Promoting effects of indium doped Cu/CeO<sub>2</sub> catalysts on CO<sub>2</sub> hydrogenation to methanol

Rossi, Marco; Vieira, Luiz H.; Rasteiro, Letícia F.; Fraga, Marco A.; Assaf, José Mansur; Assaf, Elisabete Moreira

doi:10.1039/d2re00033d

Cited by 15 publications

(10 citation statements)

References 72 publications

(124 reference statements)

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“…Various catalysts based on CuZn-, In-, or PdZn-oxides have been developed and applied for the direct CO 2 hydrogenation to methanol. The achievements related to catalyst development and understanding of the reaction mechanisms and kinetics have been analyzed in plentiful review articles. ,,, CuZn-based catalysts modified with various promoters, e.g., In, − Pd, , Ga, Al, − Mg–Al, Zr, − and Ce, − were tested at relatively low temperatures (<523 K) and with stoichiometric H 2 /CO 2 = 3 feeds. A ternary Cu–Zn–ZrO 2 material shows promising performance due to its lower hydrophilicity and abundant oxygen vacancies in the lattice of ZrO 2 . − These properties affect the methanol selectivity and the CO 2 activation.…”

Section: Introductionmentioning

confidence: 99%

Identifying Catalyst Property Descriptors for CO₂ Hydrogenation to Methanol via Big-Data Analysis

et al. 2023

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Carbon dioxide (CO 2 ) capture and valorization have great potential for mitigating emissions of this greenhouse gas and accordingly for preserving the environment for future generations. In this regard, hydrogenation of CO 2 to methanol is highly attractive because this product is a valuable energy carrier and can also be used for production of various everyday commodities. Although many research papers on this topic have been published in the past decades, there is still a lack of fundamentals relevant to control catalyst performance. Herein, we demonstrate how statistically validated Big-Data analysis of available literature data identified hidden descriptors that can be applied for purposeful catalyst development and for identification of optimal reaction conditions. In view of catalyst development, the kinds of structural promoters or supports for bulk or supported Cu-, In-, or Pd-based catalysts are the most important descriptors for methanol selectivity, with Ce and Zr being the most efficient promoters. The type and the parameters of the preparation methods as well as the kind of active component precursors are also important in this regard. To validate the conclusion about the structural promoter, a series of supported CuZn-containing catalysts were prepared. The best-performing CuZn/CeO 2 catalyst outperformed the state-of-the-art CuZn-based catalysts tested at a total pressure of up to 30 bar using a feed with the ratio of H 2 /CO 2 of 3. In addition to the catalyst composition and the preparation method, our analysis suggests that the most often used Cu-based catalysts lose their methanol selectivity due to the decomposition of this product to CO. Our control experiments with the developed CuZn-based catalysts proved that this undesired reaction can be hindered when the catalyst support contains Ce or through increasing H 2 partial pressure. This knowledge is important for further catalyst development.

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Section: Introductionmentioning

confidence: 99%

Identifying Catalyst Property Descriptors for CO₂ Hydrogenation to Methanol via Big-Data Analysis

et al. 2023

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“…It is noted that reduced 30%Cu/CeO 2 contains both Cu/CeO 2 and CeO 2 /Cu inverse-type structures, with the latter one consisting of dispersed CeO 2 species attached to large Cu particles. 41,42 The heterogeneity of copper particles in the supported Cu/ CeO 2 catalysts prepared by the deposition-precipitation method is further illustrated by H 2 -TPR. As shown in Fig.…”

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confidence: 99%

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confidence: 99%

Dynamics of the Cu/CeO₂catalyst during methanol steam reforming

Jin

Wang

et al. 2022

Catal. Sci. Technol.

