How do dissolved gases affect the sonochemical process of hydrogen production? An overview of thermodynamic and mechanistic effects - On the "hot spot theory".

Although most of researchers agree on the elementary reactions behind the sonolytic formation of molecular hydrogen (H2) from water, namely the radical attack of H2O and H2O2 and the free radicals recombination, several recent papers ignore the intervention of the dissolved gas molecules in the kinetic pathways of free radicals, and hence may wrongly assess the effect of dissolved gases on the sonochemical production of hydrogen. One may fairly ask to which extent is it acceptable to ignore the role of the dissolved gas and its eventual decomposition inside the acoustic cavitation bubble? The present opinion paper discusses numerically the ways in which the nature of dissolved gas, i.e., N2, O2, Ar and air, may influence the kinetics of sonochemical hydrogen formation. The model evaluates the extent of direct physical effects, i.e., dynamics of bubble oscillation and collapse events if any, against indirect chemical effects, i.e., the chemical reactions of free radicals formation and consequently hydrogen emergence, it demonstrates the improvement in the sonochemical hydrogen production under argon and sheds light on several misinterpretations reported in earlier works, due to wrong assumptions mainly related to initial conditions. The paper also highlights the role of dissolved gases in the nature of created cavitation and hence the eventual bubble population phenomena that may prevent the achievement of the sonochemical activity. This is particularly demonstrated experimentally using a 20 kHz Sinaptec transducer and a Photron SA 5 high speed camera, in the case of CO2-saturated water where degassing bubbles are formed instead of transient cavitation.

Does power ultrasound (26 kHz) affect the hydrogen evolution reaction (HER) on Pt polycrystalline electrode in a mild acidic electrolyte?

In this study, we investigated the effects of power ultrasound (26 kHz, up to ∼75 W/cm2, up to 100% acoustic amplitude, ultrasonic horn) on the hydrogen evolution reaction (HER) on a platinum (Pt) polycrystalline disc electrode in 0.5 M H2SO4 by cyclic and linear sweep voltammetry at 298 K. We also studied the formation of molecular hydrogen (H2) bubbles on a Pt wire in the absence and presence of power ultrasound using ultra-fast camera imaging. It was found that ultrasound significantly increases currents towards the HER i.e. a ∼250% increase in current density was achieved at maximum ultrasonic power. The potential at a current density of -10 mA/cm2 under silent conditions was found to be -46 mV and decreased to -27 mV at 100% acoustic amplitude i.e. a ΔE shift of ∼+20 mV, indicating the influence of ultrasound on improving the HER activity. A nearly 100% increase in the exchange current density (jo) and a 30% decrease in the Tafel slope (b) at maximum ultrasonic power, was observed in the low overpotential region, although in the high overpotential region, the Tafel slopes (b) were not significantly affected when compared to silent conditions. In our conditions, ultrasound did not greatly affect the "real" surface area (Ar) and roughness factor (R) i.e. the microscopic surface area available for electron transfer. Overall, it was found that ultrasound did not dramatically change the mechanism of HER but instead, increased currents at the Pt surface area through effective hydrogen bubble removal.

Assessment of the beneficial combination of electrochemical and ultrasonic activation of compounds originating from biomass.

The electro-oxidation of organic molecules at the anode with simultaneous generation of hydrogen at the cathode in electrosynthesis reactors is considered as a promising and efficient process for the co-production of hydrogen and bio-sourced value-added chemicals. In this study and for the first time, we investigated the electro-oxidation of glucose and methylglucoside in 0.1 mol L-1 NaOH on polycrystalline Pt (real surface area = 14.5 ± 0.5 cm2, roughness ≈ 5) in the potential range [0; +1.20 V vs. rhe] under silent and ultrasonic (bath, 45 kHz, Pacous = 11.20 W) conditions. A series of linear sweep voltammograms, chronoamperograms and high-performance liquid chronoamperograms were generated. It was found that higher current densities were obtained under ultrasonic conditions over the potential range of +0.25 V to +1.10 V vs. rhe, indicating that higher oxidation rates were provided under ultrasonication. It was observed that the desorption of species from the Pt surface in the medium potential region was favoured, allowing free catalytic Pt sites for further adsorption and oxidation of reactants; and in the high potential region, high peak current densities in the presence of ultrasound was due to enhanced mass transport of the electroactive species from the bulk electrolyte to the Pt-polycrystalline electrode surface. HPLC studies confirmed that higher electrochemical activity was obtained in the presence of ultrasound than in the absence. In our conditions, it was also found that low frequency ultrasound did not change the selectivity of the glucose and methylglucoside electro-oxidation reactions but instead, a significant increase in the rate of conversion was observed.

Effect of power ultrasound and Fenton reagents on the biomethane potential from steam-exploded birchwood.

The global demand for non-fossil energy sources is increasing rapidly. As a result, biogas presents a suitable alternative; however, first generation biofuels (e.g., sugar cane) potentially impact food crops globally. Second generation biofuels based on lignocellulose-based biomass are being used more frequently as they do not impact food crops. Furthermore, in Northern Europe, there is a significant interest in utilizing birchwood and paper mill waste for biogas production due to its high availability. The utilization of birchwood for biogas has significantly improved in recent years with the improvement of required pretreatment processes. To date, the most effective and economically feasible pretreatment in an industrial context is the steam explosion of lignocellulose-based biomass. Despite this, there is potential for releasing more digestible components from this biomass by efficiently degrading the lignocellulose components. This research presents another pretreatment that can be applied to steam-exploded wood based on ultrasonication and Fenton reagents. It was observed that by treating the steam exploded birchwood with ultrasonication and mild concentrations of Fenton reagents, an increase in the rate of biogas production was achievable. This would allow the increase in biogas yield of a continuously feed industrial anaerobic digester without increasing the size of the reactor.

Sonochemical and sonoelectrochemical production of hydrogen.

Reserves of fossil fuels such as coal, oil and natural gas on earth are finite. The continuous use and burning of these fossil fuel resources in the industrial, domestic and transport sectors has resulted in the extremely high emission of greenhouse gases, GHGs (e.g. CO2) and solid particulates into the atmosphere. Therefore, it is necessary to explore pollution free and more efficient energy sources in order to replace depleting fossil fuels. The use of hydrogen (H2) as an alternative fuel source is particularly attractive due to its very high specific energy compared to other conventional fuels and its zero GHG emission when used in a fuel cell. Hydrogen can be produced through various process technologies such as thermal, electrolytic, photolytic and biological processes. Thermal processes include gas reforming, renewable liquid and biooil processing, biomass and coal gasification; however, these processes release a huge amount of greenhouse gases. Production of electrolytic hydrogen from water is an attractive method to produce clean hydrogen. It could even be a more promising technology when combining water electrolysis with power ultrasound to produce hydrogen efficiently where sonication enhances the electrolytic process in several ways such as enhanced mass transfer, removal of hydrogen and oxygen (O2) gas bubbles and activation of the electrode surface. In this review, production of hydrogen through sonochemical and sonoelectrochemical methods along with a brief description of current hydrogen production methods and power ultrasound are discussed.