CO2 hydrogenation to methanol over Zr- and Ce-doped indium oxide

Salomone, Fabio; Sartoretti, Enrico; Ballauri, Sabrina; Castellino, Micaela; Novara, Chiara; Giorgis, Fabrizio; Pirone, Raffaele; Bensaid, Samir

doi:10.1016/j.cattod.2023.01.030

Cited by 13 publications

(24 citation statements)

References 48 publications

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“…Figures S3 and 1 illustrate the X‐ray diffraction patterns of supports and Pd‐containing materials, respectively. The presence of the (111), (200), (220), (311), (222), (400), (331) and (420) peaks proves the presence of the typical cubic fluorite structure of CeO 2 catalysts [22–24] . Moreover, considering that no peak splitting was observed within the patterns reported in Figure S3 and Figure 1, a solid solution between ceria and praseodymia was formed in the Ce90Pr10 samples [25] .…”

Section: Resultsmentioning

confidence: 60%

“…The presence of the (111), (200), (220), (311), ( 222), (400), (331) and (420) peaks proves the presence of the typical cubic fluorite structure of CeO 2 catalysts. [22][23][24] Moreover, considering that no peak splitting was observed within the patterns reported in Figure S3 and Figure 1, a solid solution between ceria and praseodymia was formed in the Ce90Pr10 samples. [25] This result was expected, considering the very close ionic radii of Ce 4 + /Ce 3 + and Pr 4 + /Pr 3 + ions (Ce 4 + = 0.97 Å, Ce 3 + = 1.143 Å, Pr 4 + = 0.96 Å, Pr 3 + = 1.126 Å).…”

Section: Characterization Of the Powdered Catalystsmentioning

confidence: 71%

“…The deconvolution process was made through the use of 10 peaks (five for the 3d 5/2 level and five for the 3d 3/2 level). In particular, the v 0 ‐u 0 and the v’‐u’ pairs were ascribed to the presence of Ce 3+ ions, while the v‐u, v’’‐u’’ and v’’’‐u’’’ pairs were linked to the presence of oxidized cerium ions (Ce 4+ ) [24,34,42] . Similarly, spectra in the Pr 3d core level are reported in Figure S6 and the deconvolution process was carried out with 5 peaks for the 3d 5/2 level and 5 peaks for the 3d 3/2 level.…”

Section: Resultsmentioning

confidence: 99%

“…In particular, the v 0 -u 0 and the v'-u' pairs were ascribed to the presence of Ce 3 + ions, while the v-u, v''-u'' and v'''-u''' pairs were linked to the presence of oxidized cerium ions (Ce 4 + ). [24,34,42] Similarly, spectra in the Pr 3d core level are reported in Figure S6 and the deconvolution process was carried out with 5 peaks for the 3d 5/ 2 level and 5 peaks for the 3d 3/2 level. The b 0 -a 0 and the b'-a' pairs lined to Pr 3 + ions, while the b-a, b''-a'' and b'''-a''' pairs to Pr 4 + ions.…”

Section: Samplementioning

confidence: 99%

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Mesoporous Ceria and Ceria‐Praseodymia as High Surface Area Supports for Pd‐based Catalysts with Enhanced Methane Oxidation Activity

Ballauri,

Sartoretti,

Castellino

et al. 2024

ChemCatChem

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In recent years, Pd/CeO2 materials have proven to be effective catalysts for the total oxidation of methane. In this work, three different synthesis routes were used to prepare high specific surface area supports, consisting of pure CeO2 and 10 at% Pr‐doped ceria (Ce90Pr10). Nano‐structured spheres were obtained with a microwave‐assisted synthesis, dumbbell‐like particles were produced through a urea‐based hydrothermal method, and ordered mesoporous oxides were prepared by using SBA‐15 as hard‐template. The six materials were then impregnated with 2 wt% Pd, calcined at 500 °C, and comprehensively characterized. All the samples retained their high surface area after impregnation (75–110 m2 g−1), allowing a good dispersion of palladium. No significant structural or morphological differences were observed upon Pr doping, but a higher Pd oxidation state was induced by Pr‐doped supports. However, all Pd/CeO2 and Pd/Ce90Pr10 catalysts exhibited similar activity for dry methane oxidation below 500 °C, regardless of the synthesis technique and of the Pr presence: they all achieved almost complete CH4 oxidation at 400 °C, showing a really remarkable improvement with respect to analogous low surface area supports. A promoting role of Pr was instead noticed in wet conditions, thanks to its ability to counteract water‐induced deactivation phenomena.

