Unravelling the mechanisms of CO<sub>2</sub> hydrogenation to methanol on Cu-based catalysts using first-principles multiscale modelling and experiments

Huš, Matej; Kopač, Drejc; Štefančič, Neja Strah; Jurković, Damjan Lašič; Dasireddy, Venkata D.B.C.; Likozar, Blaž

doi:10.1039/c7cy01659j

Cited by 91 publications

(67 citation statements)

References 48 publications

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“…Recent results by Kattel et al [196] indicate that the mechanism on these step-edge sites, ZnCu(211), for methanol synthesis may be better described by an Eley-Rideal model as opposed to the long accepted Langmuir-Hinshelwood model. While CO 2 only weakly physisorbs on Zn 3 O 3 /Cu, the calculations of Huš et al [192] also suggest an Eley-Rideal mechanism.…”

Section: Catalytic Reaction Mechanismmentioning

confidence: 93%

“…Huš et al. found that the amount of chemisorbed hydrogen was highest when the adjacent metal was Zn compared to Mg, Fe, and Cr (in decreasing order).…”

Section: Thermodynamics and Kineticsmentioning

confidence: 99%

“…While CO 2 only weakly physisorbs on Zn 3 O 3 /Cu, the calculations of Huš et al. also suggest an Eley‐Rideal mechanism.…”

Section: Thermodynamics and Kineticsmentioning

confidence: 99%

“…The amount of chemisorbed hydrogen on Cu catalyst surfaces varies depending on the type of metal at the Cu-metal contact. Huš et al [192] found that the amount of chemisorbed hydrogen was highest when the adjacent metal was Zn compared to Mg, Fe, and Cr (in decreasing order).…”

Section: Catalytic Reaction Mechanismmentioning

confidence: 99%

“…Methanol synthesis via the CO 2 pathway occurs via the formation of a formate intermediate, HCOO* 2) , forming HCOOH*, and then H 2 COOH*. Huš et al [192], who modelled a Zn 3 O 3 cluster on a Cu(111) surface, however, found that H 2 COO* forms prior to H 2 COOH*. The carbon oxygen bond of H 2 COOH* remains intact, yielding OH*, which leaves the surface as water, and adsorbed H 2 CO*, which is further hydrogenated via the methoxy intermediate H 3 CO* to methanol.…”

Section: Catalytic Reaction Mechanismmentioning

confidence: 99%

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Renewable Methanol Synthesis

2019

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Renewable methanol production is an emerging technology that bridges the gap in the shift from fossil fuel to renewable energy. Two thirds of the global emission of CO2 stems from humanity's increasing energy need from fossil fuels. Renewable energy, mainly from solar and wind energy, suffers from supply intermittency, which current grid infrastructures cannot accommodate. Excess renewable energy can be harnessed to power the electrolysis of water to produce hydrogen, which can be used in the catalytic hydrogenation of waste CO2 to produce renewable methanol. This review considers methanol production in the current context, regionally for Europe, which is dominated by Germany, and globally by China. Appropriate carbon‐based feedstock for renewable methanol production is considered, as well as state‐of‐the‐art renewable hydrogen production technologies. The economics of renewable methanol production necessitates the consideration of regionally relevant methanol derivatives. The thermodynamics, kinetics, catalytic reaction mechanism, operating conditions and reactor design are reviewed in the context of renewable methanol production to reveal the most up to date understanding.

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Section: Catalytic Reaction Mechanismmentioning

confidence: 93%

“…Huš et al. found that the amount of chemisorbed hydrogen was highest when the adjacent metal was Zn compared to Mg, Fe, and Cr (in decreasing order).…”

Section: Thermodynamics and Kineticsmentioning

confidence: 99%

“…While CO 2 only weakly physisorbs on Zn 3 O 3 /Cu, the calculations of Huš et al. also suggest an Eley‐Rideal mechanism.…”

Section: Thermodynamics and Kineticsmentioning

confidence: 99%

Section: Catalytic Reaction Mechanismmentioning

confidence: 99%

Section: Catalytic Reaction Mechanismmentioning

confidence: 99%

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Renewable Methanol Synthesis

