Alkanethiol Self-assembly Behavior on Gold Nanoparticles Based on Single-nanoparticle Collision Electrochemistry

doi:10.7503/cjcu20240402

Abstract

Abstract:

The self-assembly kinetics of alkanethiol on the surface of gold nanoparticles（Au NPs） was investigated by detecting dispersed individual particles in the solution based on single-nanoparticle collision electrochemistry， as well as the effects of reaction temperature， alkanethiol concentration， and molecular structure on their assembly behavior during the assembly process. The results showed that the formation of self-assembled monolayers of alkanethiol reduced the active area of Au NPs， leading to a decreased current intensity for catalyzing hydrogen evolution. Based on this， comparing the current transients of different self-assembly conditions， it was found that the increase of adsorption amount was correlated positively with the concentration of alkanethiol and the reaction temperature within limits. Controlling the reaction time to 10 min， when the concentration of 6-mercapto-1-hexanol （6-MCH） was 73 mmol/L and the reaction temperature is 45 ℃， 6-MCH adsorbed the most amount on Au NPs. Furthermore， by comparing the self-assembly kinetics curves of 6-MCH， 3-mercapto-1-propanol（3-MCP）， and 3-mercaptopropionic acid（3-MPA）， it was found that the self-assembly process consisted of diffusion controlled rapid adsorption and slow recombination. Due to the strong electrostatic repulsion between the functional head group （carboxylate） of 3-MPA and the citric acid ligand of Au NPs， the adsorption capacity of 3-MPA was significantly lower than that of the other two molecules. The maximum adsorption capacity of 3-MCP and 6-MCH was basically the same， but due to the longer alkyl chain of 6-MCH， its adsorption free energy change was about 4.0 kJ/mol higher than that of 3-MCP， and it eventually reached the maximum adsorption value later.

Key words: Self-assembly, Single-particle detection, Alkanethiol, Au NPs

CLC Number:

O657

TrendMD:

BAI Yiyan, WANG Chenyang, GAO Yang, LI Jiamin, YANG Haiying. Alkanethiol Self-assembly Behavior on Gold Nanoparticles Based on Single-nanoparticle Collision Electrochemistry[J]. Chem. J. Chinese Universities, 2025, 46(2): 20240402.

Figures/Tables 8

References 35

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