Specifically adsorbed ferrous ions modulate interfacial affinity for high-rate ammonia electrosynthesis from nitrate in neutral media.

The electrolysis of nitrate reduction to ammonia (NRA) is promising for obtaining value-added chemicals and mitigating environmental concerns. Recently, catalysts with high-performance ammonia synthesis from nitrate has been achieved under alkaline or acidic conditions. However, NRA in neutral solution still suffers from the low yield rate and selectivity of ammonia due to the low binding affinity and nucleophilicity of NO3-. Here, we confirmed that the in-situ-generated Fe(II) ions existed as specifically adsorbed cations in the inner Helmholtz plane (IHP) with a low redox potential. Inspired by this, a strategy (Fe-IHP strategy) was proposed to enhance NRA activity by tuning the affinity of the electrode-electrolyte interface. The specifically adsorbed Fe(II) ions [SA-Fe(II)] greatly alleviated the electrostatic repulsion around the interfaceresulting in a 10-fold lower in the adsorption-free energy of NO3- when compared to the case without SA-Fe(II). Meanwhile, the modulated interface accelerated the kinetic mass transfer process by 25 folds compared to the control. Under neutral conditions, a Faraday efficiency of 99.6%, a selectivity of 99%, and an extremely high NH3 yield rate of 485.8 mmol h-1 g-1 FeOOH were achieved. Theoretical calculations and in-situ Raman spectroscopy confirmed the electron-rich state of the SA-Fe(II) donated to p orbitals of N atom and favored the hydrogenation of *NO to *NOH for promoting the formation of high-selectivity ammonia. In sum, these findings complement the textbook on the specific adsorption of cations and provide insights into the design of low-cost NRA catalysts with efficient ammonia synthesis.

Electron Transfer of Activated Carbon to Anode Excites and Regulates Desalination in Flow Electrode Capacitive Deionization.

The desalination performance of flow electrode capacitive deionization (FCDI) is determined by the ion adsorption on the powdered activated carbon (PAC) and the electron transfer between the current collector and PAC. However, a comprehensive understanding of rate-limiting steps is lacking, let alone to enhance FCDI desalination by regulating the PAC characteristics. This study showed that the electron transfer between PAC and the current collector on the anode side was the rate-limiting step of FCDI desalination. Compared with W900, the desalination performance of FCDI decreased by 95% when W1200 with weak electron transfer ability was used as a flow electrode. The PAC selected in this study transferred electrons directly through the conductive carbon matrix in FCDI and was mainly affected by graphitization. The desalination performance of FCDI was improved by 20 times when the graphitization degree of PAC increased from 0.69 to 1.03. The minimum energy required for electrons to escape from the PAC surface was reduced by the high degree of graphitization, from 4.27 to 3.52 eV, thus improving the electron transfer capacity of PAC on the anode side. This study provides a direction for the optimization of flow electrodes and further promotes the development of FCDI.

Enhanced Hydrosaturation Selectivity and Electron Transfer for Electrocatalytic Chlorophenols Hydrogenation on Ru Sites.

Electrocatalytic hydrogenation is acknowledged as a promising strategy for chlorophenol dechlorination. However, the widely used Pd catalysts exhibit drawbacks, such as high costs and low selectivity for phenol hydrosaturation. Herein, we demonstrate the potential and mechanism of Ru in serving as a Pd substitute using 2,4,6-trichlorophenol (TCP) as a model pollutant. Up to 99.8% TCP removal efficiency and 99% selectivity to cyclohexanol, a value-added compound with an extremely low toxicity, were achieved on the Ru electrode. In contrast, only 66% of TCP was removed on the Pd electrode, with almost no hydrosaturation selectivity. The superiority of Ru over Pd was especially noteworthy in alkaline conditions or the presence of interfering species such as S2-. The theoretical simulation demonstrates that Ru possesses a hydrodechlorination energy barrier of 0.72 eV, which is comparable to that on Pd. Meanwhile, hydrosaturation requires an activation energy of 0.69 eV on Ru, which is much lower than that on Pd (0.92 eV). The main reaction mechanism on Ru is direct electron transfer, which is distinct from that on Pd (indirect pathway via atomic hydrogen, H*). This work thereby provides new insights into designing cost-effective electrocatalysts for halogenated phenol detoxification and resource recovery.

