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Binary Surfactant-Mediated Tunable Nanotip Growth on Gold Nanoparticles and Applications in Photothermal Catalysis.

ABSTRACT: Plasmonic nanostructures with sharp tips are widely used for optical signal enhancement because of their strong light-confining abilities. These structures have a wide range of potential applications, for example, in sensing, bioimaging, and surface-enhanced Raman scattering. Au nanoparticles, which are important plasmonic materials with high photothermal conversion efficiencies in the visible to near-infrared region, have contributed greatly to the development of photothermal catalysis. However, the existing methods for synthesizing nanostructures with tips need the assistance of poly(vinylpyrrolidone), thiols, or biomolecules. This greatly hinders signal detection because of stubborn residues. Here, we propose an efficient binary surfactant-mediated method for controlling nanotip growth on Au nanoparticle surfaces. This avoids the effects of surfactants and can be used with other Au nanostructures. The Au architecture tip growth process can be controlled well by adjusting the ratio of hexadecyltrimethylammonium bromide to hexadecyltrimethylammonium chloride. This is due to the different levels of attraction between Br^-/Cl^- and Au³⁺ ions. The surface-enhanced Raman scattering and catalytic abilities of the synthesized nanoparticles with tips were evaluated by electromagnetic simulation and photothermal catalysis experiments (with 4-nitrothiophenol). The results show good potential for use in surface-enhanced Raman scattering applications. This method provides a new strategy for designing plasmonic photothermal nanostructures for chemical and biological applications.

SUBMITTER: Mi X

PROVIDER: S-EPMC8294035 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:Mercaptoundecanoic acid (MUA) functionalized gold nanoparticles (AuNP-MUA) were synthesized and demonstrated to possess pH-triggered aggregation and re-dispersion, as well as the capability of phase transfer between aqueous and organic phases in response to changes in pH. The pH of aggregation for AuNP-MUA is consistent with the pKa of MUA (pH ~4) in solution, while AuNP-MUA phase transition between aqueous and organic phases occurs at pH ~9. The ion pair formation between the amine group in octadecylamine (ODA), the carboxylate group in MUA, and the hydrophobic alkyl chain of ODA facilitates the phase transfer of AuNP-MUA into an organic medium. The AuNP-MUA were investigated as a reusable catalyst in the catalytic reduction of 4-nitrophenol by borohydride-a model reaction for AuNPs. It was determined that 100% MUA surface coverage completely inhibits the catalytic activity of AuNPs. Decreasing the surface coverage was shown to increase catalytic activity, but this decrease also leads to decreased colloidal stability, recoverability, and reusability in subsequent reactions. At 60% MUA surface coverage, colloidal stability and catalytic activity were achieved, but the surface coverage was insufficient to enable redispersion following pH-induced recovery. A balance between AuNP colloidal stability, recoverability, and catalytic activity with reusability was achieved at 90% MUA surface coverage. The AuNP-MUA catalyst can also be recovered at different pH ranges depending on the recovery method employed. At pH ~4, protonation of the MUA results in reduced surface charge and aggregation. At pH ~9, ODA will form an ion-pair with the MUA and induce phase transfer into an immiscible organic phase. Both the pH-triggered aggregation/re-dispersion and aqueous/organic phase transfer methods were employed for catalyst recovery and reuse in subsequent reactions. The ability to recover and reuse the AuNP-MUA catalyst by two different methods and different pH regimes is significant, based on the fact that nanoparticle-catalyzed reactions may occur under different pH conditions.

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Binary Surfactant-Mediated Tunable Nanotip Growth on Gold Nanoparticles and Applications in Photothermal Catalysis.

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