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Section: Resultsmentioning

confidence: 60%

Section: Characterization Of the Powdered Catalystsmentioning

confidence: 71%

Section: Resultsmentioning

confidence: 99%

Section: Samplementioning

confidence: 99%

See 2 more Smart Citations

Mesoporous Ceria and Ceria‐Praseodymia as High Surface Area Supports for Pd‐based Catalysts with Enhanced Methane Oxidation Activity

Ballauri,

Sartoretti,

Castellino

et al. 2024

ChemCatChem

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“…Later, HCOO* was further hydrogenated into CH 3 OH via the pathway of HCOO*→H 2 CO*→H 3 CO*→CH 3 OH. Apart from ZrO 2 , Ga 2 O 3 [ 84 ], CeO 2 [ 105 ], and MnO [ 106 ] were also used to combine with In 2 O 3 for converting CO 2 into methanol, and their promotion for In 2 O 3 performance was also associated with the In 2 O 3 dispersion, metal–support interactions, or tuning of basic sites.…”

Section: In 2 O 3 -Based Cataly...mentioning

confidence: 99%

Recent Advances of Indium Oxide-Based Catalysts for CO2 Hydrogenation to Methanol: Experimental and Theoretical

Cai

Tan

et al. 2023

Materials

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Methanol synthesis from the hydrogenation of carbon dioxide (CO2) with green H2 has been proven as a promising method for CO2 utilization. Among the various catalysts, indium oxide (In2O3)-based catalysts received tremendous research interest due to the excellent methanol selectivity with appreciable CO2 conversion. Herein, the recent experimental and theoretical studies on In2O3-based catalysts for thermochemical CO2 hydrogenation to methanol were systematically reviewed. It can be found that a variety of steps, such as the synthesis method and pretreatment conditions, were taken to promote the formation of oxygen vacancies on the In2O3 surface, which can inhibit side reactions to ensure the highly selective conversion of CO2 into methanol. The catalytic mechanism involving the formate pathway or carboxyl pathway over In2O3 was comprehensively explored by kinetic studies, in situ and ex situ characterizations, and density functional theory calculations, mostly demonstrating that the formate pathway was extremely significant for methanol production. Additionally, based on the cognition of the In2O3 active site and the reaction path of CO2 hydrogenation over In2O3, strategies were adopted to improve the catalytic performance, including (i) metal doping to enhance the adsorption and dissociation of hydrogen, improve the ability of hydrogen spillover, and form a special metal-In2O3 interface, and (ii) hybrid with other metal oxides to improve the dispersion of In2O3, enhance CO2 adsorption capacity, and stabilize the key intermediates. Lastly, some suggestions in future research were proposed to enhance the catalytic activity of In2O3-based catalysts for methanol production. The present review is helpful for researchers to have an explicit version of the research status of In2O3-based catalysts for CO2 hydrogenation to methanol and the design direction of next-generation catalysts.

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The Oscillatory Behaviour of Cu‐ZSM‐5 Catalysts for N₂O Decomposition: Investigation of Cu Species by Complementary Techniques

Rizzetto,

Sartoretti,

Khoma

et al. 2024

ChemPhysChem

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Copper‐exchanged ZSM‐5 (Cu‐ZSM‐5) is a promising catalyst thanks to the Cu redox pair. A particular feature of this material consists in the presence of spontaneous isothermal oscillations which take place during N2O decomposition reaction, depending on the operating conditions. In the present work, a set of five Cu‐ZSM‐5 catalysts are synthesised by three procedures and three different copper precursor concentrations: i) wet impregnation, ii) single ion exchange, and iii) double ion exchange. Catalytic tests reveal that the ion‐exchanged samples exhibit a low catalytic activity and no oscillatory behaviour, except for the twice‐exchanged sample which achieves an average N2O conversion of 26% at 400 °C. Conversely, the impregnated samples reach higher levels of N2O conversion (66% for Cu5ZSM5_WI and 72% for Cu10ZSM5_WI) and demonstrate a similar oscillating pattern. Further investigations disclosed that the most active catalysts, characterised by the presence of oscillatory behaviour, have more abundant and easily reducible copper specis (ICP, EDX and H2‐TPR) which interacts better with the zeolitic support (FT‐IR). Catalytic tests under a long time on stream (TOS) suggest that either self‐organised patterns or deterministic chaos can be achieved during the reaction, depending on the operating conditions, such as temperature and contact time.

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CO2 hydrogenation to methanol over Zr- and Ce-doped indium oxide

Cited by 13 publications

References 48 publications

Mesoporous Ceria and Ceria‐Praseodymia as High Surface Area Supports for Pd‐based Catalysts with Enhanced Methane Oxidation Activity

Mesoporous Ceria and Ceria‐Praseodymia as High Surface Area Supports for Pd‐based Catalysts with Enhanced Methane Oxidation Activity

Recent Advances of Indium Oxide-Based Catalysts for CO2 Hydrogenation to Methanol: Experimental and Theoretical

The Oscillatory Behaviour of Cu‐ZSM‐5 Catalysts for N₂O Decomposition: Investigation of Cu Species by Complementary Techniques

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CO2 hydrogenation to methanol over Zr- and Ce-doped indium oxide

Cited by 13 publications

References 48 publications

Mesoporous Ceria and Ceria‐Praseodymia as High Surface Area Supports for Pd‐based Catalysts with Enhanced Methane Oxidation Activity

Mesoporous Ceria and Ceria‐Praseodymia as High Surface Area Supports for Pd‐based Catalysts with Enhanced Methane Oxidation Activity

Recent Advances of Indium Oxide-Based Catalysts for CO2 Hydrogenation to Methanol: Experimental and Theoretical

The Oscillatory Behaviour of Cu‐ZSM‐5 Catalysts for N2O Decomposition: Investigation of Cu Species by Complementary Techniques

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Product

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The Oscillatory Behaviour of Cu‐ZSM‐5 Catalysts for N₂O Decomposition: Investigation of Cu Species by Complementary Techniques