Physical regulation of copper catalyst with a hydrophobic promoter for enhancing CO2 hydrogenation to methanol

Li, Hangjie; Fang, Wei; Wang, Ling-Xiang; Liu, Yifeng; Liu, Lujie; Sun, Tulai; Liao, C.-C.; Zhu, Yihan; Wang, Liang; Xiao, Feng‐Shou

doi:10.1016/j.xinn.2023.100445

Cited by 7 publications

(3 citation statements)

References 46 publications

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“…Conversely, the Cu-SiO2-AE catalyst exhibits a consistently low methanol decomposition of approximately 14%. Since Cu 0 species act as the main active sites for methanol decomposition to COx, which is the main by-product of methanol decomposition in the gas phase, the observed decrease in methanol decomposition confirms a reduction in the Cu 0 species and an increase in Cu δ+ species [52,53]. In contrast, the constantly low methanol decomposition observed with the Cu-SiO2-AE catalyst indicates a sustained presence of Cu 0 species, which is consistent with the XRD and TEM results, showing a higher proportion of Cu δ+ There is a hypothesis that the Si-OH species contribute to the dispersion and stabilization of Cu nanoparticles during the calcination, reduction, and reaction processes.…”

Section: Catalytic Hydrogenation Of Methyl Formatementioning

confidence: 81%

A Cu-SiO2 Catalyst for Highly Efficient Hydrogenation of Methyl Formate to Methanol

Liu

et al. 2023

Catalysts

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The hydrogenation of methyl formate to methanol is considered one of the most effective methods for recycling methyl formate products. We recently developed a highly efficient and cost-effective Cu-SiO2 catalyst using the ammonia-evaporation (AE) method. The Cu-SiO2-AE catalyst demonstrated superior performance, achieving a methyl formate conversion of 94.2% and a methanol selectivity of 99.9% in the liquid product. The catalyst also displayed excellent stability over a durability test of 250 h. Compared to the commonly used Cu-Cr catalyst in the industry, the Cu-SiO2-AE catalyst exhibited higher conversion of methyl formate and methanol yield under the same reaction conditions. Characterization results revealed a significant presence of Si-OH groups in the Cu-SiO2-AE catalyst. These groups enhanced the hydrogen spillover effect and improved hydrogenation efficiency by preventing sintering during the reaction to stabilize the Cu species. The strategy employed in this study is applicable to the rational design of highly efficient catalysts for industrial applications.

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Section: Catalytic Hydrogenation Of Methyl Formatementioning

confidence: 81%

A Cu-SiO2 Catalyst for Highly Efficient Hydrogenation of Methyl Formate to Methanol

Liu

et al. 2023

Catalysts

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“…The role of water, an unavoidable byproduct in CO 2 hydrogenation, has yielded contradictory findings in previous research. Some authors have reported its negative impact during methanol synthesis, including the suppression of methanol formation due to competitive adsorption on active sites, the oxidation of the metal surface, and accelerated crystallization of copper and zinc in the case of Cu-ZnO-based catalysts . In contrast, others have highlighted its positive influence, where water favors the hydrolysis of methoxy species, thereby enhancing methanol desorption .…”

Section: Introductionmentioning

confidence: 99%

Water and Cu⁺ Synergy in Selective CO₂ Hydrogenation to Methanol over Cu-MgO-Al₂O₃ Catalysts

Fernández-Villanueva,

Lustemberg,

Zhao

et al. 2024

J. Am. Chem. Soc.

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The CO 2 hydrogenation reaction to produce methanol holds great significance as it contributes to achieving a CO 2 -neutral economy. Previous research identified isolated Cu + species doping the oxide surface of a Cu-MgO-Al 2 O 3 -mixed oxide derived from a hydrotalcite precursor as the active site in CO 2 hydrogenation, stabilizing monodentate formate species as a crucial intermediate in methanol synthesis. In this work, we present a molecular-level understanding of how surface water and hydroxyl groups play a crucial role in facilitating spontaneous CO 2 activation at Cu + sites and the formation of monodentate formate species. Computational evidence has been experimentally validated by comparing the catalytic performance of the Cu-MgO-Al 2 O 3 catalyst with hydroxyl groups against that of its hydrophobic counterpart, where hydroxyl groups are blocked using an esterification method. Our work highlights the synergistic effect between doped Cu + ions and adjacent hydroxyl groups, both of which serve as key parameters in regulating methanol production via CO 2 hydrogenation. By elucidating the specific roles of these components, we contribute to advancing our understanding of the underlying mechanisms and provide valuable insights for optimizing methanol synthesis processes.

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“…1–4 This is because carbon dioxide functions as a chemical raw material in this process, producing renewable chemicals without using fossil fuels. 5–7 The hydrogenation of CO 2 usually produces C 1 compounds, such as CO, CH 4 , and CH 3 OH. 8–11 Among C 1 products, CO is a resource for the synthesis of alcohols, liquid hydrocarbons, and organic acids using existing syngas conversion infrastructure.…”

Section: Introductionmentioning

confidence: 99%

Tuning the selectivity of the CO₂ hydrogenation reaction using boron-doped cobalt-based catalysts

Wang,

Liu,

Zhao

et al. 2024

RSC Adv.

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Physical regulation of copper catalyst with a hydrophobic promoter for enhancing CO2 hydrogenation to methanol

Cited by 7 publications

References 46 publications

A Cu-SiO2 Catalyst for Highly Efficient Hydrogenation of Methyl Formate to Methanol

A Cu-SiO2 Catalyst for Highly Efficient Hydrogenation of Methyl Formate to Methanol

Water and Cu⁺ Synergy in Selective CO₂ Hydrogenation to Methanol over Cu-MgO-Al₂O₃ Catalysts

Tuning the selectivity of the CO₂ hydrogenation reaction using boron-doped cobalt-based catalysts

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Physical regulation of copper catalyst with a hydrophobic promoter for enhancing CO2 hydrogenation to methanol

Cited by 7 publications

References 46 publications

A Cu-SiO2 Catalyst for Highly Efficient Hydrogenation of Methyl Formate to Methanol

A Cu-SiO2 Catalyst for Highly Efficient Hydrogenation of Methyl Formate to Methanol

Water and Cu+ Synergy in Selective CO2 Hydrogenation to Methanol over Cu-MgO-Al2O3 Catalysts

Tuning the selectivity of the CO2 hydrogenation reaction using boron-doped cobalt-based catalysts

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Product

Resources

About

Water and Cu⁺ Synergy in Selective CO₂ Hydrogenation to Methanol over Cu-MgO-Al₂O₃ Catalysts

Tuning the selectivity of the CO₂ hydrogenation reaction using boron-doped cobalt-based catalysts