Simultaneous Phenol Removal and Resource Recovery from Phenolic Wastewater by Electrocatalytic Hydrogenation.

Efficient pollutants removal and simultaneous resource recovery from wastewater are of great significance for sustainable development. In this study, an electrocatalytic hydrogenation (ECH) approach was developed to selectively and rapidly transform phenol to cyclohexanol, which possesses high economic value and low toxicity and can be easily recovered from the aqueous solution. A three-dimensional Ru/TiO2 electrode with abundant active sites and massive microflow channels was prepared for efficient phenol transformation. A pseudo-first-order rate constant of 0.135 min-1 was observed for ECH of phenol (1 mM), which was 34-fold higher than that of traditional electrochemical oxidation (EO). Both direct electron transfer and indirect reduction by atomic hydrogen (H*) played pivotal roles in the hydrogenation of phenol ring. The ECH technique also showed excellent performance in a wide pH range of 3-11 and with a high concentration of phenol (10 mM). Moreover, the functional groups (e.g., chloro- and methyl-) on phenol showed little influence on the superiority of the ECH system. This work provides a novel and practical solution for remediation of phenolic wastewater as well as recovery of valuable organic compounds.

Visualizing the Interfacial Charge Transfer between Photoactive Microcystis aeruginosa and Hydrogenated TiO2.

Exploring photoactive biotic-abiotic conjugations is of great importance for a variety of applications, but it remains difficult to probe the interfacial transfer of photoinduced charge carriers. In this work, Kelvin probe force microscopy, together with fluorescence imaging technique, were used to visually observe the spatial distribution and interfacial behavior of photocarriers in Microcystis aeruginosa/TiO2 hybrids. Experimental investigations suggested that photosynthetic microalgae cells were prone to trap photoholes from TiO2 photocatalysts. Oxygen vacancy defects in semiconductor exhibited significant impact on the charge migration, as the surface photovoltage of hydrogenated TiO2/microalgae hybrid was much higher than the pristine system. Profiting from the bioenhanced charge separation, biotic-abiotic architecture presented remarkably increased activity for photocatalytic inactivation of microalgae microorganisms. This work not only highlights the visual techniques for understanding the charge transfer around biotic-abiotic interface, but also provides a bioenhanced conjugation for the photocatalytic elimination of microorganisms in water treatment applications.

Enhanced oxidation of organic pollutants by regulating the interior reaction region of reactive electrochemical membranes.

Reactive electrochemical membrane (REM) emerges as an attractive strategy for the elimination of refractory organic pollutants that exist in wastewater. However, the limited reaction sites in traditional REMs greatly hinder its practical application. Herein, a feed-through coating methodology was developed to realize the uniform loading of SnO2-Sb catalysts on the interior surface of a REM. The uniformly coated REM (Unif-REM) exhibited 2.4 times higher reaction kinetics (0.29 min-1) than that of surface coated REM (Surf-REM) for the degradation of 2 mM 4-chlorophenol (4-CP), rendering an energy consumption as low as 0.016 kWh gTOC-1. The fast degradation of various emerging contaminants, e.g., sulfamethoxazole (SMX), ofloxacin (OFLX), and tetracycline (TC), also confirms its superior oxidation capability. Besides, the Unif-REM exhibited good performance in generating hydroxyl radicals (•OH) and a relatively long service lifetime. The simulation of spatial current distribution demonstrates that the interior reaction region in the Unif-REM channels can be drastically extended, thereby maximizing the surface coupling of mass diffusion and electron transfer. This study offers an in-depth look at the spatially confined reactions in REM and provides a reference for the design of electrochemical systems with economically efficient water purification.

