Strong Evidence of the Role of H2O in Affecting Methanol Selectivity from CO2 Hydrogenation over Cu-ZnO-ZrO2

Wang, Yuhao; Gao, Wengui; Li, Kongzhai; Zheng, Yane; Xie, Zhenhua; Wei, Na; Chen, Jingguang G.; Wang, Hua

doi:10.1016/j.chempr.2019.10.023

Cited by 162 publications

(104 citation statements)

References 58 publications

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“…In comparison, on the D4 defective In 2 O 3 (110) surface, hydrogenation of mono-H 2 CO* to H 3 CO* is the RDS with a high energy barrier of 1.14 eV . The desorption energy of H 3 CO* is 1.62 eV, suggesting its strong stability, similar to previous experimental and theoretical reports that H 3 CO* is the key intermediate in methanol synthesis. ,,, …”

Section: Resultssupporting

confidence: 81%

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: Resultssupporting

confidence: 81%

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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“…However, major concerns regarding CO 2 capture and storage lie in separation efficiency, operation costs, and long-term stability [4,5]. In comparison, transformation of cheap and abundant CO 2 to value-added products (e.g., CH 4 , CH 3 OH, C 2 -C 4 hydrocarbons) via hydrogenation has drawn tremendous attentions [1,[6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23]. In some works, CO 2 splitting (dissociation) and reversed water-gas shift (RWGS) are considered a kind of hydrogenation process; however, a reaction involving both C-O bond breaking and C-H bond formation will be mainly covered in this review, such as methanation (Equation ( 1)) and methanol production (Equation ( 2)).…”

Section: Introductionmentioning

confidence: 99%

Dielectric Barrier Discharge Plasma-Assisted Catalytic CO2 Hydrogenation: Synergy of Catalyst and Plasma

Gao

Liang

et al. 2022

Catalysts

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CO2 hydrogenation is an effective way to convert CO2 to value-added chemicals (e.g., CH4 and CH3OH). As a thermal catalytic process, it suffers from dissatisfactory catalytic performances (low conversion/selectivity and poor stability) and high energy input. By utilizing the dielectric barrier discharge (DBD) technology, the catalyst and plasma could generate a synergy, activating the whole process in a mild condition, and enhancing the conversion efficiency of CO2 and selectivity of targeted product. In this review, a comprehensive summary of the applications of DBD plasma in catalytic CO2 hydrogenation is provided in detail. Moreover, the state-of-the-art design of the reactor and optimization of reaction parameters are discussed. Furthermore, several mechanisms based on simulations and experiments are provided. In the end, the existing challenges of this hybrid system and corresponding solutions are proposed.

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“…), hydrogenating CO 2 via thermo-catalysis can not only mitigate CO 2 emissions, but also effective in providing valuable organic chemicals. [5,6] Significant progress has been made in the selective catalytic hydrogenation of CO 2 into C 2 + hydrocarbons (e. g., olefins, [7][8][9][10][11][12] isoparaffins, [13] and aromatics [14][15][16][17][18] and oxygenates (e. g., methanol [19,20] and ethanol [21] ). Among these products, olefins are basic feedstocks for the production of various important commodities.…”

Section: Introductionmentioning

confidence: 99%

Potassium as a Versatile Promoter to Tailor the Distribution of the Olefins in CO₂ Hydrogenation over Iron‐Based Catalyst

Qiao

Wang

et al. 2022

ChemCatChem

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= ) of 40 % and 27 μmol CO2 g Fe À 1 s À 1 , respectively, were obtained at 3 wt% of K under the same reaction conditions. At 3 wt% of K and above, the overall selectivity to the olefins (inclusive of light olefins and heavy olefins) remained at as high as ca. 60 % at high CO 2 conversion of ca. 50 %. Comprehensive characterizations revealed that the K promoter enhanced the basicity of the catalyst, which facilitates the formation of χ-Fe 5 C 2 , the key active phase for CO 2 hydrogenation. A good linear relationship is established between the surface basicity and the content of χ-Fe 5 C 2 . Moreover, the K promoter weakened the adsorption of the olefins, which inhibited the secondary hydrogenation of the olefins, thus improving the selectivity to the olefins. This work demonstrates that K is a highly promising promoter for the tailoring of the types of the olefinic products in CO 2 hydrogenation.

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Strong Evidence of the Role of H2O in Affecting Methanol Selectivity from CO2 Hydrogenation over Cu-ZnO-ZrO2

Cited by 162 publications

References 58 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

Dielectric Barrier Discharge Plasma-Assisted Catalytic CO2 Hydrogenation: Synergy of Catalyst and Plasma

Potassium as a Versatile Promoter to Tailor the Distribution of the Olefins in CO₂ Hydrogenation over Iron‐Based Catalyst

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Strong Evidence of the Role of H2O in Affecting Methanol Selectivity from CO2 Hydrogenation over Cu-ZnO-ZrO2

Cited by 162 publications

References 58 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

Dielectric Barrier Discharge Plasma-Assisted Catalytic CO2 Hydrogenation: Synergy of Catalyst and Plasma

Potassium as a Versatile Promoter to Tailor the Distribution of the Olefins in CO2 Hydrogenation over Iron‐Based Catalyst

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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

Potassium as a Versatile Promoter to Tailor the Distribution of the Olefins in CO₂ Hydrogenation over Iron‐Based Catalyst