Towards scaling up the sonochemical synthesis of Pt-nanocatalysts.

Large scale production of electrocatalysts for electrochemical energy conversion devices such as proton exchange membrane fuel cells must be developed to reduce their cost. The current chemical reduction methods used for this synthesis suffer from problems with achieving similar particle properties such as particle size and catalytic activity when scaling up the volume or the precursor concentration. The continuous production of reducing agents through the sonochemical synthesis method could help maintain the reducing conditions (and also the particle properties) upon increasing the reactor volume. In this work we demonstrate that the reducing conditions of Pt-nanoparticles are indeed maintained when the reactor volume is increased from 200 mL to 800 mL. Similar particle sizes, 2.1(0.3) nm at 200 mL and 2.3(0.4) nm at 800 mL, and catalytic activities towards the oxygen reduction reaction (ORR) are maintained as well. The reducing conditions were assessed through TiOSO4 dosimetry, sonochemiluminesence imaging, acoustic power measurements, and Pt(II) reduction rate measurements. Cyclic voltammetry, CO-stripping, hydrogen evolution measurements, ORR measurements, and electron microscopy were used to evaluate the catalytic activity and particle size. The similar particle properties displayed from the two reactor volumes suggest that the sonochemical synthesis of Pt-nanoparticles is suitable for large scale production.

Promotion of hydrogen evolution from seawater via poly(aniline-co-4-nitroaniline) combined with 3D nickel nanoparticles.

This work reports the synthesis of poly (aniline-co-4-nitroaniline) deposited on a three-dimensional nanostructured nickel (3D-Ni) film, where both layers were fabricated via potentiostatic electrodeposition. The obtained electrocatalyst exhibited excellent electrochemical activity for the Hydrogen Evolution Reaction (HER) with small overpotentials of - 195 and - 325 mV at - 10 and - 100 mAcm-2, respectively, and a low Tafel slope of 53.3 mV dec-1 in seawater. Additionally, the electrocatalyst exhibited good stability after 72 h operation under a constant potential of - 1.9 V vs. RHE. The efficient HER performance of the as-prepared catalyst was found to originate from the synergy between the conducting polymer and three-dimensional nickel nanoparticles with a large electrochemical active surface area. Moreover, the results obtained from electrochemical impedance spectroscopy (EIS) measurements revealed that the presence of 3D-Ni layer improved the kinetics of HER by reducing the charge transfer resistance for the electrocatalyst.

State of the Art Progress in Copper Vanadate Materials for Solar Water Splitting.

The development of a single junction photoelectrode material having specific properties is essential and challenging for the efficient application in solar water splitting for oxygen production and a high value-added product, hydrogen. Moreover, the present material solutions based on binary metal oxides offer limited catalytic activity and hydrogen production efficiency. Therefore, it is paramount to develop and exploit a unique range of materials derived from ternary metal oxides with specifically engineered properties to advance in photoelectrochemical (PEC) water splitting. Among the ternary oxides, copper vanadates offer promising characteristics, such as a narrow bandgap and catalytic surface properties along with favorable band edges for facile oxygen evolution reaction (OER), which is considered the bottleneck step in performing overall water dissociation. Furthermore, the copper vanadates allow the tuning of the stoichiometry through which a wide range of polymorphs and materials could be obtained. This review provides a complete outlook on the range of copper vanadates and the established synthesis approach, morphology, crystal structure, band edge properties, and PEC characterizations. Mainly, the underlying charge dynamic properties, carrier path length, effect of doping, and influence of surface catalysts are discussed. The review concludes that the advancement toward obtaining low-bandgap materials is a main challenge to overcome the limitations for efficient water dissociation to OER and copper vanadates, which offer a promising solution with their unique properties and advantages. Importantly, intense and strategically focused research is vital to overcome the scientific challenges involved in copper vanadates and to explore and exploit new polymorphs to set new efficiency benchmarks and PEC water splitting solutions.

Ultrasonics and sonochemistry: Editors' perspective.

