Workflow-driven catalytic modulation from single-atom catalysts to Au–alloy clusters on graphene
Abstract Gold-based (Au) nanostructures are efficient catalysts for CO oxidation, hydrogen evolution (HER), and oxygen evolution (OER) reactions, but stabilizing them on graphene (Gr) is challenging due to weak affinity from delocalized $$p_{z}$$ carbon orbitals. This study investigates forming meta...
Saved in:
| Main Authors: | , , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
Nature Portfolio
2025-01-01
|
| Series: | Scientific Reports |
| Subjects: | |
| Online Access: | https://doi.org/10.1038/s41598-025-85891-6 |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| _version_ | 1832594819238592512 |
|---|---|
| author | Gabriel Reynald Da Silva João Paulo Cerqueira Felix Celso R. C. Rêgo Alexandre C. Dias Carlos Maciel de O. Bastos Maurício J. Piotrowski Diego Guedes-Sobrinho |
| author_facet | Gabriel Reynald Da Silva João Paulo Cerqueira Felix Celso R. C. Rêgo Alexandre C. Dias Carlos Maciel de O. Bastos Maurício J. Piotrowski Diego Guedes-Sobrinho |
| author_sort | Gabriel Reynald Da Silva |
| collection | DOAJ |
| description | Abstract Gold-based (Au) nanostructures are efficient catalysts for CO oxidation, hydrogen evolution (HER), and oxygen evolution (OER) reactions, but stabilizing them on graphene (Gr) is challenging due to weak affinity from delocalized $$p_{z}$$ carbon orbitals. This study investigates forming metal alloys to enhance stability and catalytic performance of Au-based nanocatalysts. Using ab initio density functional theory, we characterize $${\text {M}_{(n-x)}\text {Au}_{x}}$$ sub-nanoclusters (M = Ni, Pd, Pt, Cu, and Ag) with atomicities $$n=1-4$$ , both in gas-phase and supported on Gr. We find that M atoms act as “anchors,” enhancing binding to Gr and modulating catalytic efficiency. Notably, $${\text {Pt}_{(n-x)}\text {Au}_{x}}$$ /Gr shows improved stability, with segregation tendencies mitigated upon adsorption on Gr. The d-band center ( $$\varepsilon _{\text {d}}$$ ) model indicates catalytic potential, correlating an optimal $$\varepsilon _{\text {d}}$$ range of $$-1 \text { to }-2$$ eV for HER and OER catalysts. Incorporating Au into $${\text{M}_n}$$ adjusts $$\varepsilon _{\text {d}}$$ closer to the Fermi level, especially for Group-10 alloys, offering designs with improved stability and efficiency comparable to pure Au nanocatalysts. Our methodology leveraged SimStack, a workflow framework enabling modeling and analysis, enhancing reproducibility, and accelerating discovery. This work demonstrates SimStack’s pivotal role in advancing the understanding of composition-dependent stability and catalytic properties of Au-alloy clusters, providing a systematic approach to optimize metal-support interactions in catalytic applications. |
| format | Article |
| id | doaj-art-30c86ab25bea4486b4ae7e727ec1a264 |
| institution | Kabale University |
| issn | 2045-2322 |
| language | English |
| publishDate | 2025-01-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Scientific Reports |
| spelling | doaj-art-30c86ab25bea4486b4ae7e727ec1a2642025-01-19T12:18:31ZengNature PortfolioScientific Reports2045-23222025-01-0115111410.1038/s41598-025-85891-6Workflow-driven catalytic modulation from single-atom catalysts to Au–alloy clusters on grapheneGabriel Reynald Da Silva0João Paulo Cerqueira Felix1Celso R. C. Rêgo2Alexandre C. Dias3Carlos Maciel de O. Bastos4Maurício J. Piotrowski5Diego Guedes-Sobrinho6Department of Chemistry, Federal University of ParanáInstitute of Physics “Armando Dias Tavares”Karlsruhe Institute of Technology, Institute of Nanotechnology Hermann-von-Helmholtz-latzInstitute of Physics and International Center of Physics, University of BrasíliaInstitute of Physics and International Center of Physics, University