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Reaction Pathways and the Underlying Mechanism of Ni 4 Cu Alloy Clusters Anchored on Graphene for CO 2 Electroreduction to Formic Acid.

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Title: Reaction Pathways and the Underlying Mechanism of Ni 4 Cu Alloy Clusters Anchored on Graphene for CO 2 Electroreduction to Formic Acid.
Authors: Zhang, Lisu1 (AUTHOR), Zou, Yanbo1 (AUTHOR) zouyb@xjnu.edu.cn, Wang, Xingguo1 (AUTHOR), Li, Qingyang1 (AUTHOR)
Source: Nanomaterials (2079-4991). Apr2026, Vol. 16 Issue 7, p434. 11p.
Subjects: Copper-nickel alloys, Formic acid, Chemical kinetics, Catalysis, Density functional theory, Charge transfer, Graphene, Carbon dioxide
Abstract: The electrochemical CO2 reduction reaction (CO2RR) offers a sustainable route for converting greenhouse gases into high-value fuels; however, its efficiency has long been constrained by the thermodynamic stability of CO2 molecules and the competing hydrogen evolution reaction. Using density functional theory (DFT) calculations, this work systematically investigates the catalytic performance of Ni5 and alloy Ni4Cu clusters anchored on divacancy graphene (DVG) for CO2RR. The results demonstrate that the introduction of Cu atoms significantly enhances the interfacial binding energy between the cluster and the support (shifting from −6.2 eV to −7.5 eV). Charge density difference analysis combined with Bader charge analysis further reveals that interfacial charge transfer and the formation of Ni–C bonds serve as the electronic origin of this improved stability. Free energy calculations show that, compared to Ni5/DVG, Ni4Cu/DVG substantially reduces the energy barrier of the rate-determining step for formic acid (HCOOH) formation from 1.18 eV to 0.26 eV, thereby significantly optimizing the reaction kinetics. Crystal orbital Hamilton population (COHP) analysis demonstrates that Cu doping modulates metal–oxygen bond strength in the key *OCHO intermediate (ICOHP: Ni-O bonds at −0.697 eV/−0.976 eV vs. Cu-O bonds at −0.408 eV/−0.492 eV), optimizing the adsorption–desorption balance and steering selectivity toward HCOOH. This work elucidates the atomic-scale electronic and bonding mechanisms underlying Ni–Cu synergistic effects, providing theoretical guidance for designing efficient non-noble metal CO2RR electrocatalysts. [ABSTRACT FROM AUTHOR]
Copyright of Nanomaterials (2079-4991) is the property of MDPI and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
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Items – Name: Title
  Label: Title
  Group: Ti
  Data: Reaction Pathways and the Underlying Mechanism of Ni 4 Cu Alloy Clusters Anchored on Graphene for CO 2 Electroreduction to Formic Acid.
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  Data: <searchLink fieldCode="AR" term="%22Zhang%2C+Lisu%22">Zhang, Lisu</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Zou%2C+Yanbo%22">Zou, Yanbo</searchLink><relatesTo>1</relatesTo> (AUTHOR)<i> zouyb@xjnu.edu.cn</i><br /><searchLink fieldCode="AR" term="%22Wang%2C+Xingguo%22">Wang, Xingguo</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Li%2C+Qingyang%22">Li, Qingyang</searchLink><relatesTo>1</relatesTo> (AUTHOR)
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  Data: <searchLink fieldCode="JN" term="%22Nanomaterials+%282079-4991%29%22">Nanomaterials (2079-4991)</searchLink>. Apr2026, Vol. 16 Issue 7, p434. 11p.
– Name: Subject
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  Data: <searchLink fieldCode="DE" term="%22Copper-nickel+alloys%22">Copper-nickel alloys</searchLink><br /><searchLink fieldCode="DE" term="%22Formic+acid%22">Formic acid</searchLink><br /><searchLink fieldCode="DE" term="%22Chemical+kinetics%22">Chemical kinetics</searchLink><br /><searchLink fieldCode="DE" term="%22Catalysis%22">Catalysis</searchLink><br /><searchLink fieldCode="DE" term="%22Density+functional+theory%22">Density functional theory</searchLink><br /><searchLink fieldCode="DE" term="%22Charge+transfer%22">Charge transfer</searchLink><br /><searchLink fieldCode="DE" term="%22Graphene%22">Graphene</searchLink><br /><searchLink fieldCode="DE" term="%22Carbon+dioxide%22">Carbon dioxide</searchLink>
– Name: Abstract
  Label: Abstract
  Group: Ab
  Data: The electrochemical CO2 reduction reaction (CO2RR) offers a sustainable route for converting greenhouse gases into high-value fuels; however, its efficiency has long been constrained by the thermodynamic stability of CO2 molecules and the competing hydrogen evolution reaction. Using density functional theory (DFT) calculations, this work systematically investigates the catalytic performance of Ni5 and alloy Ni4Cu clusters anchored on divacancy graphene (DVG) for CO2RR. The results demonstrate that the introduction of Cu atoms significantly enhances the interfacial binding energy between the cluster and the support (shifting from −6.2 eV to −7.5 eV). Charge density difference analysis combined with Bader charge analysis further reveals that interfacial charge transfer and the formation of Ni–C bonds serve as the electronic origin of this improved stability. Free energy calculations show that, compared to Ni5/DVG, Ni4Cu/DVG substantially reduces the energy barrier of the rate-determining step for formic acid (HCOOH) formation from 1.18 eV to 0.26 eV, thereby significantly optimizing the reaction kinetics. Crystal orbital Hamilton population (COHP) analysis demonstrates that Cu doping modulates metal–oxygen bond strength in the key *OCHO intermediate (ICOHP: Ni-O bonds at −0.697 eV/−0.976 eV vs. Cu-O bonds at −0.408 eV/−0.492 eV), optimizing the adsorption–desorption balance and steering selectivity toward HCOOH. This work elucidates the atomic-scale electronic and bonding mechanisms underlying Ni–Cu synergistic effects, providing theoretical guidance for designing efficient non-noble metal CO2RR electrocatalysts. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
  Label:
  Group: Ab
  Data: <i>Copyright of Nanomaterials (2079-4991) is the property of MDPI and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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RecordInfo BibRecord:
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    Identifiers:
      – Type: doi
        Value: 10.3390/nano16070434
    Languages:
      – Code: eng
        Text: English
    PhysicalDescription:
      Pagination:
        PageCount: 11
        StartPage: 434
    Subjects:
      – SubjectFull: Copper-nickel alloys
        Type: general
      – SubjectFull: Formic acid
        Type: general
      – SubjectFull: Chemical kinetics
        Type: general
      – SubjectFull: Catalysis
        Type: general
      – SubjectFull: Density functional theory
        Type: general
      – SubjectFull: Charge transfer
        Type: general
      – SubjectFull: Graphene
        Type: general
      – SubjectFull: Carbon dioxide
        Type: general
    Titles:
      – TitleFull: Reaction Pathways and the Underlying Mechanism of Ni 4 Cu Alloy Clusters Anchored on Graphene for CO 2 Electroreduction to Formic Acid.
        Type: main
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      – PersonEntity:
          Name:
            NameFull: Zhang, Lisu
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            NameFull: Zou, Yanbo
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            NameFull: Wang, Xingguo
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            NameFull: Li, Qingyang
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            – D: 01
              M: 04
              Text: Apr2026
              Type: published
              Y: 2026
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            – TitleFull: Nanomaterials (2079-4991)
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