Ultrasonic waves can induce physical and chemical changes in liquid media via acoustic cavitation. Various applications have benefitted from utilizing these effects, including but not limited to the synthesis of functional materials, emulsification, cleaning, and processing. Several books and review articles in the public domain cover both fundamental and applied aspects of ultrasonics and sonochemistry. The Editors of the Ultrasonics Sonochemistry journal possess diverse expertise in this field, from theoretical and experimental aspects of acoustic cavitation to materials synthesis, environmental remediation, and sonoprocessing. This article provides Editors' perspectives on various aspects of ultrasonics and sonochemistry that may benefit students and early career researchers.

Enhanced photoactivity towards bismuth vanadate water splitting through tantalum doping: An experimental and density functional theory study.

The activation of hole trap states in bismuth vanadate (BiVO4) is considered an effective strategy to enhance the photoelectrochemical (PEC) water-splitting activity. Herein, we propose a theoretical and experimental study of tantalum (Ta) doping to BiVO4 leading to the introduction of hole trap states for the enhanced PEC activity. The doping of Ta is found to alter the structural and chemical surroundings via displacement of vanadium (V) atoms that cause distortions in the lattice via the formation of hole trap states. A significant enhancement of photocurrent to ∼4.2 mA cm-2 was recorded attributing to the effective charge separation of efficiency of ∼96.7 %. Furthermore, the doping of Ta in the BiVO4 lattice offers improved charge transport in bulk and decreased charge transfer resistance at the electrolyte interface. The Ta-doped BiVO4 displays the effective production of hydrogen (H2) and oxygen (O2) under AM 1.5 G illumination with a faradaic efficiency of 90 %. Moreover, the density functional theory (DFT) study confirms the decrease in optical band gap and the activation of hole trap states below the conduction band (CB) with a contribution of Ta towards both valence and CB that increases the charge separation and majority charge carrier density, respectively. The findings of this work propose that the displacement of V sites with Ta atoms in BiVO4 photoanodes is an efficient approach for enhanced PEC activity.

In Situ Sonoactivation of Polycrystalline Ni for the Hydrogen Evolution Reaction in Alkaline Media.

In this investigation, we report on the development of a method for activating polycrystalline metallic nickel (Ni(poly)) surfaces toward the hydrogen evolution reaction (HER) in N2-saturated 1.0 M KOH aqueous electrolyte through continuous and pulsed ultrasonication (24 kHz, 44 ± 1.40 W, 60% acoustic amplitude, ultrasonic horn). It is found that ultrasonically activated Ni shows an improved HER activity with a much lower overpotential of -275 mV vs RHE at -10.0 mA cm-2 when compared to nonultrasonically activated Ni. It was observed that the ultrasonic pretreatment is a time-dependent process that gradually changes the oxidation state of Ni and longer ultrasonication times result in higher HER activity as compared to untreated Ni. This study highlights a straightforward strategy for activating nickel-based materials by ultrasonic treatment for the electrochemical water splitting reaction.

Recent Advancements of Polymeric Membranes in Anion Exchange Membrane Water Electrolyzer (AEMWE): A Critical Review.

Water electrolysis coupled with renewable energy is one of the principal methods for producing green hydrogen (or renewable hydrogen). Among the different electrolysis technologies, the evolving anion exchange membrane water electrolysis (AEMWE) shows the utmost promise for the manufacture of green hydrogen in an inexpensive way. In the present review, we highlight the most current and noteworthy achievements of AEMWE, which include the advancements in increasing the polymer anionic conductivity, understanding the mechanism of degradation of AEM, and the design of the electrocatalyst. The important issues affecting the AEMWE behaviour are highlighted, and future constraints and openings are also discussed. Furthermore, this review provides strategies for producing dynamic and robust AEMWE electrocatalysts.

Optimum scavenger concentrations for sonochemical nanoparticle synthesis.

Maintaining nanoparticle properties when scaling up a chemical synthesis is challenging due to the complex interplay between reducing agents and precursors. A sonochemical synthesis route does not require the addition of reducing agents as they are instead being continuously generated in-situ by ultrasonic cavitation throughout the reactor volume. To optimize the sonochemical synthesis of nanoparticles, understanding the role of radical scavengers is paramount. In this work we demonstrate that optimum scavenger concentrations exist at which the rate of Ag-nanoparticle formation is maximized. Titanyl dosimetry experiments were used in conjunction with Ag-nanoparticle formation rates to determine these optimum scavenger concentrations. It was found that more hydrophobic scavengers require lower optimum concentrations with 1-butanol < 2-propanol < ethanol < methanol < ethylene glycol. However, the optimum concentration is shifted by an order of magnitude towards higher concentrations when pyrolytic decomposition products contribute to the reduction. The reduction rate is also enhanced considerably.

