatalytic system. This superior catalytic performance is attributed to the abundant Lewis acid‐base sites, excellent light absorption capacity and hydrophobicity. Besides, in‐situ diffuse reflectance infrared Fourier transform spectroscopy demonstrates that Ce‐MOF‐derived CeO2 nanoparticles can effectively activate CO2/CH3OH to enhance the formation of the key intermediate methyl carbonate upon light irradiation. Finally, combining characterisation and experimental results, the reaction mechanism of photo‐thermal catalysis of CO2/CH3OH for DMC synthesis over Ce‐MOF‐derived CeO2 nanoparticles was proposed. This work would provide new insights into the rational design of an effective catalyst for CO2 to produce high value‐added chemicals.This article is protected by copyright. All rights reserved.

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“…Consequently, designing and developing highly efficient catalysts to overcome the barrier of reaction energy is vitally important. Various catalysts, including CeO 2 [12][13][14], ZrO 2 [15], Cu-Ni alloys [16][17][18], and CeO 2 -ZrO 2 [10,14] composites, have been investigated for direct DMC synthesis in order to enhance catalytic performance. Among these candidates, CeO 2 -based catalysts have demonstrated the highest activity among common oxide catalysts.…”

Section: Introductionmentioning

confidence: 99%

Enhancing DMC Production from CO2: Tuning Oxygen Vacancies and In Situ Water Removal

Wang,

Li,

et al. 2024

Energies

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The direct synthesis of dimethyl carbonate (DMC) from methanol and CO2 presents an attractive route to turn abundant CO2 into value-added chemicals. However, insufficient DMC yields arise due to the inert nature of CO2 and the limitations of reaction equilibrium. Oxygen vacancies are known to facilitate CO2 activation and improve catalytic performance. In this work, we have demonstrated that tuning oxygen vacancies in catalysts and implementing in situ water removal can enable highly efficient DMC production from CO2. CexZryO2 nanorods with abundant oxygen vacancies were synthesized via a hydrothermal method. In liquid-phase DMC synthesis, the Ce10Zr1O2 nanorods exhibited a 1.7- and 1.4-times higher DMC yield compared to CeO2 nanoparticles and undoped CeO2 nanorods, respectively. Zr doping yielded a CeZr solid solution with increased oxygen vacancies, promoting CO2 adsorption and activation. In addition, adding 2-cyanopyridine as an organic dehydrating agent achieved an outstanding 87% methanol conversion and >99% DMC selectivity by shifting the reaction equilibrium to the desired product. Moreover, mixing CeO2 nanoparticles with hydrophobic fumed SiO2 in gas-phase DMC synthesis led to a doubling of DMC yield. This significant increase was attributed to the faster diffusion of water molecules away from the catalyst surface, facilitated by the hydrophobic SiO2. This study illustrates an effective dual strategy of enhancing oxygen vacancies and implementing in situ water removal to boost DMC production from CO2. The strategy can also be applied to other reactions impacted by water accumulation.

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Ultrasonically assisted surface modified CeO2 nanospindle catalysts for conversion of CO2 and methanol to DMC

Cited by 23 publications

References 103 publications

Dimethyl Carbonate Synthesis from CO₂ over CeO₂ with Electron‐Enriched Lattice Oxygen Species

Dimethyl Carbonate Synthesis from CO₂ over CeO₂ with Electron‐Enriched Lattice Oxygen Species

Efficient Visible‐Light‐Assisted Synthesis of Dimethyl Carbonate from CO₂ and Methanol by Ce–Metal Organic Framework‐Derived CeO₂ Nanoparticles

Enhancing DMC Production from CO2: Tuning Oxygen Vacancies and In Situ Water Removal

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Ultrasonically assisted surface modified CeO2 nanospindle catalysts for conversion of CO2 and methanol to DMC

Cited by 23 publications

References 103 publications

Dimethyl Carbonate Synthesis from CO2 over CeO2 with Electron‐Enriched Lattice Oxygen Species

Dimethyl Carbonate Synthesis from CO2 over CeO2 with Electron‐Enriched Lattice Oxygen Species

Efficient Visible‐Light‐Assisted Synthesis of Dimethyl Carbonate from CO2 and Methanol by Ce–Metal Organic Framework‐Derived CeO2 Nanoparticles

Enhancing DMC Production from CO2: Tuning Oxygen Vacancies and In Situ Water Removal

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Dimethyl Carbonate Synthesis from CO₂ over CeO₂ with Electron‐Enriched Lattice Oxygen Species

Dimethyl Carbonate Synthesis from CO₂ over CeO₂ with Electron‐Enriched Lattice Oxygen Species

Efficient Visible‐Light‐Assisted Synthesis of Dimethyl Carbonate from CO₂ and Methanol by Ce–Metal Organic Framework‐Derived CeO₂ Nanoparticles