of BrasíliaDepartment of Physics, Federal University of PelotasDepartment of Chemistry, Federal University of ParanáAbstract Gold-based (Au) nanostructures are efficient catalysts for CO oxidation, hydrogen evolution (HER), and oxygen evolution (OER) reactions, but stabilizing them on graphene (Gr) is challenging due to weak affinity from delocalized $$p_{z}$$ carbon orbitals. This study investigates forming metal alloys to enhance stability and catalytic performance of Au-based nanocatalysts. Using ab initio density functional theory, we characterize $${\text {M}_{(n-x)}\text {Au}_{x}}$$ sub-nanoclusters (M = Ni, Pd, Pt, Cu, and Ag) with atomicities $$n=1-4$$ , both in gas-phase and supported on Gr. We find that M atoms act as “anchors,” enhancing binding to Gr and modulating catalytic efficiency. Notably, $${\text {Pt}_{(n-x)}\text {Au}_{x}}$$ /Gr shows improved stability, with segregation tendencies mitigated upon adsorption on Gr. The d-band center ( $$\varepsilon _{\text {d}}$$ ) model indicates catalytic potential, correlating an optimal $$\varepsilon _{\text {d}}$$ range of $$-1 \text { to }-2$$ eV for HER and OER catalysts. Incorporating Au into $${\text{M}_n}$$ adjusts $$\varepsilon _{\text {d}}$$ closer to the Fermi level, especially for Group-10 alloys, offering designs with improved stability and efficiency comparable to pure Au nanocatalysts. Our methodology leveraged SimStack, a workflow framework enabling modeling and analysis, enhancing reproducibility, and accelerating discovery. This work demonstrates SimStack’s pivotal role in advancing the understanding of composition-dependent stability and catalytic properties of Au-alloy clusters, providing a systematic approach to optimize metal-support interactions in catalytic applications.https://doi.org/10.1038/s41598-025-85891-6GrapheneCluster alloysDensity functional theoryWorkflow |
| spellingShingle | Gabriel Reynald Da Silva João Paulo Cerqueira Felix Celso R. C. Rêgo Alexandre C. Dias Carlos Maciel de O. Bastos Maurício J. Piotrowski Diego Guedes-Sobrinho Workflow-driven catalytic modulation from single-atom catalysts to Au–alloy clusters on graphene Scientific Reports Graphene Cluster alloys Density functional theory Workflow |
| title | Workflow-driven catalytic modulation from single-atom catalysts to Au–alloy clusters on graphene |
| title_full | Workflow-driven catalytic modulation from single-atom catalysts to Au–alloy clusters on graphene |
| title_fullStr | Workflow-driven catalytic modulation from single-atom catalysts to Au–alloy clusters on graphene |
| title_full_unstemmed | Workflow-driven catalytic modulation from single-atom catalysts to Au–alloy clusters on graphene |
| title_short | Workflow-driven catalytic modulation from single-atom catalysts to Au–alloy clusters on graphene |
| title_sort | workflow driven catalytic modulation from single atom catalysts to au alloy clusters on graphene |
| topic | Graphene Cluster alloys Density functional theory Workflow |
| url | https://doi.org/10.1038/s41598-025-85891-6 |
| work_keys_str_mv | AT gabrielreynalddasilva workflowdrivencatalyticmodulationfromsingleatomcatalyststoaualloyclustersongraphene AT joaopaulocerqueirafelix workflowdrivencatalyticmodulationfromsingleatomcatalyststoaualloyclustersongraphene AT celsorcrego workflowdrivencatalyticmodulationfromsingleatomcatalyststoaualloyclustersongraphene AT alexandrecdias workflowdrivencatalyticmodulationfromsingleatomcatalyststoaualloyclustersongraphene AT carlosmacieldeobastos workflowdrivencatalyticmodulationfromsingleatomcatalyststoaualloyclustersongraphene AT mauriciojpiotrowski workflowdrivencatalyticmodulationfromsingleatomcatalyststoaualloyclustersongraphene AT diegoguedessobrinho workflowdrivencatalyticmodulationfromsingleatomcatalyststoaualloyclustersongraphene |