Role of ZrO2 and CeO2 support on the In2O3 catalyst activity for CO2 hydrogenation

Sharma, Poonam; Ho, Phuoc Hoang; Shao, Jieling; Creaser, Derek; Olsson, Louise

doi:10.1016/j.fuel.2022.125878

Cited by 26 publications

(8 citation statements)

References 68 publications

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“…A relatively low value of BE of In 3d5/2 for IZ-comb indicated that there was less electron density around In on the surface (depth up to 5–6 nm, reference and this seemed to be characteristic of the combustion method because the I-comb sample had a similar value of binding energy of In 3d5/2 (443.5 eV) (Figure S8a). Interestingly, the In 2 O 3 prepared by thermal decomposition of the In(NO 3 ) 3 precursor also showed a similar value of In 3d5/2 at 443.6 eV in the literature . To clarify that a shift to the lower binding energy of the I-comb sample was not because of the instrumentation issue, we also performed the measurements for other indium oxide samples.…”

Section: Resultssupporting

confidence: 58%

Effect of the Preparation Methods on the Physicochemical Properties of Indium-Based Catalysts and Their Catalytic Performance for CO₂ Hydrogenation to Methanol

Ho,

Tizzanini,

Ghosh

et al. 2024

Energy Fuels

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Indium oxides (In2O3) and indium oxides supported zirconia (ZrO2) have been known possible alternatives for conventional copper-based catalysts in the CO2-hydrogenation to methanol. This study aims to investigate the effect of preparation techniques on the physicochemical properties of indium-based materials and their catalytic performance for the hydrogenation of CO2 to methanol. Two series of both single oxide In2O3 and binary In2O3–ZrO2 have been synthesized by combustion, urea hydrolysis, and precipitation with different precipitating agents (sodium carbonate and ammonia/ethanol solution). Physicochemical properties of materials are characterized by elemental analysis, XRD, N2 physisorption, SEM/EDX, micro-Raman, XPS, H2-TPR, and CO2-TPD. Cubic In2O3 was the common phase generated by all four synthesis methods, except for urea hydrolysis, where rhombohedral In2O3 was additionally present. The combustion method produced the materials with the lowest specific surface areas while the precipitation using ammonia/ethanol aided in creating more oxygen defects. The synthesis methods strongly influenced the degree of interaction between the oxides and resulted in improvements in properties that boosted the catalytic performance of the binary oxides compared to their single-oxide counterparts.

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Section: Resultssupporting

confidence: 58%

Effect of the Preparation Methods on the Physicochemical Properties of Indium-Based Catalysts and Their Catalytic Performance for CO₂ Hydrogenation to Methanol

Ho,

Tizzanini,

Ghosh

et al. 2024

Energy Fuels

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“…[29,30] Both supports, however, showed only weak interactions with CO 2 , as evident from the CO 2 -TPD spectra (Figure 2a), that exhibit a desorption peak between 100-300 °C, that can be assigned to physisorbed CO 2. [31,32] Desorption peaks assigned to chemisorbed CO 2 through thermally induced oxygen vacancies can be observed in a small amount. [12,30] Nevertheless, ZrO 2 (AA) demonstrates slightly less interaction with CO 2 compared to ZrO 2 (SG) in the low temperature area (Figure 2a, Table S3).…”

Section: Impact Of Different Zro 2 -Supports On the Catalytic Perform...mentioning

confidence: 99%

Indium‐based Catalysts for CO₂ Hydrogenation to Methanol: Key Aspects for Catalytic Performance

Wesner,

Kampe,

Herrmann

et al. 2023

ChemCatChem

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CO2 hydrogenation utilizing sustainably produced hydrogen and CO2 derived from industrial exhaust gas represents a pivotal technology for chemical energy storage and climate change mitigation. This work aimed to identify the best combination of catalyst support, synthesis method and promotor for In2O3/ZrO2 catalysts in a typical fixed‑bed configuration. Intense characterization using ICP‐OES, XRD, XPS, N2‐physisorption, CO2‐TPD, H2‐TPR and SEM‐EDX provide molecular insights into the different effects caused by various synthesis methods and doping elements. Doping the most promising In2O3/ZrO2 (M‐SG) catalyst with 0.7 wt.% NiO by wetness impregnation using an ethanol/water mixture as a solvent, an increased methanol production rate of 0.497 gMeOH∙ ⋅h‐1 could already be achieved at 250°C. Hereby, the low amount of highly dispersed NiO promotes H2 activation via hydrogen spillover, leading to sustained catalytic activity for 100 hours of time‑on‑stream.