Effect of Organic Ions on The Formation and Collapse of Nanometric Bubbles in Ionic Liquid/Water Solutions: A Molecular Dynamics Study.

Molecular dynamics simulation is applied to investigate the effect of two ionic liquids (IL) on the nucleation and growth of (nano)cavities in water under tension and on the cavities' collapse following the release of tension. Simulations of the same phenomena in two pure water samples of different sizes are carried out for comparison. The first IL, i.e., tetra-ethylammonium mesylate ([Tea][Ms]), is relatively hydrophilic and its addition to water at 25 wt % concentration decreases its tendency to nucleate cavities. Apart from quantitative details, cavity formation and collapse are similar to those taking place in water and qualitatively follow the Rayleigh-Plesset (RP) equation. The second IL, i.e., tetrabutyl phosphonium 2,4-dimethylbenzenesulfonate ([P4444][DMBS]), is amphiphilic and forms nanostructured solutions with water. At 25 wt % concentrations, [P4444][DMBS] favors the nucleation of bubbles that tend to form at the interface between water-rich and IL-rich domains. Cavity collapse in [P4444][DMBS]/water solutions are greatly hindered by a shell of ions decorating the interface between the solution and the vapor phase. A similar effect is observed for the equilibration of a population of bubbles of different sizes. The drastic slowing down of the bubbles' relaxation processes suggests ways to produce long-lived nanometric cavities in the liquid phase that could be useful for nanotechnology and drug delivery.

Novel Supercapacitor Electrode Derived from One Dimensional Cerium Hydrogen Phosphate (1D-Ce(HPO4)2.xH2O).

In this manuscript, we are reporting for the first time one dimensional (1D) cerium hydrogen phosphate (Ce(HPO4)2.xH2O) electrode material for supercapacitor application. In short, a simple hydrothermal technique was employed to prepare Ce(HPO4)2.xH2O. The maximum surface area of 82 m2 g-1 was obtained from nitrogen sorption isotherm. SEM images revealed Ce(HPO4)2.xH2O exhibited a nanorod-like structure along with particles and clusters. The maximum specific capacitance of 114 F g-1 was achieved at 0.2 A g-1 current density for Ce(HPO4)/NF electrode material in a three-electrode configuration. Furthermore, the fabricated symmetric supercapacitor (SSC) based on Ce(HPO4)2.xH2O//Ce(HPO4)2.xH2O demonstrates reasonable specific energy (2.08 Wh kg-1), moderate specific power (499.88 W kg-1), and outstanding cyclic durability (retains 92.7% of its initial specific capacitance after 5000 GCD cycles).

Sonochemical Synthesis of Cu@Pt Bimetallic Nanoparticles.

Reducing the amount of noble metals in catalysts for electrochemical conversion devices is paramount if these devices are to be commercialized. Taking advantage of the high degree of particle property control displayed by the sonochemical method, we set out to synthesize Cu@Pt bimetallic nanocatalysts in an effort to improve the mass activity towards the hydrogen evolution reaction. At least 17 times higher mass activity was found for the carbon supported Cu@Pt bimetallic nanocatalyst (737 mA mg−1, E = −20 mV) compared to carbon supported Pt nanocatalysts prepared with the same ultrasound conditions (44 mA mg−1, E = −20 mV). The synthesis was found to proceed with the sonochemical formation of Cu and Cu2O nanoparticles with the addition of PtCl4 leading to galvanic displacement of the Cu-nanoparticles and the formation of a Pt-shell around the Cu-core.

Water electrolysis: from textbook knowledge to the latest scientific strategies and industrial developments.

