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CO2 hydrogenation to HCOOH on PdZn surface and supported PdZn Cluster: A Comparative DFT study.

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Title: CO2 hydrogenation to HCOOH on PdZn surface and supported PdZn Cluster: A Comparative DFT study.
Authors: Wirmas, Marleni1 (AUTHOR), Budiantono, Reva2 (AUTHOR), Mahyuddin, Muhammad Haris1,3,4 (AUTHOR) mahyuddin133@itb.ac.id, Agusta, Mohammad Kemal1,3,4 (AUTHOR) kemal@itb.ac.id, Saputro, Adhitya Gandaryus3,4 (AUTHOR), Yudistira, Hadi Teguh5 (AUTHOR), Dipojono, Hermawan Kresno3,4 (AUTHOR)
Source: Applied Surface Science. Mar2025, Vol. 685, pN.PAG-N.PAG. 1p.
Subjects: Structural optimization, Density functional theory, Formic acid, Electronic structure, Laminated metals
Abstract: [Display omitted] • The structure modification of PdZn surface to a supported subnanometer cluster offers better stability of the intermediates. • At temperature >400 K, KPd 5 Zn/ZrO 2 (101) produces more HCOOH than PdZn(101) and PdZn(111) surfaces. • HCOO and COOH pathways are competing in Pd 5 Zn/ZrO 2 (101), whereas the HCOO pathway is favored on the PdZn(101) surface. • In the two observed pathways, the HCOO and COOH formation are the rate-limiting steps for both catalyst systems. Modifying heterogeneous catalysts for supported cluster-based types is important to design catalysts with better activity, stability, and selectivity. Alloying Pd with Zn and supported by ZrO 2 is a promising way to design catalysts for CO 2 hydrogenation to HCOOH, but the nature of the active catalytic sites and the mechanism remain unknown. Two representative models have been investigated: subnanometer cluster Pd 5 Zn/ZrO 2 and PdZn(101) surface. DFT calculations combined with microkinetic simulations are used to identify the optimum structure and configurations for the reaction. Compared to the PdZn(101) surface, the Pd 5 Zn/ZrO 2 offers much more stable adsorption and formation of intermediate species. Moreover, the formate route is more likely to proceed on PdZn(101) surface from the viewpoint of thermodynamic and kinetic. In contrast, the supported Pd 5 Zn/ZrO 2 cluster prefers the carboxyl pathway, where the interface site between cluster-support is ascribed to a far more stable configuration. Electronic structure analysis reveals the nature of the transition state on intermediate formation, particularly the role of Pd and Zn edge atoms on the selectivity towards the carboxyl pathway on Pd 5 Zn/ZrO 2. Finally, the comparison of microkinetic simulation results shows a preference for HCOOH formation on Pd 5 Zn/ZrO 2 than PdZn(101) surface at medium to higher temperature. [ABSTRACT FROM AUTHOR]
Copyright of Applied Surface Science is the property of Elsevier B.V. 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: CO2 hydrogenation to HCOOH on PdZn surface and supported PdZn Cluster: A Comparative DFT study.
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  Data: <searchLink fieldCode="AR" term="%22Wirmas%2C+Marleni%22">Wirmas, Marleni</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Budiantono%2C+Reva%22">Budiantono, Reva</searchLink><relatesTo>2</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Mahyuddin%2C+Muhammad+Haris%22">Mahyuddin, Muhammad Haris</searchLink><relatesTo>1,3,4</relatesTo> (AUTHOR)<i> mahyuddin133@itb.ac.id</i><br /><searchLink fieldCode="AR" term="%22Agusta%2C+Mohammad+Kemal%22">Agusta, Mohammad Kemal</searchLink><relatesTo>1,3,4</relatesTo> (AUTHOR)<i> kemal@itb.ac.id</i><br /><searchLink fieldCode="AR" term="%22Saputro%2C+Adhitya+Gandaryus%22">Saputro, Adhitya Gandaryus</searchLink><relatesTo>3,4</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Yudistira%2C+Hadi+Teguh%22">Yudistira, Hadi Teguh</searchLink><relatesTo>5</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Dipojono%2C+Hermawan+Kresno%22">Dipojono, Hermawan Kresno</searchLink><relatesTo>3,4</relatesTo> (AUTHOR)
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  Data: <searchLink fieldCode="JN" term="%22Applied+Surface+Science%22">Applied Surface Science</searchLink>. Mar2025, Vol. 685, pN.PAG-N.PAG. 1p.
