# Investigation of the Effect of Alkyl Chain Length on the Size and Distribution of Thiol-Stabilized Silver Nanoparticles for Proton Exchange Membrane Fuel Cell Applications

## TL;DR

This study shows how the length of alkyl chains in thiol-stabilized silver nanoparticles affects their size and performance in proton exchange membrane fuel cells.

## Contribution

The study demonstrates that C12 thiol-stabilized Ag NPs enhance PEMFC performance and CO resistance when deposited at optimal surface pressure.

## Key findings

- C12 thiol-stabilized Ag NPs showed better uniformity and no agglomeration compared to shorter alkyl chains.
- C12 Ag NPs deposited at 6 mN/m surface pressure increased power density by 26.5% in PEMFCs.
- C12 Ag NPs exhibited the highest resistance to CO poisoning compared to other alkyl chain lengths.

## Abstract

This article reports on how the length of the alkyl chain influences the morphological properties of thiol-stabilized silver nanoparticles (Ag NPs) and their subsequent effects on the performance and durability of proton exchange membrane fuel cells (PEMFCs). We synthesized thiol-stabilized Ag NPs by varying the alkyl chain length: 1-hexane thiol (C6), 1-octanethiol (C8), 1-decanethiol (C10), 1-dodecanethiol (C12), and 1-tetradecanethiol (C14), which we achieved using the two–phase Brust–Schiffrin method. X-ray Diffraction (XRD) patterns confirm the formation of crystalline Ag NPs. A morphological study conducted using a Transmission Electron Microscope (TEM) demonstrated that smaller alkyl chain length thiols (C6, C8, and C10) tend to coalesce, while C12 shows better uniformity with no agglomeration. C14 produces larger nanoparticles. A distinct pressure-area isotherm was observed when Ag NPs were spread at the water/air interface of a Langmuir–Blodgett (LB) trough. After obtaining the monolayer formation pressure range, we coated the Nafion 117 membrane of a polymer electrolyte membrane fuel cell with these nanoparticles to form monolayers of different Ag NPs (C6, C8, C12, C14) at various surface pressures (2 mN/m, 6 mN/m and 10 mN/m). Maximum power output enhancement was observed for C12, while other nanoparticles (C6, C8, C10, C14) did not exhibit noticeable power enhancement for PEMFCs. C12 Ag NPs deposited at surface pressure 6 mN/m give maximum power density increase (26.5%) at the fuel cell test station. In addition, we examined the carbon monoxide (CO) resistance test by mixing 0.1% CO with hydrogen (H2), and C12 Ag NPs showed the highest resistance to CO poisoning. However, no enhancement in power or CO tolerance was observed when C12 Ag NPs were coated by spray coating. These outcomes showcase that alkyl chain length plays a critical role in controlling the size and distribution of thiol-stabilized nanoparticles, which eventually has a direct impact on the performance and CO resistance of PEMFCs when applied to polymer electrolyte (Nafion 117). In addition, surface pressure during monolayer formation controls the distribution of Ag NPs (the distance between nanoparticles at the membrane interface), which is necessary to achieve catalytic activity for power improvement and to prevent platinum (Pt) poisoning by CO oxidation at ambient conditions.