Replacing fossil fuels with energy sources and carriers that are sustainable, environmentally benign, and affordable is amongst the most pressing challenges for future socio-economic development. To that goal, hydrogen is presumed to be the most promising energy carrier. Electrocatalytic water splitting, if driven by green electricity, would provide hydrogen with minimal CO2 footprint. The viability of water electrolysis still hinges on the availability of durable earth-abundant electrocatalyst materials and the overall process efficiency. This review spans from the fundamentals of electrocatalytically initiated water splitting to the very latest scientific findings from university and institutional research, also covering specifications and special features of the current industrial processes and those processes currently being tested in large-scale applications. Recently developed strategies are described for the optimisation and discovery of active and durable materials for electrodes that ever-increasingly harness first-principles calculations and machine learning. In addition, a technoeconomic analysis of water electrolysis is included that allows an assessment of the extent to which a large-scale implementation of water splitting can help to combat climate change. This review article is intended to cross-pollinate and strengthen efforts from fundamental understanding to technical implementation and to improve the 'junctions' between the field's physical chemists, materials scientists and engineers, as well as stimulate much-needed exchange among these groups on challenges encountered in the different domains.

Sonoactivated polycrystalline Ni electrodes for alkaline oxygen evolution reaction.

The development of cost-effective and active water-splitting electrocatalysts is an essential step toward the realization of sustainable energy. Its success requires an intensive improvement in the kinetics of the anodic half-reaction of the oxygen evolution reaction (OER), which determines the overall system efficiency to a large extent. In this work, we designed a facile and one-route strategy to activate the surface of metallic nickel (Ni) for the OER in alkaline media by ultrasound (24 kHz, 44 W, 60% acoustic amplitude, ultrasonic horn). Sonoactivated Ni showed enhanced OER activity with a much lower potential at + 10 mA cm-2 of + 1.594 V vs. RHE after 30 min ultrasonic treatment compared to + 1.617 V vs. RHE before ultrasonication. In addition, lower charge transfer resistance of 11.1 Ω was observed for sonoactivated Ni as compared to 98.5 Ω for non-sonoactivated Ni. In our conditions, ultrasound did not greatly affect the electrochemical surface area (Aecsa) and Tafel slopes however, the enhancement of OER activity can be due to the formation of free OH• radicals resulting from cavitation bubbles collapsing at the electrode/electrolyte interface.

Frequency controlled agglomeration of pt-nanoparticles in sonochemical synthesis.

Optimizing the surface area of nanoparticles is key to achieving high catalytic activities for electrochemical energy conversion devices. In this work, the frequency range (200 kHz-500 kHz) for maximum sonochemical radical formation was investigated for the sonochemical synthesis of Pt-nanoparticles to assess whether an optimum frequency exists or if the entire range provides reproducible particle properties. Through physical and electrochemical characterization, it was found that the frequency dependent mechanical effects of ultrasound resulted in smaller, more open agglomerates at lower frequencies with agglomerate sizes of (238 ± 4) nm at 210 kHz compared to (274 ± 2) nm at 326 kHz, and electrochemical surface areas of (12.4 ± 0.9) m2g-1 at 210 kHz compared to (3.4 ± 0.5) m2g-1 at 326 kHz. However, the primary particle size (2.1 nm) and the catalytic activity towards hydrogen evolution, (19 ± 2) mV at 10mA cm2,remained unchanged over the entire frequency range. Highly reproducible Pt-nanoparticles are therefore easily attainable within a broad range of ultrasonic frequencies for the sonochemical synthesis route.

Understanding the Effects of Ultrasound (408 kHz) on the Hydrogen Evolution Reaction (HER) and the Oxygen Evolution Reaction (OER) on Raney-Ni in Alkaline Media.

The hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) occurring at the Raney-Ni mesh electrode in 30 wt.-% aqueous KOH solution were studied in the absence (silent) and presence of ultrasound (408 kHz, ∼54 W, 100% acoustic amplitude) at different electrolyte temperatures (T = 25, 40 and 60 °C). Linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS) experiments were performed to analyse the electrochemical behaviour of the Raney-Ni electrode under these conditions. Under silent conditions, it was found that the electrocatalytic activity of Raney-Ni towards the HER and the OER depends upon the electrolyte temperature, and higher current densities at lower overpotentials were achieved at elevated temperatures. It was also observed that the HER activity of Raney-Ni under ultrasonic conditions increased at low temperatures (e.g., 25 °C) while the ultrasonic effect on the OER was found to be insignificant. In addition, it was observed that the ultrasonic effect on both the HER and OER decreases by elevating the temperature. In our conditions, it is suggested that ultrasound enhances the electrocatalytic performance of Raney-Ni towards the HER due to principally the efficient gas bubble removal from the electrode surface and the dispersion of gas bubbles into the electrolyte, and this effect depends upon the behaviour of the hydrogen and oxygen gas bubbles in alkaline media.