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“…Another effective strategy to promote the activity of Cu‐based catalysts is the doping of a second selective metal (such as Au 24 and In 25 ). It has been well documented that this strategy can enable the formation of additional oxygen vacancies and more active sites for CO 2 activation and methanol formation.…”

Section: Introductionmentioning

confidence: 99%

“…17,[19][20][21][22][23] However, the unmodified Cu/ZrO 2 catalyst still shows moderate activity and selectivity for methanol synthesis (methanol selectivity <50% at high reaction temperatures, e.g., 300 C), which need to be further improved. 19 Another effective strategy to promote the activity of Cu-based catalysts is the doping of a second selective metal (such as Au 24 and In 25 ). It has been well documented that this strategy can enable the formation of additional oxygen vacancies and more active sites for CO 2 activation and methanol formation.…”

Section: Introductionmentioning

confidence: 99%

In situDRIFTS examining the impact of indium doping on activity of CuIn/ZrO₂ catalyst for CO₂ hydrogenation to methanol

Chen,

Wu,

Shao

et al. 2023

AIChE Journal

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We describe the synthesis of CuIn/ZrO2 catalysts via a facile mechanochemical synthesis method. In doping was demonstrated to promote the formation of strong Cu–In2O3 interactions and increase the number of Cu+ sites. The CuIn0.05/ZrO2 catalyst shows relatively high selectivity and space–time yield of methanol (~50% and ~1.25 , respectively) at 300°C and 5 MPa, outperforming those of the Cu/ZrO2 catalyst (~25% and ~1.12 , respectively). Time‐resolved in situ DRIFTS results acquired under various reaction conditions (typically H2/D2 isotope exchange) demonstrate that the surface Cu+–bound formate was the most reactive intermediate and the subsequent hydrogenation process should be the rate‐limiting step, which was positively promoted by the inclusion of In. The strong Cu–In2O3 interaction promotes a decrease in Cu0 sites, leading to a weak interaction of the Cu0‐bound CO intermediates, thus facilitating further hydrogenation of these species rather than releasing CO product.

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Promoting effects of indium doped Cu/CeO₂ catalysts on CO₂ hydrogenation to methanol

Abstract: Cu-based materials have been extensively reported as promising catalysts to convert CO2 into value-added chemicals and fuels. Herein, we report In-promoted Cu/CeO2 catalysts (CuCeIn5 and CuCeIn10) prepared by surfactant-assisted co-precipitation...

Cited by 15 publications

References 72 publications

Identifying Catalyst Property Descriptors for CO₂ Hydrogenation to Methanol via Big-Data Analysis

Identifying Catalyst Property Descriptors for CO₂ Hydrogenation to Methanol via Big-Data Analysis

Dynamics of the Cu/CeO₂catalyst during methanol steam reforming

In situDRIFTS examining the impact of indium doping on activity of CuIn/ZrO₂ catalyst for CO₂ hydrogenation to methanol

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Promoting effects of indium doped Cu/CeO2 catalysts on CO2 hydrogenation to methanol

Abstract: Cu-based materials have been extensively reported as promising catalysts to convert CO2 into value-added chemicals and fuels. Herein, we report In-promoted Cu/CeO2 catalysts (CuCeIn5 and CuCeIn10) prepared by surfactant-assisted co-precipitation...

Cited by 15 publications

References 72 publications

Identifying Catalyst Property Descriptors for CO2 Hydrogenation to Methanol via Big-Data Analysis

Identifying Catalyst Property Descriptors for CO2 Hydrogenation to Methanol via Big-Data Analysis

Dynamics of the Cu/CeO2catalyst during methanol steam reforming

In situDRIFTS examining the impact of indium doping on activity of CuIn/ZrO2 catalyst for CO2 hydrogenation to methanol

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Promoting effects of indium doped Cu/CeO₂ catalysts on CO₂ hydrogenation to methanol

Identifying Catalyst Property Descriptors for CO₂ Hydrogenation to Methanol via Big-Data Analysis

Identifying Catalyst Property Descriptors for CO₂ Hydrogenation to Methanol via Big-Data Analysis

Dynamics of the Cu/CeO₂catalyst during methanol steam reforming

In situDRIFTS examining the impact of indium doping on activity of CuIn/ZrO₂ catalyst for CO₂ hydrogenation to methanol