A DFT study of dimethyl carbonate synthesis from methanol and CO2 on zirconia: Effect of crystalline phases

Wang, Xuhui; Zhao, Jinxian; Sun, Wei; Pei, Yongli; An, Jiangwei; Li, Zhong; Ren, Jun

doi:10.1016/j.commatsci.2018.12.011

Cited by 18 publications

(8 citation statements)

References 65 publications

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“…One is that the Zn_D9 model should actually be considered as a stoichiometric system, despite it having an oxygen vacancy as the Zn dopant has two less valence electrons than the replaced Zr atom. The second is that the ZrO 2 system has been shown to be well described by the GGA approach. , The last one is that the GGA + U approach involves crucial empirical parameters whereas the hybrid functionals are still too expensive to be used for surface calculations in a large scale. An energy cut-off of 400 eV and the Gaussian smearing width of 0.05 eV were employed.…”

Section: Computation Methodsmentioning

confidence: 99%

“…The second is that the ZrO 2 system has been shown to be well described by the GGA approach. 32,33 The last one is that the GGA + U approach involves crucial empirical parameters whereas the hybrid functionals are still too expensive to be used for surface calculations in a large scale. An energy cut-off of 400 eV and the Gaussian smearing width of 0.05 eV were employed.…”

Section: Computation Methodsmentioning

confidence: 99%

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Insights into the High Activity and Methanol Selectivity of the Zn/ZrO₂ Solid Solution Catalyst for CO₂ Hydrogenation

Zhou

2020

J. Phys. Chem. C

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Selective hydrogenation of CO2 to methanol is vital for mitigating the massive CO2 emission by utilizing the captured CO2 for chemical and fuel productions. Here, the key intermediates and mechanism of CO2 hydrogenation to methanol over the Zn/ZrO2 solid solution catalyst are thoroughly investigated by density functional theory calculations. Our calculations show that CO2 is highly activated when strongly adsorbed on the surface in a carbonate-like configuration, which may be the reason for the high CO2 conversion rate in methanol synthesis. In addition, CO formation from the dissociation of CO2 or COOH* is suppressed because of the stability of carbonate or the high energy barrier of COOH* formation, respectively. When compared with the traditional bi-HCOO route, where breaking the C–O bond is predicted to be the rate-determining step (RDS) with a modest energy barrier of 1.11 eV, a novel route is found to be kinetically much more favorable with a much lower energy barrier of 0.76 eV for the RDS of bi-H2CO* → mono-H2CO*. This alternative route starts from a newly found HCO3 * species in a tetrahedral configuration with the central C atom surrounded by an H atom and three O atoms, denoted as tri-HCOO*. It can be stepwise hydrogenated to methanol through the bi-HCO*, bi-H2CO*, mono-H2CO*, and H3CO* intermediates. These theoretical predictions suggest the high activity of the carbonate species in methanol synthesis over the Zn/ZrO2 solid solution catalyst, different from that on the pure metal oxide surfaces.

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Section: Computation Methodsmentioning

confidence: 99%

Section: Computation Methodsmentioning

confidence: 99%

Insights into the High Activity and Methanol Selectivity of the Zn/ZrO₂ Solid Solution Catalyst for CO₂ Hydrogenation

Zhou

2020

J. Phys. Chem. C

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“…According to the reaction mechanism about the direct synthesis of DMC from CO 2 and CH 3 OH reported by Kumar et al, 33 Kang et al, 34 and Desidery et al, 35 the acidic− basic properties played an important role in the synthesis process. Furthermore, Wang et al 36 examined the effect of ZrO 2 crystalline phases on the DMC yield from CH 3 OH and CO 2 using density functional theory (DFT) calculations and deeply discussed the adsorption of reactants and possible intermediates and even the reaction mechanism. Considering the experimental data and DFT calculations, the possible reaction mechanism was elaborated as follows: CH 3 OH could desorb on the basic and acidic sites of the catalysts, which were supplied by the oxygen ions (O 2− ) and yttrium ions (Y 3+ ) in yttrium oxide, respectively.…”

Section: Thermodynamic Calculation For Thementioning

confidence: 99%

Study of Thermodynamics and Experiment on Direct Synthesis of Dimethyl Carbonate from Carbon Dioxide and Methanol over Yttrium Oxide

Sun

Zheng

Wang

et al. 2020

Ind. Eng. Chem. Res.

