We explore the use of two-dimensional (2D) MoS2 nanosheets as an electrocatalyst for the Hydrogen Evolution Reaction (HER). Using four commonly employed commercially available carbon based electrode support materials, namely edge plane pyrolytic graphite (EPPG), glassy carbon (GC), boron-doped diamond (BDD) and screen-printed graphite electrodes (SPE), we critically evaluate the reported electrocatalytic performance of unmodified and MoS2 modified electrodes towards the HER. Surprisingly, current literature focuses almost exclusively on the use of GC as an underlying support electrode upon which HER materials are immobilised. 2D MoS2 nanosheet modified electrodes are found to exhibit a coverage dependant electrocatalytic effect towards the HER. Modification of the supporting electrode surface with an optimal mass of 2D MoS2 nanosheets results in a lowering of the HER onset potential by ca. 0.33, 0.57, 0.29 and 0.31 V at EPPG, GC, SPE and BDD electrodes compared to their unmodified counterparts respectively. The lowering of the HER onset potential is associated with each supporting electrode's individual electron transfer kinetics/properties and is thus distinct. The effect of MoS2 coverage is also explored. We reveal that its ability to catalyse the HER is dependent on the mass deposited until a critical mass of 2D MoS2 nanosheets is achieved, after which its electrocatalytic benefits and/or surface stability curtail. The active surface site density and turn over frequency for the 2D MoS2 nanosheets is determined, characterised and found to be dependent on both the coverage of 2D MoS2 nanosheets and the underlying/supporting substrate. This work is essential for those designing, fabricating and consequently electrochemically testing 2D nanosheet materials for the HER.
Using advanced mass spectrometry the chemistry of ionic species present in an atmospheric pressure parallel plate dielectric barrier discharge (DBD) with a single dielectric on the powered electrode have been identified. The discharge was driven in helium with controllable concentrations of water vapour using an excitation frequency of 10 kHz and an applied voltage of 1.2 kV. Both negative and positive ions were identified and their relative intensity , with n up to 9 in both cases. Negative and positive ions responded in a similar way to changes in the operating parameters, with the particular response depending on the ion mass. Increasing the inter-electrode spacing and the water concentration in the discharge led to an increase in the intensity of large mass ionic water clusters. However, increasing the residence time of the species in the plasma region and increasing the applied power resulted in fragmentation of large water clusters to produce smaller ions.
A dielectric barrier discharge microfluidic plasma reactor, operated at atmospheric pressure, was studied for its potential to treat organic contaminants in water. Microfluidic technology represents a compelling approach for plasma-based water treatment due to inherent characteristics such as a large surface-area-to-volume ratio and flow control, in inexpensive and portable devices. The microfluidic device in this work incorporated a dielectric barrier discharge generated in a continuous gas flow stream of a two-phase annular flow regime in the microchannels of the device. Methylene blue in solution was used to investigate plasma induced degradation of dissolved organic compounds within the microfluidic device. The relative degradation rates of methylene blue were influenced by the residence time of the sample solution in the discharge zone, type of gas applied, channel depth and flow rate. Increasing the residence time inside the plasma region led to higher levels of degradation. Oxygen was found to be the most effective gas, with the spectra obtained using Liquid Chromatography-Mass Spectroscopy indicating the most significant degradation. By reducing the channel depth from 100 to 50 µm, the best results were obtained, achieving a greater than 97% level of methylene blue degradation. The microfluidic system presented here demonstrates proof-of-concept that plasma technology can be utilised as an advanced oxidation process for water treatment, with the potential to eliminate water treatment consumables such as filters and disinfectants.
Fluorine dopant inhibited the oxidation process in CsSnI3−xFx films with high carrier concentration, low resistivity and wide light absorption.
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