2019

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Highly Efficient CO₂ to CO Transformation over Cu‐Based Catalyst Derived from a CuMgAl‐Layered Double Hydroxide (LDH)

et al. 2020

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Supported Cu‐based catalysts are promising catalysts for RWGS reactions. Herein, CuMgAl‐LDHs (LDHs: Layered double hydroxides) were used as the precursors to obtain supported Cu with good dispersion and high stability. The reduction of CuMgAl‐LDH at 400 °C led to the formation of 0.3CuMgAl‐LDH‐400, with Cu nanoparticles well dispersed on MgO/Al2O3, which exhibited superior activity and high stability for RWGS. 33.5 % of CO2 was converted, with selectivity of almost 100 % to CO at 350 °C under a high space velocity, among the highest for RWGS ever reported for Cu‐based catalysts, especially at a low reaction temperature. In‐situ DRIFTS and CO2‐TPD revealed that its superior performance is attributed to high Cu dispersion which is beneficial for the dissociation of H2, as well as the presence of variety of basic sites for adsorption towards CO2 to facilitate the formation of formates. This study demonstrates the great opportunity of LDHs in the preparations of supported metal‐based catalysts.

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Understanding the Origin of Structure Sensitivity in Nano Crystalline Mixed Cu/Mg−Al Oxides Catalyst for Low‐Pressure Methanol Synthesis

et al. 2021

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Cu nanoparticles of size 5-10 nm supported on MgÀ Al mixed oxide were prepared by the sol-gel method. Cu loading was varied from 2.5 to 10 wt % on the support to investigate the effect on particle size and activity/selectivity of the catalyst. The Cu/MgÀ Al catalysts containing small copper nanoparticles favor high selectivity of methanol, while the rate of CO formation was higher for larger copper particles. The high methanol selectivity (~99 %) and methanol formation rate (0.016 mol g Cu À 1 h À 1 ) over the 4.8Cu/MgÀ Al catalyst was due to the combined effect of the presence of high Cu dispersion, Cu surface area, and strong interaction between small Cu particles with MgÀ Al support. The high stability of the catalyst was attributed to the strong binding of the Cu cluster (À 179.7 kJ/mol) to the MgO/γ-Al 2 O 3 support, as shown by the DFT study. Additionally, the adsorption energy calculated using DFT showed preferential adsorption of CO 2 and H 2 at the Cu/MgO(100) active site (À 120.9 kJ/mol, À 130.4 kJ/mol) compared to the Cu/γ-Al 2 O 3 (100) (À 64.2 kJ/mol, À 85.7 kJ/mol)active site. The high selectivity of the catalyst towards methanol can be attributed to the higher stability of the formate (HCOO) intermediate (À 257.2 kJ/mol) compared to the carboxylate (COOH) intermediate (À 131.0 kJ/mol).

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Unravelling the mechanisms of CO₂ hydrogenation to methanol on Cu-based catalysts using first-principles multiscale modelling and experiments

Abstract: Multi-scale modelling of various copper-based catalysts showed how and why different catalysts perform in methanol synthesis via carbon dioxide hydrogenation.

Cited by 91 publications

References 48 publications

Renewable Methanol Synthesis

Renewable Methanol Synthesis

Highly Efficient CO₂ to CO Transformation over Cu‐Based Catalyst Derived from a CuMgAl‐Layered Double Hydroxide (LDH)

Understanding the Origin of Structure Sensitivity in Nano Crystalline Mixed Cu/Mg−Al Oxides Catalyst for Low‐Pressure Methanol Synthesis

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Unravelling the mechanisms of CO2 hydrogenation to methanol on Cu-based catalysts using first-principles multiscale modelling and experiments

Abstract: Multi-scale modelling of various copper-based catalysts showed how and why different catalysts perform in methanol synthesis via carbon dioxide hydrogenation.

Cited by 91 publications

References 48 publications

Renewable Methanol Synthesis

Renewable Methanol Synthesis

Highly Efficient CO2 to CO Transformation over Cu‐Based Catalyst Derived from a CuMgAl‐Layered Double Hydroxide (LDH)

Understanding the Origin of Structure Sensitivity in Nano Crystalline Mixed Cu/Mg−Al Oxides Catalyst for Low‐Pressure Methanol Synthesis

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Resources

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Unravelling the mechanisms of CO₂ hydrogenation to methanol on Cu-based catalysts using first-principles multiscale modelling and experiments

Highly Efficient CO₂ to CO Transformation over Cu‐Based Catalyst Derived from a CuMgAl‐Layered Double Hydroxide (LDH)