Electrochemical nutrient removal from natural wastewater sources and its impact on water quality.

In this study, a suite of natural wastewater sources is tested to understand the effects of wastewater composition and source on electrochemically driven nitrogen and phosphorus nutrient removal. Kinetics, electrode behavior, and removal efficiency were evaluated during electrochemical precipitation, whereby a sacrificial magnesium (Mg) anode was used to drive precipitation of ammonium and phosphate. The electrochemical reactor demonstrated fast kinetics in the natural wastewater matrices, removing up to 54% of the phosphate present in natural wastewater within 1 min, with an energy input of only 0.04 kWh.m-3. After 1 min, phosphate removal followed a zero-order rate law in the 1 min - 30 min range. The zero-order rate constant (k) appears to depend upon differences in wastewater composition, where a faster rate constant is associated with higher Cl- and NH4+ concentrations, lower Ca2+ concentrations, and higher organic carbon content. The sacrificial Mg anode showed the lowest corrosion resistance in the natural industrial wastewater source, with an increased corrosion rate (vcorr) of 15.8 mm.y-1 compared to 1.9-3.5 mm.y-1 in municipal wastewater sources, while the Tafel slopes (ß) showed a direct correlation with the natural wastewater composition and origin. An overall improvement of water quality was observed where important water quality parameters such as total organic carbon (TOC), total suspended solids (TSS), and turbidity showed a significant decrease. An economic analysis revealed costs based upon experimental Mg consumption are estimated to range from 0.19 $.m-3 to 0.30 $.m-3, but costs based upon theoretical Mg consumption range from 0.09 $.m-3 to 0.18 $.m-3. Overall, this study highlights that water chemistry parameters control nutrient recovery, while electrochemical treatment does not directly produce potable water, and that economic analysis should be based upon experimentally-determined Mg consumption data. Synopsis Statement: Magnesium-driven electrochemical precipitation of natural wastewater sources enables fast kinetics for phosphate removal at low energy input.

In situ grown oxygen-vacancy-rich copper oxide nanosheets on a copper foam electrode afford the selective oxidation of alcohols to value-added chemicals.

Selective oxidation of low-molecular-weight aliphatic alcohols like methanol and ethanol into carboxylates in acid/base hybrid electrolytic cells offers reduced process operating costs for the generation of fuels and value-added chemicals, which is environmentally and economically more desirable than their full oxidation to CO2. Herein, we report the in-situ fabrication of oxygen-vacancies-rich CuO nanosheets on a copper foam (CF) via a simple ultrasonication-assisted acid-etching method. The CuO/CF monolith electrode enables efficient and selective electrooxidation of ethanol and methanol into value-added acetate and formate with ~100% selectivity. First principles calculations reveal that oxygen vacancies in CuO nanosheets efficiently regulate the surface chemistry and electronic structure, provide abundant active sites, and enhance charge transfer that facilitates the adsorption of reactant molecules on the catalyst surface. The as-prepared CuO/CF monolith electrode shows excellent stability for alcohol oxidation at current densities >200 mA·cm2 for 24 h. Moreover, the abundant oxygen vacancies significantly enhance the intrinsic indicators of the catalyst in terms of specific activity and outstanding turnover frequencies of 5.8k s-1 and 6k s-1 for acetate and formate normalized by their respective faradaic efficiencies at an applied potential of 1.82 V vs. RHE.

Ultrasonically Surface-Activated Nickel Foam as a Highly Efficient Monolith Electrode for the Catalytic Oxidation of Methanol to Formate.