In situ regulation of selectivity and permeability by electrically tuning pore size in trans-membrane ion process.

Regulating ion transport behavior through pore size variation is greatly attractive for membrane to meet the need for precise separation, but fabricating nanofiltration (NF) membranes with tunable pore size remains a huge challenge. Herein, a NF membrane with electrically tunable pores was fabricated by intercalating polypyrrole into reduced graphene oxide interlayers. As the potential switches from reduction to oxidation, the membrane pore size shrinks by 11%, resulting in a 16.2% increase in salt rejection. The membrane pore size expands/contracts at redox potentials due to the polypyrrole volume swelling/shrinking caused by the insertion/desertion of cations, respectively. In terms of the inserted cation, Na+ and K+ induce larger pore-size stretching range for the membrane than Ca2+ due to greater binding energy and larger doping amount. Such an electrical response characteristic remained stable after multiple cycles and enabled application in ion selective separation; e.g., the Na+/Mg2+ separation factor in the reduced state is increased by 41% compared to that in the oxide state. This work provides electrically tunable nanochannels for high-precision separation applications such as valuable substance purification and resource recovery from wastewater.

Unveiling the spatially confined oxidation processes in reactive electrochemical membranes.

Electrocatalytic oxidation offers opportunities for sustainable environmental remediation, but it is often hampered by the slow mass transfer and short lives of electro-generated radicals. Here, we achieve a four times higher kinetic constant (18.9 min-1) for the oxidation of 4-chlorophenol on the reactive electrochemical membrane by reducing the pore size from 105 to 7 µm, with the predominate mechanism shifting from hydroxyl radical oxidation to direct electron transfer. More interestingly, such an enhancement effect is largely dependent on the molecular structure and its sensitivity to the direct electron transfer process. The spatial distributions of reactant and hydroxyl radicals are visualized via multiphysics simulation, revealing the compressed diffusion layer and restricted hydroxyl radical generation in the microchannels. This study demonstrates that both the reaction kinetics and the electron transfer pathway can be effectively regulated by the spatial confinement effect, which sheds light on the design of cost-effective electrochemical platforms for water purification and chemical synthesis.

Pumping and sliding of droplets steered by a hydrogel pattern for atmospheric water harvesting.

Atmospheric water harvesting is an emerging strategy for decentralized and potable water supplies. However, water nucleation and microdroplet coalescence on condensing surfaces often result in surface flooding owing to the lack of a sufficient directional driving force for shedding. Herein, inspired by the fascinating properties of lizards and catfish, we present a condensing surface with engineered hydrogel patterns that enable rapid and sustainable water harvesting through the directional pumping and drag-reduced sliding of water droplets. The movement of microscale condensed droplets is synergistically driven by the surface energy gradient and difference in Laplace pressure induced by the arch hydrogel patterns. Meanwhile, the superhydrophilic hydrogel surface can strongly bond inner-layer water molecules to form a lubricant film that reduces drag and facilitates the sliding of droplets off the condensing surface. Thus, this strategy is promising for various water purification techniques based on liquid-vapor phase-change processes.

Anode passivation mitigation by homogenizing current density distribution in electrocoagulation.

Electrode passivation is the most challenging technical problem in electrocoagulation (EC) water treatment process, but research on understanding and mitigating passivation evolution are still lacking. Herein, homogenization of current density (CD) distribution was found to be a critical factor in alleviating the anode passivation during EC process. Decreasing electrode area decelerated the growth of passivation layer on anode through homogenizing CD distribution, which was quantified by the ratios of CD distributed at the electrode edges and centers. When aluminum anode area decreased from 8 cm2 to 2 cm2 with a constant CD, the homogenization degree increased by 24.0%, and passivation was reduced by 24.3%. The depth profiles of passivated anodes confirmed the inhomogeneity of the anode passivation. Thicker passivation layers were observed at edges due to high CD distributions, which originated from the "edge effect" of electric field distribution between parallel plate electrodes. A facile strategy to homogenize CD distribution by splitting electrodes into smaller electrodes is then proposed for passivation mitigation, which can save energy consumption by 21.8% with unchanged removal efficiency. This study provides a unique insight into anode passivation mitigation and a feasible electrode design in EC.

