Decoupled supercapacitive electrolyzer for membrane-free water splitting.

Green hydrogen production via water splitting is vital for decarbonization of hard-to-abate industries. Its integration with renewable energy sources remains to be a challenge, due to the susceptibility to hazardous gas mixture during electrolysis. Here, we report a hybrid membrane-free cell based on earth-abundant materials for decoupled hydrogen production in either acidic or alkaline medium. The design combines the electrocatalytic reactions of an electrolyzer with a capacitive storage mechanism, leading to spatial/temporal separation of hydrogen and oxygen gases. An energy efficiency of 69% lower heating value (48 kWh/kg) at 10 mA/cm2 (5 cm-by-5 cm cell) was achieved using cobalt-iron phosphide bifunctional catalyst with 99% faradaic efficiency at 100 mA/cm2. Stable operation over 20 hours in alkaline medium shows no apparent electrode degradation. Moreover, the cell voltage breakdown reveals that substantial improvements can be achieved by tunning the activity of the bifunctional catalyst and improving the electrodes conductivity. The cell design offers increased flexibility and robustness for hydrogen production.

Enhanced Electrocatalytic Conversion of Nitrates to Ammonia: Fuel from Waste.

Ammonia (NH3) is globally one of the most produced chemicals. Despite being known for its use as a fuel and as a precursor of multiple chemicals, during its production, it is responsible for more than 1.2 % of the total global CO2 emission and consumes a large amount of energy. In this work, we studied a flow-through membrane-free electrocatalytic device (CMED) to produce continuous stream of NH3 from a common water contaminant, nitrate (NO3 -). Indium-palladium (In-Pd) nanoparticles were impregnated in activated carbon cloth (ACC) and used as a cathode in the electrochemical device. It is found that in the counter electrode, adding oxygen evolution reaction (OER) active catalysts like platinum (Pt) for the regeneration of hydrogen ions enhances the rate of ammonia conversion to 7.28 µmol min-1 cm-2, eliminate the production of toxic nitrite by-products, as well as provide a platform for a stable energy consumption over long periods of time. This method for the conversion of NO3 - into NH3 promises a way forward for sustainable resource utilization while generating fuel from waste and contributing to future circular economies, and managing the nitrogen cycle in water that is a major challenge of the 21st century society.

Cerium Oxide on a Fluorinated Carbon-Based Electrode as a Promising Catalyst for Hypochlorite Production.

Sodium hypochlorite (NaOCl) is widely used as a disinfectant agent for water treatment and surface cleaning. A straightforward way to produce NaOCl is by the electrolysis of an aqueous sodium chloride (NaCl) solution. This process presents several side reactions decreasing its efficiency with hypochlorite reduction on the cathode surface being one of the main detrimental reactions. In this work, we have studied carbon-based electrodes modified with cerium oxide (CeO2), fluorine, and platinum nanoparticles as cathodes for hypochlorite production. Fluorination was carried out electrochemically; the polyol method was used to synthesize platinum nanoparticles; and the hydrothermal process was applied to form a CeO2 layer. Scanning electron microscopy, FTIR, and inductively coupled plasma (ICP) indicated the presence of cerium oxide as a film, fluorine groups on the substrate, and a load of 3.2 mg/cm2 of platinum nanoparticles and 2.7 mg/cm2 of CeO2. From electrochemical impedance spectroscopy, it was possible to demonstrate that incorporating platinum and fluorine decreases the charge transfer resistance by 16% and 28%, respectively. Linear sweep voltammetry showed a significant decrease in hypochlorite reduction when the substrate was doped with fluorine from -16.6 mA/cm2 at -0.6 V to -9.64 mA/cm2 that further reduced to -8.78 mA/cm2 with cerium oxide covered fluorinated electrodes. The performance of the cathode materials during hypochlorite production improved by 80% compared with pristine activated carbon cloth (ACC) electrodes. The improvement toward hindering NaOCl reduction is probably caused by the incorporation of a partial negative charge upon doping with fluorine.

Effect of Surface Charge on the Fabrication of Hierarchical Mn-Based Prussian Blue Analogue for Capacitive Desalination.

Multiple and hierarchical manganese (Mn)-based Prussian blue analogues obtained on different substrates are successfully prepared using a universal, facile, and simple strategy. Different functional groups and surface charge distributions on carbon cloth have significant effects on the morphologies and nanostructures of Mn-based Prussian blue analogues, thereby indirectly affecting their physicochemical properties. Combined with the advantages of the modified carbon cloth and the nanostructured Mn-based Prussian blue analogues, the composite with negative surface charge formed by the electronegativity differences shows good electrochemical properties, leading to improvement in charge efficiency during capacitive desalination. An asymmetric device fabricated with Mn-based Prussian blue analogue-modified F-doped carbon cloth as the cathode and acid-treated carbon cloth as the anode presents the highest salt adsorption capacity of 10.92 mg g-1 with a charge efficiency of 82.28% and the lowest energy consumption of 0.45 kW h m-3 at 1 V due to the main influencing factor from the negative surface charge leading to co-ion expulsion boosting the capacitive deionization performance. We provide insights for further exploration of the relationship between second-phase materials and carbon cloth, while offering some guidance for the design and preparation of electrodes for desalination and beyond.

Sodium to cesium ions: a general ladder mechanism of ion diffusion in prussian blue analogs.

Prussian blue analogs (PBAs) form crystals with large lattice voids that are suitable for the capture, transport and storage of various interstitial ions. Recently, we introduced the concept of a ladder mechanism to describe how sodium ions inside a PBA crystal structure diffuse by climbing the frames formed by aligned cyanide groups in the host structure. The current work uses semi-empirical tight-binding density functional theory (DFTB) in a multiscale approach to investigate how differences in the size of the monovalent cation affect the qualitative and quantitative aspects of the diffusion process. The results show that the ladder mechanism represents a unified framework, from which both similarities and differences between cation types can be understood. Fundamental Coulombic interactions make all positive cations avoid the open vacant areas in the structure, while cavities surrounded by partially negatively charged cyanide groups form diffusion bottlenecks and traps for larger cations. These results provide a new and quantitative way of understanding the suppression of cesium adsorption that has previously been reported for PBAs characterized by a low vacancy density. In conclusion, this work provides a unified picture of the cation adsorption in PBAs based on the newly formulated ladder mechanism.

Ladder Mechanisms of Ion Transport in Prussian Blue Analogues.

Prussian blue (PB) and its analogues (PBAs) are drawing attention as promising materials for sodium-ion batteries and other applications, such as desalination of water. Because of the possibilities to explore many analogous materials with engineered, defect-rich environments, computational optimization of ion-transport mechanisms that are key to the device performance could facilitate real-world applications. In this work, we have applied a multiscale approach involving quantum chemistry, self-consistent mean-field theory, and finite-element modeling to investigate ion transport in PBAs. We identify a cyanide-mediated ladder mechanism as the primary process of ion transport. Defects are found to be impermissible to diffusion, and a random distribution model accurately predicts the impact of defect concentrations. Notably, the inclusion of intermediary local minima in the models is key for predicting a realistic diffusion constant. Furthermore, the intermediary landscape is found to be an essential difference between both the intercalating species and the type of cation doping in PBAs. We also show that the ladder mechanism, when employed in multiscale computations, properly predicts the macroscopic charging performance based on atomistic results. In conclusion, the findings in this work may suggest the guiding principles for the design of new and effective PBAs for different applications.