DFT study of CO2 catalytic conversion by H2 over Ni13 cluster

Ke, Qiang; Kang, Liming; Chen, Xin; Wu, You

doi:10.1007/s12039-020-01857-3

Cited by 14 publications

(8 citation statements)

References 50 publications

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“…The lowest energy structures found are in agreement with our previous studies, which reported a symmetry decrease from Fe 13 to Cu 13 (from space group I h to C 2 ) . Those results are in contrast to different studies, which reported a high symmetry icosahedral structure for the Ni 13 and Cu 13 clusters as the lowest energy structure. , However, our models for Ni 13 and Cu 13 were 23 and 78 meV/atom lower than the energy for the icosahedral model, respectively.…”

Section: Theoretical Approach and Computational Detailssupporting

confidence: 89%

Ab Initio Study of the C–O Bond Dissociation in CO₂ Reduction by Redox and Carboxyl Routes on 3d Transition Metal Systems

2021

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The C−O bond dissociation of the CO 2 molecule via the reverse water gas shift reaction is crucial for several reactions used as renewable alternatives for fuel synthesis. However, our atomistic understanding of this process on transition metal (TM) clusters, where quantum-size effects might play a significant role, is far from complete. Here, we addressed the C−O bond dissociation by redox and carboxyl routes on 13-atom TM (Fe, Co, Ni, Cu) clusters using density functional theory calculations and the climbing image nudged elastic band algorithm. From the potential energy profiles, we found that CO 2 is prone to dissociate into adsorbed CO via the redox route with lower activation energies, E a 's, than the carboxyl route on all studied TM 13 systems. Our results suggested that the smaller activation barrier found on the Co 13 cluster is due to the stronger adsorption exhibited for both CO 2 and O. By increasing the d-state occupation (from Fe to Cu), the E a differences between CO 2 dissociation and COOH formation decrease. We associated this behavior with a decrease in the (CO 2 + H) adsorption energy from Fe 13 to Cu 13 that facilitates the COO−H bond formation and H−TM bond cleavage, i.e., favoring the carboxyl route. Also, our analyses indicate that the adsorption energies of the CO 2 and trans-COOH species are the best descriptors for the C−O bond dissociation via the redox and carboxyl routes, respectively.

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Section: Theoretical Approach and Computational Detailssupporting

confidence: 89%

Ab Initio Study of the C–O Bond Dissociation in CO₂ Reduction by Redox and Carboxyl Routes on 3d Transition Metal Systems

2021

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“…For example, the CO 2 adsorption energy on Ni 13 is −1.25 eV (ref. 51) or −120.2 kJ mol −1 (ref. 51) and −100 kJ mol −1 , 52 while it is −58 kJ mol −1 on Ni 55 .…”

Section: Co2 Adsorptionmentioning

confidence: 99%

“…51) or −120.2 kJ mol −1 (ref. 51) and −100 kJ mol −1 , 52 while it is −58 kJ mol −1 on Ni 55 . 52 These suggest that CO 2 adsorption can be enhanced by increasing the defects ( e.g.…”

Section: Co2 Adsorptionmentioning

confidence: 99%

Advances in studies of the structural effects of supported Ni catalysts for CO₂hydrogenation: from nanoparticle to single atom catalyst

et al. 2022

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“…3,8,72 Furthermore, the barrier heights for the HCOO* intermediate and HCOOH formed on the Cu 2 dimer through the E−R mechanism are comparatively lower than those on the Cu 2 + dimer. The barrier height of the steps on the Cu 2 − dimer when compared with the respective steps on Cu 2 and Cu 2 + dimers illustrates that the reaction on the Cu 2 − dimer is kinetically least favorable.…”

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confidence: 89%

Reaction Mechanism and Kinetics for the Selective Hydrogenation of Carbon Dioxide to Formic Acid and Methanol over the [Cu₂]^0,±1 Dimer