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The thermodynamics on the direct synthesis of dimethyl carbonate (DMC) from CO2 and CH3OH was calculated and analyzed. Using Y(NO3)3·6H2O as the precursor, a series of Y2O3 were prepared through the one-pot calcination method, which were employed to catalyze DMC synthesis. The decomposition temperature of Y(NO3)3·6H2O was measured by thermogravimetric analysis, and Y2O3 was obtained after the precursor calcination at desired temperatures, denoted as Y2O3-T (°C). The catalysts were characterized by X-ray diffraction, Brunauer–Emmett–Teller method, transmission electron microscopy, NH3/CO2 temperature-programmed desorption, and X-ray photoelectron spectroscopy to detect the crystal phase, surface property, particle size, acidity–basicity amounts, and oxidation state, respectively. The characterization results indicated that Y2O3-750 can favor the formation of moderate acidic and basic sites and facilitate the activation of CO2 and CH3OH. The catalytic performance evaluation was experimentally investigated, and Y2O3-750 owned the highest DMC yield of 1.02 mmol/g·cat under 90 °C, 8 MPa, and 6 h, which also exhibited reliable recycle ability.

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“…The mechanism of the title reaction on ZrO 2 was proposed by Jung et al 130,134 Methanol is adsorbed on unsaturated Zr 4+ cations, leading to the formation of a methoxide group and water, which occurs through the reaction of a proton and a hydroxy group provided by ZrO 2 . Then, the intermediate monodentate methyl carbonate is formed by the combination of CO 2 with the methoxide group.…”

Section: Strategies For the Improvement Of Direct Dmc Synthesis From Co2 And Methanolmentioning

confidence: 99%

Catalytic processes for the direct synthesis of dimethyl carbonate from CO₂ and methanol: a review

et al. 2022

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A DFT study of dimethyl carbonate synthesis from methanol and CO2 on zirconia: Effect of crystalline phases

Cited by 18 publications

References 65 publications

Insights into the High Activity and Methanol Selectivity of the Zn/ZrO₂ Solid Solution Catalyst for CO₂ Hydrogenation

Insights into the High Activity and Methanol Selectivity of the Zn/ZrO₂ Solid Solution Catalyst for CO₂ Hydrogenation

Study of Thermodynamics and Experiment on Direct Synthesis of Dimethyl Carbonate from Carbon Dioxide and Methanol over Yttrium Oxide

Catalytic processes for the direct synthesis of dimethyl carbonate from CO₂ and methanol: a review

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A DFT study of dimethyl carbonate synthesis from methanol and CO2 on zirconia: Effect of crystalline phases

Cited by 18 publications

References 65 publications

Insights into the High Activity and Methanol Selectivity of the Zn/ZrO2 Solid Solution Catalyst for CO2 Hydrogenation

Insights into the High Activity and Methanol Selectivity of the Zn/ZrO2 Solid Solution Catalyst for CO2 Hydrogenation

Study of Thermodynamics and Experiment on Direct Synthesis of Dimethyl Carbonate from Carbon Dioxide and Methanol over Yttrium Oxide

Catalytic processes for the direct synthesis of dimethyl carbonate from CO2 and methanol: a review

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Product

Resources

About

Insights into the High Activity and Methanol Selectivity of the Zn/ZrO₂ Solid Solution Catalyst for CO₂ Hydrogenation

Insights into the High Activity and Methanol Selectivity of the Zn/ZrO₂ Solid Solution Catalyst for CO₂ Hydrogenation

Catalytic processes for the direct synthesis of dimethyl carbonate from CO₂ and methanol: a review