How the interaction between In2O3-ZrO2 promotes the isobutene synthesis from ethanol?

Bronsato, Bruna J. da S.; Zonetti, Priscila C.; Moreira, Carla R.; Mendoza, Cesar D.; Costa, M.E.H. Maia da; Alves, Odivaldo C.; Avillez, Roberto R. de; Appel, Lucia G.

doi:10.1016/j.cattod.2020.07.004

Cited by 6 publications

(13 citation statements)

References 54 publications

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“…While almost exclusive formation of methanol was found on In 2 O 3 -based catalysts in early studies, methanol selectivity ranging from 20% to 90% has since been reported. ,,− , By tuning the loading of In 2 O 3 onto a ZrO 2 support (0.1–5 wt %), Chen et al found the stepwise hydrogenation of a key reaction intermediate, e.g., *HCOO, and a shift of the products from CO to methanol . To probe the unique role of m- ZrO 2 , Frei et al prepared solid solutions of In 2 O 3 –ZrO 2 and found no electronic communications between ZrO 2 and In 2 O 3 ; instead, m- ZrO 2 was found to exhibit less favorable epitaxial lattice matching with In 2 O 3 and induced tensile strain at the In 2 O 3 / m- ZrO 2 interface that lead to a higher concentration of oxygen vacancies (O-vacancies) in In 2 O 3 . It was concluded that the defect chemistry of ZrO 2 could lead to the elucidation of the role of ZrO 2 as a unique support and the reaction mechanism of In 2 O 3 / m- ZrO 2 catalyzed CO 2 HR to form methanol …”

Section: Introductionmentioning

confidence: 99%

Support Effect and Surface Reconstruction in In₂O₃/m-ZrO₂ Catalyzed CO₂ Hydrogenation

et al. 2022

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We investigate the chemical and structural dynamics at the interface of In 2 O 3 /m-ZrO 2 and their consequences on the CO 2 hydrogenation reaction (CO 2 HR) under reaction conditions. While acting to enrich CO 2 , monoclinic zirconia (m-ZrO 2 ) was also found to serve as a chemical and structural modifier of In 2 O 3 that directly governs the outcome of the CO 2 HR. These modifying effects include the following: (1) Under reaction conditions (above 623 K), partially reduced In 2 O 3 , i.e., InO x (0 < x < 1.5), was found to migrate in and out of the subsurface of m-ZrO 2 in a semireversible manner, where m-ZrO 2 accommodates and stabilizes InO x by serving as a reservoir. The decreased concentration of surface InO x under elevated temperatures coincides with significantly decreased selectivity toward methanol and a sharp increase of the reverse water−gas shift reaction. The reconstruction-induced variation of InO x concentration appears to be one of the most important factors contributing to the altered catalytic performance of CO 2 HR at different reaction conditions. (2) The strong interactions and reactions between m-ZrO 2 and In 2 O 3 result in the activation of a pool of In−O bonds at the In 2 O 3 /m-ZrO 2 interface to form oxygen vacancies. On the other hand, the high dispersity of In 2 O 3 nanostructures onto m-ZrO 2 prevents their over-reduction under catalytically relevant conditions (up to 673 K), when bare In 2 O 3 is unavoidably reduced into the metallic phase (In 0 ). The relationship between the extent of reduction of In 2 O 3 and catalytic performance (CO 2 conversion, CH 3 OH selectivity, or yield of CH 3 OH) suggests the presence of an optimum coverage of surface InO x and oxygen vacancies under reaction conditions. The conventional model that links catalytic performance solely to the coverage of oxygen vacancies appears invalid in the present case. In situ analysis also allows the observation of surface reaction intermediates and their interconversions, including the reduction of CO 3 * into formate, a precursor for the formation of methanol and CO. The combinative ex situ and in situ study sheds light on the reaction mechanism of the CO 2 HR on In 2 O 3 /m-ZrO 2 -based catalysts. Our findings on the large-scale surface reconstructions, support effect, and the reaction mechanism of In 2 O 3 /m-ZrO 2 for CO 2 HR may apply to other related metal oxide catalyzed CO 2 reduction reactions. KEYWORDS: In 2 O 3 /m-ZrO 2 , support effect, in situ, CO 2 hydrogenation, reconstruction, ambient pressure X-ray photoelectron spectroscopy