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“…In situ DRIFTS experiments were conducted to study the different behavior between Ni/In 2 O 3 and 5Al 2 O 3 /Ni/In 2 O 3 catalysts in the reduction and consecutive oxidation processes. It can be seen from Figure a that the −OH band intensity (3200–3600 cm –1 ) of the Ni/In 2 O 3 catalyst exhibited a more obvious increase in the H 2 reduction process as compared to the 5Al 2 O 3 /Ni/In 2 O 3 catalyst, which suggested that the O species of Ni/In 2 O 3 were more likely to react with H 2 (high reducibility). Surprisingly, the weak −OH signal was found on 5Al 2 O 3 /Ni/In 2 O 3 compared to Ni/In 2 O 3 because of the considerably faster reduction rate on the Ni/In 2 O 3 sample by H 2 compared to 5Al 2 O 3 /Ni/In 2 O 3 .…”

Section: Resultsmentioning

confidence: 99%

Antiover-Reduction of Ni/In₂O₃ Nanocatalysts by Atomic Layer Deposition of Al₂O₃ Films for Durable CO₂ Hydrogenation to Methanol

Cai,

Lin,

Cha

et al. 2024

ACS Catal.

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The supported Ni/In 2 O 3 catalysts are of great interest in CO 2 hydrogenation, but the formation of the In 0 or Ni− In alloy phases due to over-reduction would lead to rapid catalyst deactivation. Herein, thin Al 2 O 3 films were deposited on the Ni/ In 2 O 3 surface by atomic layer deposition (ALD) as an antireduction agent, which enables the In 2 O 3 catalyst to maintain a significant abundance of active In 3+ species even during hightemperature H 2 treatment (400 °C, 2 h), thereby effectively resisting the deactivation caused by over-reduction of In 2 O 3 . Various characterization methods confirm the antiover-reduction effect of ALD-Al 2 O 3 films, namely, inhibiting the formation of In 0 and In 3 Ni 2 alloys during high-temperature H 2 treatment and facilitating the reoxidation of low-valence In to form the active In 2 O 3−x phase in the presence of a CO 2 atmosphere. As treated with H 2 at 400 °C, the 5Al 2 O 3 /Ni/In 2 O 3 -R400 catalyst exhibited an STY MeOH of 7.39 g MeOH h −1 g Ni −1 and a methanol selectivity of 64% (reaction conditions: 3 MPa, 300 °C, and 12,000 mL g cat −1 h −1 ). Particularly, the STY MeOH increased by 11.5 times as compared with that of the Ni/In 2 O 3 -R400 catalyst without coating the ALD-Al 2 O 3 layer (0.59 g MeOH h −1 g Ni −1 ). Density functional theory (DFT) calculations validate the effectiveness of specific charge transfer tendencies in suppressing the over-reduction of high-valence In species. Through the analysis of the crystal orbital Hamilton population (COHP) and projected density of states (PDOS) electronic structures of the adsorbate species, the Al 2 O 3 /Ni/In 2 O 3 catalyst is shown to significantly enhance CO 2 activation and further catalytic reactions. Accordingly, this study unveils the deactivation mechanism of In 2 O 3 -based catalysts due to over-reduction and provides a method to regulate their reduction level by depositing ALD-Al 2 O 3 films on the In 2 O 3 -based catalysts.

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Role of ZrO2 and CeO2 support on the In2O3 catalyst activity for CO2 hydrogenation

Cited by 26 publications

References 68 publications

Effect of the Preparation Methods on the Physicochemical Properties of Indium-Based Catalysts and Their Catalytic Performance for CO₂ Hydrogenation to Methanol

Effect of the Preparation Methods on the Physicochemical Properties of Indium-Based Catalysts and Their Catalytic Performance for CO₂ Hydrogenation to Methanol

Indium‐based Catalysts for CO₂ Hydrogenation to Methanol: Key Aspects for Catalytic Performance

Antiover-Reduction of Ni/In₂O₃ Nanocatalysts by Atomic Layer Deposition of Al₂O₃ Films for Durable CO₂ Hydrogenation to Methanol

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Role of ZrO2 and CeO2 support on the In2O3 catalyst activity for CO2 hydrogenation

Cited by 26 publications

References 68 publications

Effect of the Preparation Methods on the Physicochemical Properties of Indium-Based Catalysts and Their Catalytic Performance for CO2 Hydrogenation to Methanol

Effect of the Preparation Methods on the Physicochemical Properties of Indium-Based Catalysts and Their Catalytic Performance for CO2 Hydrogenation to Methanol

Indium‐based Catalysts for CO2 Hydrogenation to Methanol: Key Aspects for Catalytic Performance

Antiover-Reduction of Ni/In2O3 Nanocatalysts by Atomic Layer Deposition of Al2O3 Films for Durable CO2 Hydrogenation to Methanol

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Product

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Effect of the Preparation Methods on the Physicochemical Properties of Indium-Based Catalysts and Their Catalytic Performance for CO₂ Hydrogenation to Methanol

Effect of the Preparation Methods on the Physicochemical Properties of Indium-Based Catalysts and Their Catalytic Performance for CO₂ Hydrogenation to Methanol

Indium‐based Catalysts for CO₂ Hydrogenation to Methanol: Key Aspects for Catalytic Performance

Antiover-Reduction of Ni/In₂O₃ Nanocatalysts by Atomic Layer Deposition of Al₂O₃ Films for Durable CO₂ Hydrogenation to Methanol