Heterogeneously Catalyzed
            <scp>CO</scp>
            <sub>2</sub>
            Hydrogenation to Alcohols

Phongprueksathat, Nat; Urakawa, Atsushi

doi:10.1002/9783527824113.ch8

Cited by 3 publications

(6 citation statements)

References 124 publications

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“…Since the hydrogenation of surface formate species has been discussed as the rate-limiting step in the methanol synthesis over Cu-based catalysts (although the rate-limiting step may change to methanol desorption at high CO 2 conversion), , the observation of kinetically favored methoxy species in Cu–Zn(5)/SiO 2 implies a critical role of Zn in the catalytic cycle. It is noteworthy that the band due to μ-HCOO*(Cu) is not observed in our Cu–Zn(5)/SiO 2 catalyst, which is in contrast to other Cu–Zn-based catalysts. ,– …”

Section: Resultsmentioning

confidence: 99%

Combining Atomic Layer Deposition with Surface Organometallic Chemistry to Enhance Atomic-Scale Interactions and Improve the Activity and Selectivity of Cu–Zn/SiO₂ Catalysts for the Hydrogenation of CO₂ to Methanol

Zhou,

Docherty,

Phongprueksathat

et al. 2023

JACS Au

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The direct synthesis of methanol via the hydrogenation of CO2, if performed efficiently and selectively, is potentially a powerful technology for CO2 mitigation. Here, we develop an active and selective Cu–Zn/SiO2 catalyst for the hydrogenation of CO2 by introducing copper and zinc onto dehydroxylated silica via surface organometallic chemistry and atomic layer deposition, respectively. At 230 °C and 25 bar, the optimized catalyst shows an intrinsic methanol formation rate of 4.3 g h–1 gCu –1 and selectivity to methanol of 83%, with a space-time yield of 0.073 g h–1 gcat –1 at a contact time of 0.06 s g mL–1. X-ray absorption spectroscopy at the Cu and Zn K-edges and X-ray photoelectron spectroscopy studies reveal that the CuZn alloy displays reactive metal support interactions; that is, it is stable under H2 atmosphere and unstable under conditions of CO2 hydrogenation, indicating that the dealloyed structure contains the sites promoting methanol synthesis. While solid-state nuclear magnetic resonance studies identify methoxy species as the main stable surface adsorbate, transient operando diffuse reflectance infrared Fourier transform spectroscopy indicates that μ-HCOO*(ZnO x ) species that form on the Cu–Zn/SiO2 catalyst are hydrogenated to methanol faster than the μ-HCOO*(Cu) species that are found in the Zn-free Cu/SiO2 catalyst, supporting the role of Zn in providing a higher activity in the Cu–Zn system.

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Section: Resultsmentioning

confidence: 99%

Combining Atomic Layer Deposition with Surface Organometallic Chemistry to Enhance Atomic-Scale Interactions and Improve the Activity and Selectivity of Cu–Zn/SiO₂ Catalysts for the Hydrogenation of CO₂ to Methanol

Zhou,

Docherty,

Phongprueksathat

et al. 2023

JACS Au

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“…Even though long-chain alkenes and alcohols are favored thermodynamically, they are generally difficult to form in CO 2 hydrogenation due to the high kinetic barrier for carbon chain propagation. 27 The favorability of C 3 and C 4 alcohol isomers differ obviously. Figure 5 presents the product selectivity when hydrocarbons are not included in the simulation.…”

Section: Resultsmentioning

confidence: 99%

“…The favorability of alkenes and alcohols generally increases with a longer carbon chain; however, propene and 2-propanol are exceptions. Even though long-chain alkenes and alcohols are favored thermodynamically, they are generally difficult to form in CO 2 hydrogenation due to the high kinetic barrier for carbon chain propagation . The favorability of C 3 and C 4 alcohol isomers differ obviously.…”

Section: Resultsmentioning

confidence: 99%

“…Even though hydrogenation of CO 2 to higher alcohols has been extensively studied for years focusing on thermodynamic analysis as well as the design and development of highly active catalysts, ,,,, its commercial application is still absent due to the low selectivity to higher alcohols. Generally, the hydrogenation of CO 2 in the gas phase possesses a low selectivity to higher alcohols with ethanol as the main higher alcohol .…”

