Synthesis of Dimethyl Carbonate from CO2 and Methanol over Zr-Based Catalysts with Different Chemical Environments

Huo, Linmeng; Tian, Wang; Xuan, Keng; Li, Lei; Pu, Yanfeng; Li, Chenxin; Qiao, Congzhen; Yang, Hao; Bai, Yan

doi:10.3390/catal11060710

Cited by 14 publications

(3 citation statements)

References 64 publications

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“…The different surface OH groups, which were attributed to the different Si contents in the Zr–O–Si structures, were further verified by XPS analysis with O 1s peaks, and the results are displayed in Figure . The O 1s peak can be deconvoluted with four different oxygen environments such as Zr–O–Zr, Zr–OH, Zr–O–Si, and Si–OH at their respective BEs of ∼530.3, ∼531.7, ∼532.6, and ∼533.2 eV , as summarized in supplementary Table S1. In general, the incorporation of Si atoms to the Zr(OH) 4 structures can generate different surface OH groups such as the terminal (t O(OH) ) as well as bridged (b O ) groups on the Zr(OH) 4 surfaces, ,− which can alter the surface density of OH groups resulting in changing catalytic activity .…”

Section: Resultsmentioning

confidence: 99%

Catalytic Conversion of Biomass-Derived Levulinic Acid to γ-Valerolactone over Amphoteric Zirconium Hydroxide

Zhao,

Kasipandi,

Shin

et al. 2023

ACS Catal.

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A series of acid−base amphoteric amorphous Zr(OH) 4 catalysts, synthesized with different amounts of leached SiO 2 , were investigated for catalytic transfer hydrogenation of liquid-phase levulinic acid (LA) to produce γ-valerolactone (GVL) with isopropanol as a hydrogen-donor solvent. The prepared Zr(OH) 4 at pH of ∼10 under a reflux condition of water caused an inevitable dissolution of silicon species from glassware, which eventually altered the surface acid−basic properties of the amorphous Zr(OH) 4 . The number of Lewis and total acidic as well as medium-strength basic sites, prepared by simply changing the aging days of Zr(OH) 4 , was mainly responsible for an enhanced LA conversion of 91.5% and GVL selectivity of 77.6% with an apparent activation energy of ∼33.9 kJ/mol over Zr(OH) 4 aged for 7 days [ZrOH ( 7)]. In addition, catalytic and thermal stabilities of ZrOH (7) were found with a stable LA conversion with smaller coke depositions, which were attributed to the stable preservation of the active sites caused by a proper amount of thermally stable Zr−O−Si phase formation.

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Section: Resultsmentioning

confidence: 99%

Catalytic Conversion of Biomass-Derived Levulinic Acid to γ-Valerolactone over Amphoteric Zirconium Hydroxide

Zhao,

Kasipandi,

Shin

et al. 2023

ACS Catal.

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“…The high-resolution energy level spectrum of N 1s for CoFe@CSC-700 (Figure 3c), can be categorized into three separate peaks. The binding energies of these peaks were 398.6 eV, 400.7 eV, and 402.5 eV, which were attributed to pyridine N, pyrrole N, and graphite N. As shown in Figure 3d, the O 1s XPS high-resolution energy spectrum can be fitted to three distinct peaks, the peaks of M-O (lattice oxygen), M-O-H (adsorbed oxygen), and impurity water, which are located at 530.4 eV, 532.3 eV, and 534.7 eV, respectively [32]. Figure 3e demonstrates the electronic state characteristics of Fe 2p, which specifically consists of two spin orbitals, Fe 2p 1/2 and Fe 2p 3/2 .…”

Section: Catalyst Characterizationmentioning

confidence: 92%

Preparation of Bimetallic CoFe@CSC-700 Carbonated Microspheres and Activated Peroxymonosulfate for Degradation of Levofloxacin

Hu,

Chen,

Guo

et al. 2024

Water

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The exploration of efficient, low-leaching, and recyclable transition-metal-based catalysts is of great importance for the removal of pollutants from peroxymonosulfate (PMS) in water purification processes. In this study, a bimetallic CoFe@CSC-700 composite was prepared by an alkaline gel pyrolysis reduction method using chitosan as a forming agent and applied to activate PMS to degrade levofloxacin (LEV). The leaching concentration of both cobalt and iron ions in the CoFe@CSC-700 catalyst was reduced by about 8-fold compared to the monometallic composite pellet catalyst. In addition, the removal efficiency of the CoFe@CSC-700 catalyst can still reach 90% after five cycles, showing good recyclability, recoverability and stability. Both free radical pathways (SO4·−, ·OH, and ·O2−) and non-free radical pathways (1O2) were detected in the oxidation reaction, with free radical pathways as the main contributor. The possible degradation pathways of LEV were proposed by LC-MS tests. Overall, this study provides new insights into the construction of efficient and stable PMS catalysts for wastewater treatment.

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“…Thus, the Ce10Zr1O2 NRs possessed the greatest acid site density, attributed to the oxygen vacancies functioning as Lewis acid sites. Acid-basic site pairs present on the surfaces of ZrO2, CeO2, and CeO2-ZrO2 catalysts have been identified as active sites for DMC synthesis [55][56][57]. Therefore, the marked enhancement in both acid and basic sites explains the superior DMC yield achieved by the Ce10Zr1O2 NRs.…”

Section: Similarly Wei Et Al Used I600/i460 Values To Indicate the Am...mentioning

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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Synthesis of Dimethyl Carbonate from CO2 and Methanol over Zr-Based Catalysts with Different Chemical Environments

Cited by 14 publications

References 64 publications

Catalytic Conversion of Biomass-Derived Levulinic Acid to γ-Valerolactone over Amphoteric Zirconium Hydroxide

Catalytic Conversion of Biomass-Derived Levulinic Acid to γ-Valerolactone over Amphoteric Zirconium Hydroxide

Preparation of Bimetallic CoFe@CSC-700 Carbonated Microspheres and Activated Peroxymonosulfate for Degradation of Levofloxacin

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

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