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  Data: <searchLink fieldCode="DE" term="%22Structural+optimization%22">Structural optimization</searchLink><br /><searchLink fieldCode="DE" term="%22Density+functional+theory%22">Density functional theory</searchLink><br /><searchLink fieldCode="DE" term="%22Formic+acid%22">Formic acid</searchLink><br /><searchLink fieldCode="DE" term="%22Electronic+structure%22">Electronic structure</searchLink><br /><searchLink fieldCode="DE" term="%22Laminated+metals%22">Laminated metals</searchLink>
– Name: Abstract
  Label: Abstract
  Group: Ab
  Data: [Display omitted] • The structure modification of PdZn surface to a supported subnanometer cluster offers better stability of the intermediates. • At temperature >400 K, KPd 5 Zn/ZrO 2 (101) produces more HCOOH than PdZn(101) and PdZn(111) surfaces. • HCOO and COOH pathways are competing in Pd 5 Zn/ZrO 2 (101), whereas the HCOO pathway is favored on the PdZn(101) surface. • In the two observed pathways, the HCOO and COOH formation are the rate-limiting steps for both catalyst systems. Modifying heterogeneous catalysts for supported cluster-based types is important to design catalysts with better activity, stability, and selectivity. Alloying Pd with Zn and supported by ZrO 2 is a promising way to design catalysts for CO 2 hydrogenation to HCOOH, but the nature of the active catalytic sites and the mechanism remain unknown. Two representative models have been investigated: subnanometer cluster Pd 5 Zn/ZrO 2 and PdZn(101) surface. DFT calculations combined with microkinetic simulations are used to identify the optimum structure and configurations for the reaction. Compared to the PdZn(101) surface, the Pd 5 Zn/ZrO 2 offers much more stable adsorption and formation of intermediate species. Moreover, the formate route is more likely to proceed on PdZn(101) surface from the viewpoint of thermodynamic and kinetic. In contrast, the supported Pd 5 Zn/ZrO 2 cluster prefers the carboxyl pathway, where the interface site between cluster-support is ascribed to a far more stable configuration. Electronic structure analysis reveals the nature of the transition state on intermediate formation, particularly the role of Pd and Zn edge atoms on the selectivity towards the carboxyl pathway on Pd 5 Zn/ZrO 2. Finally, the comparison of microkinetic simulation results shows a preference for HCOOH formation on Pd 5 Zn/ZrO 2 than PdZn(101) surface at medium to higher temperature. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
  Label:
  Group: Ab
  Data: <i>Copyright of Applied Surface Science is the property of Elsevier B.V. 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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      – Type: doi
        Value: 10.1016/j.apsusc.2024.162095
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      – Code: eng
        Text: English
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        PageCount: 1
        StartPage: N.PAG
    Subjects:
      – SubjectFull: Structural optimization
        Type: general
      – SubjectFull: Density functional theory
        Type: general
      – SubjectFull: Formic acid
        Type: general
      – SubjectFull: Electronic structure
        Type: general
      – SubjectFull: Laminated metals
        Type: general
    Titles:
      – TitleFull: CO2 hydrogenation to HCOOH on PdZn surface and supported PdZn Cluster: A Comparative DFT study.
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            NameFull: Wirmas, Marleni
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            NameFull: Budiantono, Reva
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            NameFull: Mahyuddin, Muhammad Haris
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            NameFull: Dipojono, Hermawan Kresno
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            – D: 15
              M: 03
              Text: Mar2025
              Type: published
              Y: 2025
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              Value: 685
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            – TitleFull: Applied Surface Science
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