C<sub>2</sub>product formation in the CO<sub>2</sub>electroreduction on boron-doped graphene anchored copper clusters

Barhács, Balázs; Janssens, Ewald; Höltzl, Tibor

doi:10.1039/d2cp01316a

Cited by 9 publications

(9 citation statements)

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“…All of the COVPs together describe the charge transfer between the fragments exactly. ,, Major contribution to the bonding between the fragments is often given by only a few of these pairs, so it is usually sufficient to consider only those to qualitatively interpret the contribution of the charge transfer interactions to the intermolecular binding. Recently, COVPs have been used successfully to explain the CO 2 binding on doped copper clusters and also to explain copper cluster binding to boron-doped graphene …”

Section: Resultsmentioning

confidence: 99%

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Multistep CO₂ Activation and Dissociation Mechanisms on Pd_xPt_4–x Clusters in the Gas Phase

Sechi

Höltzl

2023

J. Phys. Chem. A

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Palladium, platinum, and their alloys are promising catalysts for electrochemical CO 2 reduction reactions (CO 2 RR), leading to the design of durable and efficient catalysts for the production of useful chemicals in a more sustainable way. However, a deep understanding of the CO 2 RR mechanisms is still challenging because of the complexity and the factors influencing the system. The purpose of this study is to investigate at the atomic scale the first steps of the CO 2 RR, CO 2 activation and dissociation mechanisms on Pd x Pt 4−x clusters in the gas phase.To do it, we use Density Functional Theory (DFT)-based reaction path and ab initio molecular dynamics (AIMD) computations. Our research focuses on the description of CO 2 activation and dissociation processes via the computation of multistep reaction paths, providing insights into the site and binding mode dependent reactivity. Detailed understanding of the CO 2 −cluster interaction mechanisms and estimating of the reaction energy barriers facilitate comprehension of why and how catalysts are poisoned and identification of the most stable activated adducts configurations. We show that increasing the platinum content induces fluxional behavior of the cluster structure and biases CO 2 dissociation; in fact, our computations unveiled several dissociated CO 2 isomers that are very stable and that there are various isomerization processes leading to a dissociated structure (possibly a CO poisoned state) from an intactly bound CO 2 one (activated state). On the basis of the comparison of the Pd x Pt 4−x reaction paths, we can observe the promising catalytic activity of Pd 3 Pt in the studied context. Not only does this cluster composition favor CO 2 activation against dissociation (thereby expected to facilitate the hydrogenation reactions of CO 2 ), the potential energy surface (PES) is very flat among activated CO 2 isomers.

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Section: Resultsmentioning

confidence: 99%

“…Recently, COVPs have been used successfully to explain the CO 2 binding on doped copper clusters 79 and also to explain copper cluster binding to borondoped graphene. 92 We defined the tetranuclear Pd x Pt 4−x as one fragment and the CO 2 as the second fragment. Our EDA was limited to the adducts with intact CO 2 .…”

Section: ■ Computational Methodsmentioning

confidence: 99%

Multistep CO₂ Activation and Dissociation Mechanisms on Pd_xPt_4–x Clusters in the Gas Phase

Sechi

Höltzl

2023

J. Phys. Chem. A

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“…Recent studies have shown that graphene‐supported metal clusters can lower the reaction energy barrier and further improve the reaction efficiency of molecules on metal clusters. For examples, boron‐doped graphene‐supported Cu n (n=3–8) clusters have high catalytic activity in carbon dioxide reduction reaction [21] . DFT shows that Cu 55 clusters supported by defective graphene can enhance the electrochemical reduction of carbon dioxide (CO 2 ) to hydrocarbon fuel [22] .…”

Section: Introductionmentioning

confidence: 99%

“…For examples, borondoped graphene-supported Cu n (n = 3-8) clusters have high catalytic activity in carbon dioxide reduction reaction. [21] DFT shows that Cu 55 clusters supported by defective graphene can enhance the electrochemical reduction of carbon dioxide (CO 2 ) to hydrocarbon fuel. [22] In the hydrogenation of acetylene and ethylene hydrogenation, the graphene-supported Cu 11 nanocluster has good activity and selectivity for the hydrogenation of acetylene.…”

Section: Introductionmentioning

confidence: 99%

Ab Initio Molecular Dynamics Study of H₂ Dissociation Mechanisms on Cu₁₃ and Defective Graphene‐supported Cu₁₃ Clusters: Active Sites, Energy Barriers and Adsorption States

