Morphology-engineered highly active and stable Pd/TiO2 catalysts for CO2 hydrogenation into formate

Zhang, JJing; Liao, Weiqi; Zheng, Hao; Zhang, Yunshang; Xia, Lebing; Teng, Botao; Lu, Ji-Qing; Huang, Weixin; Zhang, Zhenhua

doi:10.1016/j.jcat.2021.11.035

Cited by 41 publications

(38 citation statements)

References 49 publications

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“…This could be due to the transformation of surface carbonaceous species into formate species occurred in the H 2 atmosphere over the Ni/CeO 2 catalysts with high Ni loadings, as previously reported results. 40,48,51 Therefore, these results demonstrate the formate species acting as the dominant intermediate species for CO 2 hydrogenation over the Ni/CeO 2 catalysts. Afterward, the stepwise reactions were further conducted, and the results are shown in Figure 9.…”

Section: Resultsmentioning

confidence: 99%

“…Although the consumption of formate species is still the largest among different carbonaceous species after H 2 purging for 30 min, interestingly, the decreasing fractions of formate species are not significantly different at the first 5 min over the 0.1%Ni/CeO 2 catalyst and even becomes slower than other carbonaceous species at the initial 10 min over the 5%Ni/CeO 2 catalysts. This could be due to the transformation of surface carbonaceous species into formate species occurred in the H 2 atmosphere over the Ni/CeO 2 catalysts with high Ni loadings, as previously reported results. ,, Therefore, these results demonstrate the formate species acting as the dominant intermediate species for CO 2 hydrogenation over the Ni/CeO 2 catalysts.…”

Section: Resultsmentioning

confidence: 99%

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Unveiling the Key Factors in Determining the Activity and Selectivity of CO₂ Hydrogenation over Ni/CeO₂ Catalysts

et al. 2022

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Identification of the key factors governing the activity and product selectivity of CO2 hydrogenation is crucial for developing improved catalysts but is still challenging. Herein, CeO2-supported Ni catalysts (Ni/CeO2) with different Ni particle sizes were used for CO2 hydrogenation. The results reveal that the catalytic activity and product selectivity are tightly associated with interfacial oxygen vacancies and the structure of supported Ni species, respectively. With the increase of Ni loading, more surface oxygen vacancies located at the Ni–CeO2 interfaces are responsible for the adsorption and activation of CO2, contributing to reaction activity. Meanwhile, the increased Ni particle size together with more percentage of metallic Ni species is beneficial for both hydrogenation properties and CO binding capacity, resulting in the product selectivity gradually transforming from CO to CH4. The in situ diffuse reflectance infrared Fourier transform spectroscopy results confirm the CO generated by an associated mechanism involving the key intermediate of formate species. These results greatly deepen the fundamental understanding of Ni/CeO2 catalysts for CO2 hydrogenation.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Unveiling the Key Factors in Determining the Activity and Selectivity of CO₂ Hydrogenation over Ni/CeO₂ Catalysts

et al. 2022

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“…Catalytic CO 2 hydrogenation is an important reaction since such a reaction can realize the oriented conversion of the emitted CO 2 toward valuable chemicals and has drawn extensive attention. − Previous studies revealed that supported metal catalysts are regarded as a superb candidate for this reaction, and their catalytic properties are sensitive to the interfacial structures. − ,− For instance, Yan et al reported that the CO 2 hydrogenation selectivity could be tuned via metal–oxide interfacial sites, in which the Ni–ZrO 2 interfaces are the active sites of CO 2 methanation, while the reverse water–gas shift (RWGS) reaction proceeds over the Ni-FeO x interfaces . Similar results were also observed on supported Rh catalysts.…”

Section: Introductionmentioning

confidence: 99%

Decoupling the Interfacial Catalysis of CeO₂-Supported Rh Catalysts Tuned by CeO₂ Morphology and Rh Particle Size in CO₂ Hydrogenation

et al. 2023

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Metal–oxide interfaces play a crucial role in catalyzing CO2 conversion, while comprehensively decoupling interfacial catalysis is challenging due to their structural complexity. Herein, Rh/CeO2 catalysts, whose interfacial structures are finely tuned by altering the CeO2 morphologies and Rh particle sizes, were employed for CO2 hydrogenation. The results reveal that the density of interfacial oxygen vacancies that varies with the CeO2 morphologies determines the catalytic activity, while the product selectivity strongly depends on the nature of supported Rh species. With a decrease in Rh particle size, the weakened metallicity results in the suppression of the Sabatier reaction and thus the low CH4 selectivity. Meanwhile, the enhanced reverse water–gas shift process that is more easily catalyzed than the Sabatier reaction contributes to the promotion of catalytic CO2 efficiency. Interestingly, the CH4 selectivity increases with the reaction temperature rise at fine Rh particles, which could be ascribed to the enhanced H-spillover effect at high temperatures. Spectroscopic results confirm CO2 hydrogenation proceeding through a redox mechanism to generate an adsorbed CO intermediate that either is further hydrogenated into CH4 with strong CO adsorption capacity/H-spillover effect or desorbs directly into CO.