Most of the current electrocatalysts for the methanol oxidation reaction are precious group metals such as Pt, Pd, and Ru. However, their use is limited due to their high cost, scarcity, and issues with carbon monoxide poisoning. We developed a simple method to prepare a nickel foam (NF)-based monolith electrode with a NiO nanosheet array structure as an efficient electrocatalyst toward the oxidation of methanol to produce formate. By a simple ultrasonic acid treatment and air oxidation at room temperature, an inert NF was converted to NiO/NF as a catalytically active electrode due to the uniform NiO nanosheet array that was rapidly formed on the surface of NiO/NF. In alkaline electrolytes containing methanol, the as-prepared NiO/NF catalysts exhibited a lower methanol oxidation reaction (MOR) potential of +1.53 V vs RHE at 100 mA cm-2 compared to that of inert NF samples. The difference in potentials between the EMOR and the EOER at that current density was found to be 280 mV, indicating that methanol oxidation occurred at lower potentials as compared to the oxygen evolution reaction (OER). We also observed that the NiO/NF could also efficiently catalyze the oxidation of CO without being poisoned by it. NiO/NF retained close to 100% of its initial activity after 20,000 s of methanol oxidation tests at high current densities above 200 mA cm-2. Because of the simple synthesis method and the enhanced catalytic performance and stability of NiO/NF, this allows methanol to be used as an OER masking agent for the energy-efficient generation of value-added products such as formic acid and hydrogen.

Does power ultrasound affect hydrocarbon Ionomers?

The effect of low-frequency high-power ultrasound on hydrocarbon-based ionomers, cation exchange sulfonated phenylated polyphenylene (sPPB-H+) and anion exchange hexamethyl-p-terphenyl poly(benzimidazolium) (HMT-PMBI), was studied. Ionomer solutions were subjected to ultrasonication at fixed ultrasonic frequencies (f = 26 and 42 kHz) and acoustic power (Pacous = 2.1 - 10.6 W) in a laboratory-grade ultrasonication bath, and a probe ultrasonicator; both commonly employed in catalyst ink preparation in research laboratory scale. Power ultrasound reduced the polymer solution viscosity of both hydrocarbon-based ionomers. The molecular weight of sPPB-H+ decreased with irradiation time. Changes in viscosity and molecular weight were exacerbated when ultrasonicated in an ice bath; but reduced when the solutions contained carbon black, as typically used in Pt/C-based catalyst inks. Spectroscopic analyses revealed no measurable changes in polymer structure upon ultrasonication, except for very high doses, where evidence for free-radical induced degradation was observed. Ionomers subjected to ultrasound were used to prepare catalyst layers and membrane electrode assemblies (MEA)s. Despite the changes in the ionomer described above, no significant differences in electrochemical performance were found between MEAs prepared with ionomers pre-subjected to ultrasound and those that were not, suggesting that fuel cell performance is tolerant to ionomers subjected to ultrasound.

Sonochemical conversion of CO2 into hydrocarbons: The Sabatier reaction at ambient conditions.

In this study, we investigated an alternative method for the chemical CO2 reduction reaction in which power ultrasound (488 kHz ultrasonic plate transducer) was applied to CO2-saturated (up to 3%) pure water, NaCl and synthetic seawater solutions. Under ultrasonic conditions, the converted CO2 products were found to be mainly CH4, C2H4 and C2H6 including large amount of CO which was subsequently converted into CH4. We have found that introducing molecular H2 plays a crucial role in the CO2 conversion process and that increasing hydrogen concentration increased the yields of hydrocarbons. However, it was observed that at higher hydrogen concentrations, the overall conversion decreased since hydrogen, a diatomic gas, is known to decrease cavitational activity in liquids. It was also found that 1.0 M NaCl solutions saturated with 2% CO2 + 98% H2 led to maximum hydrocarbon yields (close to 5%) and increasing the salt concentrations further decreased the yield of hydrocarbons due to the combined physical and chemical effects of ultrasound. It was shown that CO2 present in a synthetic industrial flue gas (86.74% N2, 13% CO2, 0.2% O2 and 600 ppm of CO) could be converted into hydrocarbons through this method by diluting the flue gas with hydrogen. Moreover, it was observed that in addition to pure water, synthetic seawater can also be used as an ultrasonicating media for the sonochemical process where the presence of NaCl improves the yields of hydrocarbons by ca. 40%. We have also shown that by using low frequency high-power ultrasound in the absence of catalysts, it is possible to carry out the conversion process at ambient conditions i.e., at room temperature and pressure. We are postulating that each cavitation bubble formed during ultrasonication act as a "micro-reactor" where the so-called Sabatier reaction -CO2+4H2→UltrasonicationCH4+2H2O - takes place upon collapse of the bubble. We are naming this novel approach as the "Islam-Pollet-Hihn process".