Wang

2023

ChemPhysChem

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Ab initio molecular dynamics calculations were performed to study H2 dissociation mechanisms on Cu13 and defective graphene‐supported Cu13 clusters. The study reveals that seven types of corresponding dissociation processes are found on the two clusters. The average dissociation energy barriers are 0.51 eV on the Cu13 cluster and 0.12 eV on the defective graphene‐supported Cu13 cluster, which are lowered by ~19 % and ~81 % compared with the pristine Cu(111) surface, respectively. Furthermore, compared with the pure Cu13 cluster, the average dissociation energy barrier on the defective graphene‐supported Cu13 cluster is substantially reduced by about 76 %. The preferred dissociation mechanisms on the two clusters are H2 located at a top‐bridge site with the barrier heights of 0.30 eV on the Cu13 cluster and −0.31 eV on the defective graphene‐supported Cu13 cluster. Analysis of the H−Cu bond interactions in the transition states shows that the antibonding‐orbital center shifts upward on the defective graphene‐supported Cu13 cluster compared with the one on the Cu13 cluster, which explains the reduction of the dissociation energy barrier. The average adsorption energy of dissociated H atoms is also greatly enhanced on the defective graphene‐supported Cu13 cluster, about twice that on the Cu13 cluster.

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“…[35] For CO 2 hydrogenation an optimal cluster size of Cu 19 has been predicted using DFT computations. [36] It has also been shown that small copper clusters deposited on ZnO are more active catalysts for the CO 2 hydrogenation to CO than the larger particles. [37] Copper subnano clusters have also been found to be active in CO 2 hydrogenation in various other surfaces, like Fe 2 O 3 [38] or TiO 2 .…”

Section: Introductionmentioning

confidence: 99%

CO₂ and H₂ Activation on Zinc‐Doped Copper Clusters

Zamora,

Nyulászi,

Höltzl

2023

ChemPhysChem

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Here we systematically investigate the CO2 and H2 activation and dissociation on small CunZn0/+ (n=3–6) clusters using Density Functional Theory. We show that Cu6Zn is a superatom, displaying an increased HOMO‐LUMO gap and is inert towards CO2 or H2 activation or dissociation. While other neutral clusters weakly activate CO2, the cationic clusters preferentially bind the CO2 in monodentate nonactivated way. Notably, Cu4Zn allows for the dissociation of activated CO2, whereas larger clusters destabilize all activated CO2 binding modes. Conversely, H2 dissociation is favored on all clusters examined, except for Cu6Zn. Cu3Zn+ and Cu4Zn, favor the formation of formate through the H2 dissociation pathway rather than CO2 dissociation. These findings suggest the potential of these clusters as synthetic targets and underscore their significance in the realm of CO2 hydrogenation.

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C₂product formation in the CO₂electroreduction on boron-doped graphene anchored copper clusters

Abstract: A possible remedy for the increasing atmospheric CO2 concentration is capturing and reducing it into valuable chemicals like methane, methanol, ethylene, ethanol. However, the suitable catalyst for this process is...

Cited by 9 publications

References 74 publications

Multistep CO₂ Activation and Dissociation Mechanisms on Pd_xPt_4–x Clusters in the Gas Phase

Multistep CO₂ Activation and Dissociation Mechanisms on Pd_xPt_4–x Clusters in the Gas Phase

Ab Initio Molecular Dynamics Study of H₂ Dissociation Mechanisms on Cu₁₃ and Defective Graphene‐supported Cu₁₃ Clusters: Active Sites, Energy Barriers and Adsorption States

CO₂ and H₂ Activation on Zinc‐Doped Copper Clusters

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C2product formation in the CO2electroreduction on boron-doped graphene anchored copper clusters

Abstract: A possible remedy for the increasing atmospheric CO2 concentration is capturing and reducing it into valuable chemicals like methane, methanol, ethylene, ethanol. However, the suitable catalyst for this process is...

Cited by 9 publications

References 74 publications

Multistep CO2 Activation and Dissociation Mechanisms on PdxPt4–x Clusters in the Gas Phase

Multistep CO2 Activation and Dissociation Mechanisms on PdxPt4–x Clusters in the Gas Phase

Ab Initio Molecular Dynamics Study of H2 Dissociation Mechanisms on Cu13 and Defective Graphene‐supported Cu13 Clusters: Active Sites, Energy Barriers and Adsorption States

CO2 and H2 Activation on Zinc‐Doped Copper Clusters

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C₂product formation in the CO₂electroreduction on boron-doped graphene anchored copper clusters

Multistep CO₂ Activation and Dissociation Mechanisms on Pd_xPt_4–x Clusters in the Gas Phase

Multistep CO₂ Activation and Dissociation Mechanisms on Pd_xPt_4–x Clusters in the Gas Phase

Ab Initio Molecular Dynamics Study of H₂ Dissociation Mechanisms on Cu₁₃ and Defective Graphene‐supported Cu₁₃ Clusters: Active Sites, Energy Barriers and Adsorption States

CO₂ and H₂ Activation on Zinc‐Doped Copper Clusters