Optimal Icosahedral Copper-Based Bimetallic Clusters for the Selective Electrocatalytic CO<sub>2</sub> Conversion to One Carbon Products
Electrochemical CO<sub>2</sub> reduction reactions can lead to high value-added chemical and materials production while helping decrease anthropogenic CO<sub>2</sub> emissions. Copper metal clusters can reduce CO<sub>2</sub> to more than thirty different hydrocarb...
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MDPI AG
2022-12-01
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| Series: | Nanomaterials |
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| Online Access: | https://www.mdpi.com/2079-4991/13/1/87 |
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| author | Azeem Ghulam Nabi Aman-ur-Rehman Akhtar Hussain Gregory A. Chass Devis Di Tommaso |
| author_facet | Azeem Ghulam Nabi Aman-ur-Rehman Akhtar Hussain Gregory A. Chass Devis Di Tommaso |
| author_sort | Azeem Ghulam Nabi |
| collection | DOAJ |
| description | Electrochemical CO<sub>2</sub> reduction reactions can lead to high value-added chemical and materials production while helping decrease anthropogenic CO<sub>2</sub> emissions. Copper metal clusters can reduce CO<sub>2</sub> to more than thirty different hydrocarbons and oxygenates yet they lack the required selectivity. We present a computational characterization of the role of nano-structuring and alloying in Cu-based catalysts on the activity and selectivity of CO<sub>2</sub> reduction to generate the following one-carbon products: carbon monoxide (CO), formic acid (HCOOH), formaldehyde (H<sub>2</sub>C=O), methanol (CH<sub>3</sub>OH) and methane (CH<sub>4</sub>). The structures and energetics were determined for the adsorption, activation, and conversion of CO<sub>2</sub> on monometallic and bimetallic (decorated and core@shell) 55-atom Cu-based clusters. The dopant metals considered were Ag, Cd, Pd, Pt, and Zn, located at different coordination sites. The relative binding strength of the intermediates were used to identify the optimal catalyst for the selective CO<sub>2</sub> conversion to one-carbon products. It was discovered that single atom Cd or Zn doping is optimal for the conversion of CO<sub>2</sub> to CO. The core@shell models with Ag, Pd and Pt provided higher selectivity for formic acid and formaldehyde. The Cu-Pt and Cu-Pd showed lowest overpotential for methane formation. |
| first_indexed | 2024-03-09T03:28:16Z |
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| id | doaj.art-499f4e53fcfd4dbb96fa76a5d07dcf9e |
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| issn | 2079-4991 |
| language | English |
| last_indexed | 2024-03-09T03:28:16Z |
| publishDate | 2022-12-01 |
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| series | Nanomaterials |
| spelling | doaj.art-499f4e53fcfd4dbb96fa76a5d07dcf9e2023-12-03T14:58:28ZengMDPI AGNanomaterials2079-49912022-12-011318710.3390/nano13010087Optimal Icosahedral Copper-Based Bimetallic Clusters for the Selective Electrocatalytic CO<sub>2</sub> Conversion to One Carbon ProductsAzeem Ghulam Nabi0Aman-ur-Rehman1Akhtar Hussain2Gregory A. Chass3Devis Di Tommaso4Department of Chemistry, School of Physical and Chemical Sciences, Queen Mary University of London, Mile End Road, London E1 4NS, UKDepartment of Physics and Applied Mathematics, Pakistan Institute of Engineering and Applied Sciences, Nilore, Islamabad 45650, PakistanTheoretical Physics Division, Pakistan Institute of Nuclear Science& Technology (PINSTECH), Nilore, Islamabad 45650, PakistanDepartment of Chemistry, School of Physical and Chemical Sciences, Queen Mary University of London, Mile End Road, London E1 4NS, UKDepartment of Chemistry, School of Physical and Chemical Sciences, Queen Mary University of London, Mile End Road, London E1 4NS, UKElectrochemical CO<sub>2</sub> reduction reactions can lead to high value-added chemical and materials production while helping decrease anthropogenic CO<sub>2</sub> emissions. Copper metal clusters can reduce CO<sub>2</sub> to more than thirty different hydrocarbons and oxygenates yet they lack the required selectivity. We present a computational characterization of the role of nano-structuring and alloying in Cu-based catalysts on the activity and selectivity of CO<sub>2</sub> reduction to generate the following one-carbon products: carbon monoxide (CO), formic acid (HCOOH), formaldehyde (H<sub>2</sub>C=O), methanol (CH<sub>3</sub>OH) and methane (CH<sub>4</sub>). The structures and energetics were determined for the adsorption, activation, and conversion of CO<sub>2</sub> on monometallic and bimetallic (decorated and core@shell) 55-atom Cu-based clusters. The dopant metals considered were Ag, Cd, Pd, Pt, and Zn, located at different coordination sites. The relative binding strength of the intermediates were used to identify the optimal catalyst for the selective CO<sub>2</sub> conversion to one-carbon products. It was discovered that single atom Cd or Zn doping is optimal for the conversion of CO<sub>2</sub> to CO. The core@shell models with Ag, Pd and Pt provided higher selectivity for formic acid and formaldehyde. The Cu-Pt and Cu-Pd showed lowest overpotential for methane formation.https://www.mdpi.com/2079-4991/13/1/87CO<sub>2</sub> reductioncopper catalystsmetal dopingdensity functional calculations |
| spellingShingle | Azeem Ghulam Nabi Aman-ur-Rehman Akhtar Hussain Gregory A. Chass Devis Di Tommaso Optimal Icosahedral Copper-Based Bimetallic Clusters for the Selective Electrocatalytic CO<sub>2</sub> Conversion to One Carbon Products Nanomaterials CO<sub>2</sub> reduction copper catalysts metal doping density functional calculations |
| title | Optimal Icosahedral Copper-Based Bimetallic Clusters for the Selective Electrocatalytic CO<sub>2</sub> Conversion to One Carbon Products |
| title_full | Optimal Icosahedral Copper-Based Bimetallic Clusters for the Selective Electrocatalytic CO<sub>2</sub> Conversion to One Carbon Products |
| title_fullStr | Optimal Icosahedral Copper-Based Bimetallic Clusters for the Selective Electrocatalytic CO<sub>2</sub> Conversion to One Carbon Products |
| title_full_unstemmed | Optimal Icosahedral Copper-Based Bimetallic Clusters for the Selective Electrocatalytic CO<sub>2</sub> Conversion to One Carbon Products |
| title_short | Optimal Icosahedral Copper-Based Bimetallic Clusters for the Selective Electrocatalytic CO<sub>2</sub> Conversion to One Carbon Products |
| title_sort | optimal icosahedral copper based bimetallic clusters for the selective electrocatalytic co sub 2 sub conversion to one carbon products |
| topic | CO<sub>2</sub> reduction copper catalysts metal doping density functional calculations |
| url | https://www.mdpi.com/2079-4991/13/1/87 |
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