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Section: Introductionmentioning

confidence: 99%

Support Effect and Surface Reconstruction in In₂O₃/m-ZrO₂ Catalyzed CO₂ Hydrogenation

et al. 2022

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“…Moreover, it is known that Lewis acid sites are present on ZrO 2 . 29 Adding Zn to m-ZrO 2 (6ZnZr), the number of strong acidic sites decreases, whereas the number of strong basic sites slightly increase. In addition, the selectivity to ethene drops from 74% to 2% (Table 5), whereas the selectivity to acetone, CO 2 and isobutene increases.…”

Section: Resultsmentioning

confidence: 99%

“…Taking into account the data shown in the previous section and also pieces of information from the literature related to In, Zr-based catalysts, 1,29 the following steps can be proposed for the isobutene synthesis from ethanol: firstly, the oxidative dehydrogenation of ethanol forms acetaldehyde; then, this aldehyde is oxidized to acetate species which condense, generating acetone; next, this ketone undergoes an aldol condensation; finally, the intermediate generated is degraded, forming isobutene and acetaldehyde (Fig. 9).…”

Section: The Ethanol-to-isobutene Conversion Mechanismmentioning

confidence: 99%

The role of oxygen vacancies and Zn in isobutene synthesis from ethanol employing Zn, Zr-based catalysts

Pinheiro,

de Souza,

Chagas

et al. 2024

Catal. Sci. Technol.

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“…Also, two forms of Zr 3+ defects are detected in this sample: axially symmetric Zr 3+ ions (g = 1.973) and another signal with g = 1.962. The latter is caused by a paramagnetic defect, 55 known as the T center. The Zr 3+ cations might be associated with coordinatively unsaturated sites generated with OVs.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Highly Efficient Hydrosilylation of Ethyne over Pt/ZrO₂ Catalysts with Size-Dependent Metal–Support Interactions

Zhang

Zheng

et al. 2022

Ind. Eng. Chem. Res.

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Replacing homogeneous noble-metal catalysts with supported catalysts in hydrosilylation reactions can overcome the difficulties of catalyst recovery and regeneration. Here, we report the scalable synthesis of heterogeneous Pt/ZrO2 catalysts with 1–5 wt % Pt supported on commercial ZrO2 nanocrystals. Pt/ZrO2 can effectively catalyze the hydrosilylation of triethoxysilane (TES) with ethyne to high-value triethoxyvinylsilane, even superior to the common homogeneous catalyst (H2PtCl6). Intensive characterizations indicate that the coating of ZrO x on Pt greatly depends on the size of Pt, with more ZrO x overlayers on smaller Pt metal particles. Among all the catalysts, 2Pt/ZrO2 exhibits the highest activity, optimal selectivity, and reusability toward hydrosilylation of TES with ethyne. The unusual catalytic properties of 2Pt/ZrO2 can be attributed to its more abundant surface PtO x species and the electron transfer between Pt and ZrO2. This change in local electronic properties promotes catalytic activity, which is also supported by the corresponding theoretical calculation. This work advances the understanding of metal–support interactions and provides a powerful approach to designing environmentally friendly heterogeneous catalysts for the industrially important hydrosilylation process.

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How the interaction between In2O3-ZrO2 promotes the isobutene synthesis from ethanol?

Cited by 6 publications

References 54 publications

Support Effect and Surface Reconstruction in In₂O₃/m-ZrO₂ Catalyzed CO₂ Hydrogenation

Support Effect and Surface Reconstruction in In₂O₃/m-ZrO₂ Catalyzed CO₂ Hydrogenation

The role of oxygen vacancies and Zn in isobutene synthesis from ethanol employing Zn, Zr-based catalysts

Highly Efficient Hydrosilylation of Ethyne over Pt/ZrO₂ Catalysts with Size-Dependent Metal–Support Interactions

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How the interaction between In2O3-ZrO2 promotes the isobutene synthesis from ethanol?

Cited by 6 publications

References 54 publications

Support Effect and Surface Reconstruction in In2O3/m-ZrO2 Catalyzed CO2 Hydrogenation

Support Effect and Surface Reconstruction in In2O3/m-ZrO2 Catalyzed CO2 Hydrogenation

The role of oxygen vacancies and Zn in isobutene synthesis from ethanol employing Zn, Zr-based catalysts

Highly Efficient Hydrosilylation of Ethyne over Pt/ZrO2 Catalysts with Size-Dependent Metal–Support Interactions

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Product

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Support Effect and Surface Reconstruction in In₂O₃/m-ZrO₂ Catalyzed CO₂ Hydrogenation

Support Effect and Surface Reconstruction in In₂O₃/m-ZrO₂ Catalyzed CO₂ Hydrogenation

Highly Efficient Hydrosilylation of Ethyne over Pt/ZrO₂ Catalysts with Size-Dependent Metal–Support Interactions