Protonated carbon nitride elicits microalgae for water decontamination.

Comprehending the effects of synthetic nanomaterials on natural microorganisms is critical for the development of emerging nanotechnologies. Compared to artificial inactivation of microbes, the up-regulation of biological functions should be more attractive due to the possibility of discovering unexpected properties. Herein, a nanoengineering strategy was employed to tailor g-C3N4 for the metabolic regulation of algae. We found that surface protonated g-C3N4 (P-C3N4) as a nanopolymeric elicitor enabled the reinforced biological activity of Microcystis aeruginosa and Scenedesmus for harmful substances removal. Metabolomics analysis suggested that synthetic nanoarchitectures induced moderate oxidative stress of algae, with up-regulated biosynthesis of extracellular polymeric substances (EPS) for resisting the physiological damage caused by toxic substances in water. The formation of oxidative .O2- contributed to over five-fold enhancement in the biodecomposition of harmful aniline. Our study demonstrates a synergistic biotic-abiotic platform with valuable outcomes for various customized applications.

Enhanced struvite generation and separation by magnesium anode electrolysis coupled with cathode electrodeposition.

Adding magnesium ions (Mg2+) to produce struvite is an important method to recover nitrogen and phosphorus from wastewater. Both the Mg2+ source and subsequent separation of struvite are key factors for the utilization of struvite. In this study, we developed an efficient method to recover nutrient salts from wastewater using sacrificial Mg anodes to generate struvite, with its simultaneous separation through cathode electrodeposition. The anode-released Mg2+ reacted with NH4+-N and PO43--P in bulk solution to form struvite, which was more intense on the cathode surface due to the relatively higher pH environment from hydrogen evolution, resulting in most of the struvite being deposited on the cathode surface and simultaneously separated out of the bulk solution. Using a cathode with a higher solution-cathode interface area and relatively low current density facilitated struvite deposition. Results showed that under optimal electrolysis condition (5.76 A/m2, pH 8.5, 180 min, and 1.2:1.0 Mg:P), 91% of the undissolved substances as the phosphate precipitation were deposited on the graphite cathode surface, and the proportion of struvite in the deposition reached 41.52%. This study provides a novel electrochemical method for struvite synthesis and separation for the recovery of nitrogen and phosphorus from wastewater.

Controllable Ferroelastic Switching in Epitaxial Self-Assembled Aurivillius Nanobricks.

Layered perovskites with Aurivillius phase have drawn tremendous attention recently, owing to their high ferroelectric Curie temperatures, large spontaneous polarization, and fatigue-free and environment-friendly characteristics. Bi2WO6 is one of the simplest members in the Aurivillius family with superior ferroelastic and photo-electrochemical behaviors. The self-assembly fabrication of its nanoarchitectures and strategic modulation of their ferroelastic switching are crucial toward highly efficient nanoscale applications. In this work, Bi2WO6 nanobrick arrays were epitaxially grown along the orthorhombic direction in a self-assembled way. Such a nanoscale topology supports out-of-plane and in-plane vectors of ferroelectric polarizations, enabling a perpendicular voltage manipulation of these emerging ferroelectric/elastic domains. Combining the scanning probe technique and transmission electron microscopy, we confirmed the in-plane polarization vectors of 78.6 and 101.4° within the crystallographic axes of the nanobricks with respect to the (110) plane of the substrate. Thus, this work provides new opportunities for ferroelectric/elastic engineering in Bi2WO6 nanostructures for a wide range of applications, such as sensing, actuating, and catalysis.