Agglomeration of Nanoparticles Inhibits Solvent‐Driven Ligand Stripping
Abstract The colloidal stability of nanoparticles (NPs) is significantly affected by complex solvent‐ligand interactions, with poor solvents often inducing NP agglomeration and ligand desorption from the surface. Despite the frequent occurrence of these phenomena in post‐synthetic experiments, the u...
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| Format: | Article |
| Language: | English |
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Wiley-VCH
2025-08-01
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| Series: | Advanced Materials Interfaces |
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| Online Access: | https://doi.org/10.1002/admi.202500234 |
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| author | Akhlak U. Mahmood Mehedi H. Rizvi Joseph B. Tracy Yaroslava G. Yingling |
| author_facet | Akhlak U. Mahmood Mehedi H. Rizvi Joseph B. Tracy Yaroslava G. Yingling |
| author_sort | Akhlak U. Mahmood |
| collection | DOAJ |
| description | Abstract The colloidal stability of nanoparticles (NPs) is significantly affected by complex solvent‐ligand interactions, with poor solvents often inducing NP agglomeration and ligand desorption from the surface. Despite the frequent occurrence of these phenomena in post‐synthetic experiments, the underlying mechanisms remain elusive. In this study, dynamic light scattering (DLS), thermogravimetric analysis (TGA), and large‐scale all‐atom molecular dynamics (MD) simulations are used to investigate solvent‐driven oleylamine ligand removal from Fe3O4 NPs. Eight experimentally relevant NP systems under replicated solvent conditions are modeled, enabling direct comparison and yielding deep insights into solvent‐mediated ligand stripping with excellent agreement. These findings reveal that ethanol's ability to strip oleylamine ligands from Fe3O4 NPs is impeded by NP agglomeration, where stripped and interdigitated ligands create a steric barrier, preventing solvent molecules from accessing the NP surface. This effect becomes more pronounced with increasing NP size due to the greater ligand surface density that enhances interdigitation. Moreover, the presence of a threshold concentration of the poor solvent in binary mixtures is identified, below which the maximum number of ligands can be stripped without initiating agglomeration. These insights provide a framework for optimizing solvent‐mediated ligand exchange, with implications for NP applications in catalysis, energy storage, optoelectronics, and biomedical engineering. |
| format | Article |
| id | doaj-art-b572d965678041bbb50398168dfe8347 |
| institution | Kabale University |
| issn | 2196-7350 |
| language | English |
| publishDate | 2025-08-01 |
| publisher | Wiley-VCH |
| record_format | Article |
| series | Advanced Materials Interfaces |
| spelling | doaj-art-b572d965678041bbb50398168dfe83472025-08-25T08:06:18ZengWiley-VCHAdvanced Materials Interfaces2196-73502025-08-011216n/an/a10.1002/admi.202500234Agglomeration of Nanoparticles Inhibits Solvent‐Driven Ligand StrippingAkhlak U. Mahmood0Mehedi H. Rizvi1Joseph B. Tracy2Yaroslava G. Yingling3Department of Materials Science and Engineering NC State University Raleigh NC 27695 USADepartment of Materials Science and Engineering NC State University Raleigh NC 27695 USADepartment of Materials Science and Engineering NC State University Raleigh NC 27695 USADepartment of Materials Science and Engineering NC State University Raleigh NC 27695 USAAbstract The colloidal stability of nanoparticles (NPs) is significantly affected by complex solvent‐ligand interactions, with poor solvents often inducing NP agglomeration and ligand desorption from the surface. Despite the frequent occurrence of these phenomena in post‐synthetic experiments, the underlying mechanisms remain elusive. In this study, dynamic light scattering (DLS), thermogravimetric analysis (TGA), and large‐scale all‐atom molecular dynamics (MD) simulations are used to investigate solvent‐driven oleylamine ligand removal from Fe3O4 NPs. Eight experimentally relevant NP systems under replicated solvent conditions are modeled, enabling direct comparison and yielding deep insights into solvent‐mediated ligand stripping with excellent agreement. These findings reveal that ethanol's ability to strip oleylamine ligands from Fe3O4 NPs is impeded by NP agglomeration, where stripped and interdigitated ligands create a steric barrier, preventing solvent molecules from accessing the NP surface. This effect becomes more pronounced with increasing NP size due to the greater ligand surface density that enhances interdigitation. Moreover, the presence of a threshold concentration of the poor solvent in binary mixtures is identified, below which the maximum number of ligands can be stripped without initiating agglomeration. These insights provide a framework for optimizing solvent‐mediated ligand exchange, with implications for NP applications in catalysis, energy storage, optoelectronics, and biomedical engineering.https://doi.org/10.1002/admi.202500234agglomerationcolloidal nanoparticlesligand strippingmolecular dynamics simulationssolvent effectsTGA and DLS |
| spellingShingle | Akhlak U. Mahmood Mehedi H. Rizvi Joseph B. Tracy Yaroslava G. Yingling Agglomeration of Nanoparticles Inhibits Solvent‐Driven Ligand Stripping Advanced Materials Interfaces agglomeration colloidal nanoparticles ligand stripping molecular dynamics simulations solvent effects TGA and DLS |
| title | Agglomeration of Nanoparticles Inhibits Solvent‐Driven Ligand Stripping |
| title_full | Agglomeration of Nanoparticles Inhibits Solvent‐Driven Ligand Stripping |
| title_fullStr | Agglomeration of Nanoparticles Inhibits Solvent‐Driven Ligand Stripping |
| title_full_unstemmed | Agglomeration of Nanoparticles Inhibits Solvent‐Driven Ligand Stripping |
| title_short | Agglomeration of Nanoparticles Inhibits Solvent‐Driven Ligand Stripping |
| title_sort | agglomeration of nanoparticles inhibits solvent driven ligand stripping |
| topic | agglomeration colloidal nanoparticles ligand stripping molecular dynamics simulations solvent effects TGA and DLS |
| url | https://doi.org/10.1002/admi.202500234 |
| work_keys_str_mv | AT akhlakumahmood agglomerationofnanoparticlesinhibitssolventdrivenligandstripping AT mehedihrizvi agglomerationofnanoparticlesinhibitssolventdrivenligandstripping AT josephbtracy agglomerationofnanoparticlesinhibitssolventdrivenligandstripping AT yaroslavagyingling agglomerationofnanoparticlesinhibitssolventdrivenligandstripping |