Neog,

Dowerah,

Biswakarma

et al. 2023

J. Phys. Chem. A

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With the rapid growth of industrialization, deforestation, and burning of fossil fuels, undeniably there has been an incredible escalation of the CO 2 concentration in the atmosphere. In order to mitigate the problem, the capture and utilization of CO 2 in different value-added chemicals have thus remained topics of concerned research for more than a decade. Accordingly, we have performed molecular -level catalytic hydrogenation of CO 2 to formic acid using bare [Cu 2 ] 0,±1 dimers as catalysts. The entire investigation has been performed using a density functional theory (DFT) method employing the Perdew−Burke−Ernzerhof (PBE) functional with the def2TZVPP basis set to explore the different possible routes and efficiency of the catalysts. Results reveal the feasibility of H 2 dissociation on all three Cu 2 , Cu 2 + , and Cu 2 − dimers. The negatively charged hydride formed during H 2 dissociation on Cu 2 and Cu 2 + dimers facilitates the formation of the HCOO* intermediate over COOH*, thereby providing product selectivity for HCOOH above CO. However, the reaction on the Cu 2 − dimer forms both HCOO* and COOH* intermediates, but HCOO*, being kinetically more favorable, results in HCOOH production. The free-energy change suggests that the complete reaction on Cu 2 and Cu 2 + dimers forms a stable product compared to the Cu 2 − dimer. Furthermore, H 3 COH production is studied using the title catalysts via the obtained HCOOH* intermediate from the reaction channel. Transition state theory (TST) has been considered to evaluate the rate constants for each step of the reaction. Overall results suggest Cu 2 to be better compared to Cu 2 + and Cu 2 − dimers for HCOOH formation and Cu 2 + over Cu 2 and Cu 2 − dimers to be more efficient for H 3 COH formation. This work opens the way for further investigation of the reaction mechanism and development of an efficient catalyst for CO 2 hydrogenation.

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DFT study of CO2 catalytic conversion by H2 over Ni13 cluster

Cited by 14 publications

References 50 publications

Ab Initio Study of the C–O Bond Dissociation in CO₂ Reduction by Redox and Carboxyl Routes on 3d Transition Metal Systems

Ab Initio Study of the C–O Bond Dissociation in CO₂ Reduction by Redox and Carboxyl Routes on 3d Transition Metal Systems

Advances in studies of the structural effects of supported Ni catalysts for CO₂hydrogenation: from nanoparticle to single atom catalyst

Reaction Mechanism and Kinetics for the Selective Hydrogenation of Carbon Dioxide to Formic Acid and Methanol over the [Cu₂]^0,±1 Dimer

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DFT study of CO2 catalytic conversion by H2 over Ni13 cluster

Cited by 14 publications

References 50 publications

Ab Initio Study of the C–O Bond Dissociation in CO2 Reduction by Redox and Carboxyl Routes on 3d Transition Metal Systems

Ab Initio Study of the C–O Bond Dissociation in CO2 Reduction by Redox and Carboxyl Routes on 3d Transition Metal Systems

Advances in studies of the structural effects of supported Ni catalysts for CO2hydrogenation: from nanoparticle to single atom catalyst

Reaction Mechanism and Kinetics for the Selective Hydrogenation of Carbon Dioxide to Formic Acid and Methanol over the [Cu2]0,±1 Dimer

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Resources

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Ab Initio Study of the C–O Bond Dissociation in CO₂ Reduction by Redox and Carboxyl Routes on 3d Transition Metal Systems

Ab Initio Study of the C–O Bond Dissociation in CO₂ Reduction by Redox and Carboxyl Routes on 3d Transition Metal Systems

Advances in studies of the structural effects of supported Ni catalysts for CO₂hydrogenation: from nanoparticle to single atom catalyst

Reaction Mechanism and Kinetics for the Selective Hydrogenation of Carbon Dioxide to Formic Acid and Methanol over the [Cu₂]^0,±1 Dimer