Detection of free chlorine in water using graphene-like carbon based chemiresistive sensors

Free chlorine is the most commonly used water disinfectant. Measuring its concentration during and after water treatment is crucial to ensure its effectiveness. However, many of the existing methods do not allow for continuous on-line monitoring. Here we demonstrate a solid state chemiresistive sensor using graphene-like carbon (GLC) that overcomes that issue. GLC films that were either bare or non-covalently functionalized with the redox-active phenyl-capped aniline tetramer (PCAT) were successfully employed to quantify aqueous free chlorine, although functionalized devices showed better performance. The response of the sensors to increasing concentrations of free chlorine followed a Langmuir adsorption isotherm in the two tested ranges: 0.01-0.2 ppm and 0.2-1.4 ppm. The limit of detection was estimated to be 1 ppb, permitting the detection of breaches in chlorine filters. The devices respond to decreasing levels of free chlorine without the need for a reset, allowing for the continuous monitoring of fluctuations in the concentration. The maximum sensor response and saturation concentration were found to depend on the thickness of the GLC film. Hence, the sensitivity and dynamic range of the sensors can be tailored to different applications by adjusting the thickness of the films. Tap water samples from a residential area were tested using these sensors, which showed good agreement with standard colorimetric measurement methods. The devices did not suffer from interferences in the presence of ions commonly found in drinking water. Overall, these sensors are a cost-effective option for the continuous automated monitoring of free chlorine in drinking water.