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“…This provides an excellent candidate to realize the study of structure‐activity relationships by employing oxide‐based NC model catalysts with one or two types of crystal planes exposed. In the past several years, increasing number of examples of morphology‐dependent catalytic properties of uniform oxide‐based NCs, such as Cu 2 O, [ 31‐36 ] Co 3 O 4 , [ 37 ] TiO 2 , [ 38‐39 ] ZnO, [ 40‐41 ] and Fe 2 O 3 [ 42‐43 ] have been comprehensively explored, also including several nice reviews published on this topic. [ 16‐24,44‐52 ]…”

Section: Introductionmentioning

confidence: 99%

Morphology‐Dependent Catalysis of CeO₂‐Based Nanocrystal Model Catalysts

et al. 2022

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Comprehensive Summary Recent progress in colloidal synthesis has realized the preparations of uniform nanocrystal (NC) model catalysts with rich and well‐controlled morphologies that were employed to explore structure‐activity relationships of powder catalysts, similar to single‐crystal‐based model catalysts under ultrahigh vacuum conditions but can work at the same conditions as powder catalysts without the “materials gap” and “pressure gap”. In this perspective, the CeO2‐based NC model catalysts with various morphologies are included and their relevant progresses are critically reviewed. The detailed descriptions of morphology‐controlled synthesis and characterizations of uniform CeO2 NCs, and morphology‐dependent catalysis of CeO2‐based NC model catalysts containing pure CeO2 NCs, CeO2‐supported oxide catalysts, and CeO2‐supported metal catalysts, provide us a comprehensive cognition in CeO2‐involved catalytic reactions and also open up a new approach for the fundamental studies of complex heterogeneous catalysis. Finally, a concept of oxide‐based NC model catalysts and outlook of oxide NCs acting not only as model catalysts for the fundamental study but also as the support in tailoring structures and optimizing performance of oxide‐involved catalysts are discussed.

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Morphology-engineered highly active and stable Pd/TiO2 catalysts for CO2 hydrogenation into formate

Cited by 41 publications

References 49 publications

Unveiling the Key Factors in Determining the Activity and Selectivity of CO₂ Hydrogenation over Ni/CeO₂ Catalysts

Unveiling the Key Factors in Determining the Activity and Selectivity of CO₂ Hydrogenation over Ni/CeO₂ Catalysts

Decoupling the Interfacial Catalysis of CeO₂-Supported Rh Catalysts Tuned by CeO₂ Morphology and Rh Particle Size in CO₂ Hydrogenation

Morphology‐Dependent Catalysis of CeO₂‐Based Nanocrystal Model Catalysts

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Morphology-engineered highly active and stable Pd/TiO2 catalysts for CO2 hydrogenation into formate

Cited by 41 publications

References 49 publications

Unveiling the Key Factors in Determining the Activity and Selectivity of CO2 Hydrogenation over Ni/CeO2 Catalysts

Unveiling the Key Factors in Determining the Activity and Selectivity of CO2 Hydrogenation over Ni/CeO2 Catalysts

Decoupling the Interfacial Catalysis of CeO2-Supported Rh Catalysts Tuned by CeO2 Morphology and Rh Particle Size in CO2 Hydrogenation

Morphology‐Dependent Catalysis of CeO2‐Based Nanocrystal Model Catalysts

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Unveiling the Key Factors in Determining the Activity and Selectivity of CO₂ Hydrogenation over Ni/CeO₂ Catalysts

Unveiling the Key Factors in Determining the Activity and Selectivity of CO₂ Hydrogenation over Ni/CeO₂ Catalysts

Decoupling the Interfacial Catalysis of CeO₂-Supported Rh Catalysts Tuned by CeO₂ Morphology and Rh Particle Size in CO₂ Hydrogenation

Morphology‐Dependent Catalysis of CeO₂‐Based Nanocrystal Model Catalysts