Chemical Batteries with CO<sub>2</sub>

Schlögl, Robert

doi:10.1002/anie.202007397

Cited by 27 publications

(22 citation statements)

References 289 publications

(280 reference statements)

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“…It is the tendency of the system to remove structural imperfections within the lattice (stacking faults) and at the subsurface (residual oxygen) that provide the energy for the microstructural changes observed. Also, this behavior of “methanol copper” is fully in line with the observations on technical catalysts used for CO 2 hydrogenation. The present work provides solid and complementary evidence for the non-perfect nature of active Cu.…”

Section: Discussionsupporting

confidence: 87%

Shape-Dependent CO₂ Hydrogenation to Methanol over Cu₂O Nanocubes Supported on ZnO

et al. 2023

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The hydrogenation of CO2 to methanol over Cu/ZnO-based catalysts is highly sensitive to the surface composition and catalyst structure. Thus, its optimization requires a deep understanding of the influence of the pre-catalyst structure on its evolution under realistic reaction conditions, including the formation and stabilization of the most active sites. Here, the role of the pre-catalyst shape (cubic vs spherical) in the activity and selectivity of ZnO-supported Cu nanoparticles was investigated during methanol synthesis. A combination of ex situ, in situ, and operando microscopy, spectroscopy, and diffraction methods revealed drastic changes in the morphology and composition of the shaped pre-catalysts under reaction conditions. In particular, the rounding of the cubes and partial loss of the (100) facets were observed, although such motifs remained in smaller domains. Nonetheless, the initial pre-catalyst structure was found to strongly affect its subsequent transformation in the course of the CO2 hydrogenation reaction and activity/selectivity trends. In particular, the cubic Cu particles displayed an increased activity for methanol production, although at the cost of a slightly reduced selectivity when compared to similarly sized spherical particles. These findings were rationalized with the help of density functional theory calculations.

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Section: Discussionsupporting

confidence: 87%

Shape-Dependent CO₂ Hydrogenation to Methanol over Cu₂O Nanocubes Supported on ZnO

et al. 2023

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“…In a recent review, Schlogl has named this still elusive active phase "methanol copper". 40 3.1. The Role of Cu.…”

Section: The Active Phasementioning

confidence: 99%

From CO₂ to Methanol on Cu/ZnO/Al₂O₃ Industrial Catalyst. What Do We Know about the Active Phase and the Reaction Mechanism?

Pacchioni

2024

ACS Catal.

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For more than half a century, the industrial production of methanol in the world has been based on a heterogeneous Cu/ ZnO/Al 2 O 3 catalyst where Cu nanoparticles are dispersed on an alumina support with ZnO particles as promoters. The reaction starts with syngas, a mixture of CO, CO 2 , and hydrogen, and the hydrogenation of carbon dioxide is an essential part of the process. Despite the technological importance and the high number of studies dedicated to identifying the structure of the functioning catalyst, there are still several open questions on the nature of the active sites and phases. Over the years, various hypotheses have been formulated. The most accredited versions concern the formation of CuZn alloys, the migration of ZnO over the Cu nanoparticles which become covered by an ultrathin oxide layer, and the role of the Cu−ZnO interface and, in particular, of the presence of Cu + ions. The role of alumina as a promoter has also been widely discussed, suggesting that the oxide provides acidic sites where intermediates are stabilized or that Al dopants enter the ZnO phase, altering its properties. The reality, as discussed in this brief overview, is that all these mechanisms are probably contributing but under different conditions of temperature, pressure, and reagent composition. This results in a dynamic catalyst that makes unambiguous identification of active sites difficult, if not impossible. Less controversial is the reaction mechanism, although even in this case the path followed by the reaction is a delicate function of various conditions, including the composition of the reaction mixture and the presence of water or other contaminants.

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“…The electrocatalytic pathway for renewable energy conversion into valuable chemicals plays a pivotal role in the transition to an energetically sustainable society, with CO 2 and H 2 O as the cornerstone molecules. [1,2] In this way, the electrochemical reduction of CO 2 to valuable hydrocarbons and oxygenated products is proposed to occur in multiple steps: the reduction of CO 2 to CO and its subsequent conversion into oxygenates and hydrocarbon products. [3,4] The efficiency of this process competes against the parasitic hydrogen evolution reaction (HER) during the cathodic CO 2 reduction reaction (CO 2 RR).…”

Section: Introductionmentioning

confidence: 99%

Cationic Copper Species Stabilized by Zinc during the Electrocatalytic Reduction of CO₂ Revealed by In Situ X‐Ray Spectroscopy

Velasco‐Vélez

Poon

Gao

et al. 2023

Advanced Sustainable Systems

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Advanced in situ X‐ray absorption spectroscopy characterization of electrochemically co‐electrodeposited bi‐element copper alloy electrodes shows that zinc yields the formation of a stable cationic Cu species during the electroreduction of CO2 at high cathodic polarization. In contrast, the formation/stabilization of cationic Cu species in copper oxides, or doping Cu with another element, like Ni, is not possible. It is found that the pure and mixed Cu:Zn electrodes behave similarly in term of electrocatalytic selectivity to multi‐carbon products. At higher Zn concentrations the electrode behaves like the pure Zn catalyst, which indicates that the Cu cationic species do not have a significant influence on the selectivity to multi‐carbon products. It is found that in the non‐monotonically distribution of products is dominated in term of surface energy in which copper prefers the surface. Otherwise, this work highlights the importance of in situ characterization to uncover the mechanisms mediating the catalytic reactions in contrast to ex situ or post mortem analysis, which can be a source of misinterpretation.

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Chemical Batteries with CO₂

Cited by 27 publications

References 289 publications

Shape-Dependent CO₂ Hydrogenation to Methanol over Cu₂O Nanocubes Supported on ZnO

Shape-Dependent CO₂ Hydrogenation to Methanol over Cu₂O Nanocubes Supported on ZnO

From CO₂ to Methanol on Cu/ZnO/Al₂O₃ Industrial Catalyst. What Do We Know about the Active Phase and the Reaction Mechanism?

Cationic Copper Species Stabilized by Zinc during the Electrocatalytic Reduction of CO₂ Revealed by In Situ X‐Ray Spectroscopy

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Chemical Batteries with CO2

Cited by 27 publications

References 289 publications

Shape-Dependent CO2 Hydrogenation to Methanol over Cu2O Nanocubes Supported on ZnO

Shape-Dependent CO2 Hydrogenation to Methanol over Cu2O Nanocubes Supported on ZnO

From CO2 to Methanol on Cu/ZnO/Al2O3 Industrial Catalyst. What Do We Know about the Active Phase and the Reaction Mechanism?

Cationic Copper Species Stabilized by Zinc during the Electrocatalytic Reduction of CO2 Revealed by In Situ X‐Ray Spectroscopy

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Product

Resources

About

Chemical Batteries with CO₂

Shape-Dependent CO₂ Hydrogenation to Methanol over Cu₂O Nanocubes Supported on ZnO

Shape-Dependent CO₂ Hydrogenation to Methanol over Cu₂O Nanocubes Supported on ZnO

From CO₂ to Methanol on Cu/ZnO/Al₂O₃ Industrial Catalyst. What Do We Know about the Active Phase and the Reaction Mechanism?

Cationic Copper Species Stabilized by Zinc during the Electrocatalytic Reduction of CO₂ Revealed by In Situ X‐Ray Spectroscopy