Johnson Dalmieda


DOI bib
Tuning the Chemical and Mechanical Properties of Conductive MoS<sub>2</sub> Thin Films by Surface Modification with Aryl Diazonium Salts
Dipankar Saha, Shayan Angizi, Maryam Darestani-Farahani, Johnson Dalmieda, P. Ravi Selvaganapathy, Peter Kruse
Langmuir, Volume 38, Issue 12

Molybdenum disulfide (MoS2) is a promising material for applications in sensors, energy storage, energy conversion devices, solar cells, and fuel cells. Because many of those applications require conductive materials, we recently developed a method for preparing a conductive form of MoS2 (c-MoS2) using dilute aqueous hydrogen peroxide in a simple and safe way. Here, we investigate modulating the chemical and mechanical surface properties of c-MoS2 thin films using diazonium chemistry. In addition to a direct passivation strategy of c-MoS2 with diazonium salts for electron-withdrawing groups, we also propose a novel in situ synthetic pathway for modification with electron-donating groups. The obtained results are examined by Raman spectroscopy and X-ray photoelectron spectroscopy. The degree of surface passivation of pristine and functionalized c-MoS2 films was tested by exposing them to aqueous solutions of different metal cations (Fe2+, Zn2+, Cu2+, and Co2+) and detecting the chemiresistive response. While pristine films were found to interact with several of the cations, modified films did not. We propose that a surface charge transfer mechanism is responsible for the chemiresistive response of the pristine films, while both modification routes succeeded at complete surface passivation. Functionalization was also found to lower the coefficient of friction for semiconducting 2H-MoS2, while all conductive materials (modified or not) also had lower coefficients of friction. This opens up a pathway to a palette of dry lubricant materials with improved chemical stability and tunable conductivity. Thus, both in situ and direct diazonium chemistries are powerful tools for tuning chemical and mechanical properties of conductive MoS2 for new devices and lubricants based on conductive MoS2.


DOI bib
Chemiresistive detection of silver ions in aqueous media
Johnson Dalmieda, Ana Zubiarrain-Laserna, Devanjith Ganepola, P. Ravi Selvaganapathy, Peter Kruse
Sensors and Actuators B: Chemical, Volume 328

• Chemiresistive sensors can be fabricated from percolation networks of few-layer graphene (FLG) flakes. • Functionalization with suitable ligands can achieve selective sensor response to Ag + ions in the 3 ppb to 1 ppm range. • Sensors are robust and reusable, can be reset at pH3 due to a shift in the complexation equilibrium. • The sensor response was tested in an environmental sample (river water) and found to correlate well with ICP-MS data. Silver is used as a water disinfectant in hospital settings as well as in purifiers for potable water. Although there are no strict regulations on the concentration of silver in water, adverse effects such as argyria and respiratory tract irritation have been correlated to excess silver consumption. Based on this, the levels of silver in water are recommended to be maintained below 100 ppb to ensure safety for human consumption. In this work, we present a silver sensor for use in aqueous media that utilizes bathocuproine, a silver selective chromophore, adsorbed onto few-layer graphene (FLG) flake networks for the chemiresistive detection of silver. Complexation of silver to bathocuproine modulates the conductivity of the FLG film, which can be probed by applying a small voltage bias. The decrease in resistance of the film correlates with the concentration of silver in solution between 3 ppb and 1 ppm. Exposing the sensor to a lower pH resets the sensor, allowing it to be reused and reset multiple times. This sensor demonstrates a new pathway to chemiresistive cation sensing using known selective complexing agents adsorbed onto graphitic thin films. This concept can be expanded to the detection of other relevant analytes in domestic, industrial and environmental water sources.