Section: Introductionmentioning

confidence: 99%

“…18 In addition, ED95, a bioethanol fuel for heavy diesel vehicles provided by SEKAB, containing ethanol (0.95) and an ignition improver (0.05), has been successfully used in modified diesel engines. 16,17 Even though hydrogenation of CO 2 to higher alcohols has been extensively studied for years focusing on thermodynamic analysis as well as the design and development of highly active catalysts, 10,11,13,27,28 its commercial application is still absent due to the low selectivity to higher alcohols. Generally, the hydrogenation of CO 2 in the gas phase possesses a low selectivity to higher alcohols with ethanol as the main higher alcohol.…”

Section: Introductionmentioning

confidence: 99%

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Thermodynamic Analysis of CO₂ Hydrogenation to Higher Alcohols (C_2–4OH): Effects of Isomers and Methane

Liu

et al. 2022

ACS Omega

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Synthesis of higher alcohols (C 2–4 OH) by CO 2 hydrogenation presents a promising way to convert CO 2 into value-added fuels and chemicals. Understanding the thermodynamics of CO 2 hydrogenation is of great importance to tailor the reaction network toward synthesis of higher alcohols; however, the thermodynamic effects of various alcohol isomers and methane in the reaction system have not yet been fully understood. Thus, we used Aspen Plus to perform thermodynamic analysis of CO 2 hydrogenation to higher alcohols, studying the effects of alcohol isomers and methane. Thermodynamically, methane is the most favorable product in a reaction system containing CO, CO 2 , and H 2 , as well as C 1–4 alkanes, alkenes, and alcohols. The thermodynamic favorability of alcohol isomers varies significantly. The presence of methane generally deteriorates the formation of higher alcohols. However, low temperature, high pressure, high H 2 /CO 2 ratio, and formation of alcohols with a longer carbon chain can reduce the effects of methane. Our current study, therefore, provides new insights for enhancing the synthesis of higher alcohols by CO 2 hydrogenation.

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NiFe and CoFe nanocatalysts supported on highly dispersed alumina-silica: Structure, surface properties, and performance in CO2 methanation

Dyachenko,

Ischenko,

Pryhunova

et al. 2024

Environmental Research

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Heterogeneously Catalyzed CO ₂ Hydrogenation to Alcohols

Cited by 3 publications

References 124 publications

Combining Atomic Layer Deposition with Surface Organometallic Chemistry to Enhance Atomic-Scale Interactions and Improve the Activity and Selectivity of Cu–Zn/SiO₂ Catalysts for the Hydrogenation of CO₂ to Methanol

Combining Atomic Layer Deposition with Surface Organometallic Chemistry to Enhance Atomic-Scale Interactions and Improve the Activity and Selectivity of Cu–Zn/SiO₂ Catalysts for the Hydrogenation of CO₂ to Methanol

Thermodynamic Analysis of CO₂ Hydrogenation to Higher Alcohols (C_2–4OH): Effects of Isomers and Methane

NiFe and CoFe nanocatalysts supported on highly dispersed alumina-silica: Structure, surface properties, and performance in CO2 methanation

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Heterogeneously Catalyzed CO 2 Hydrogenation to Alcohols

Cited by 3 publications

References 124 publications

Combining Atomic Layer Deposition with Surface Organometallic Chemistry to Enhance Atomic-Scale Interactions and Improve the Activity and Selectivity of Cu–Zn/SiO2 Catalysts for the Hydrogenation of CO2 to Methanol

Combining Atomic Layer Deposition with Surface Organometallic Chemistry to Enhance Atomic-Scale Interactions and Improve the Activity and Selectivity of Cu–Zn/SiO2 Catalysts for the Hydrogenation of CO2 to Methanol

Thermodynamic Analysis of CO2 Hydrogenation to Higher Alcohols (C2–4OH): Effects of Isomers and Methane

NiFe and CoFe nanocatalysts supported on highly dispersed alumina-silica: Structure, surface properties, and performance in CO2 methanation

Contact Info

Product

Resources

About

Heterogeneously Catalyzed CO ₂ Hydrogenation to Alcohols

Combining Atomic Layer Deposition with Surface Organometallic Chemistry to Enhance Atomic-Scale Interactions and Improve the Activity and Selectivity of Cu–Zn/SiO₂ Catalysts for the Hydrogenation of CO₂ to Methanol

Combining Atomic Layer Deposition with Surface Organometallic Chemistry to Enhance Atomic-Scale Interactions and Improve the Activity and Selectivity of Cu–Zn/SiO₂ Catalysts for the Hydrogenation of CO₂ to Methanol

Thermodynamic Analysis of CO₂ Hydrogenation to Higher Alcohols (C_2–4OH): Effects of Isomers and Methane