N-doped carbon-iron heterointerfaces for boosted electrocatalytic active and selective ammonia production.

The electrochemical conversion of waste nitrate (NO3-) to valuable ammonia (NH3) is an economical and environmentally friendly technology for sustainable NH3 production. It is beneficial for environmental nitrogen pollution management and is also an appealing alternative to the current Haber-Bosch process for NH3 production. However, owing to the competing hydrogen evolution reaction, it is necessary to design highly efficient and stable electrocatalysts with high selectivity. Herein, we report a rational design of Fe nanoparticles wrapped in N-doped carbon (Fe@N10-C) as a high NH3 selective and efficient electrocatalyst using a metal-organic framework precursor. We constructed a catalyst with new active sites by doping with nitrogen, which activated neighboring carbon atoms and enhanced metal-to-carbon electron transfer, resulting in high catalytic activity. These doped N sites play a key role in the NO3- electroreduction. As a result, the Fe@N10-C nanoparticles with optimal doping of N demonstrated remarkable performance, with a record-high NO3- removal capacity of 125.8 ± 0.5 mg N gcat-1 h-1 and nearly 100 % (99.7 ± 0.1%) selectivity. The catalyst also delivers an impressive NH3 production rate of 2647.7 µg h-1 cm-2 and high faradaic efficiency of 91.8 ± 0.1%. This work provides a new route for N-doped carbon-iron catalysis application and paves the way for addressing energy and environmental issues.

High-ammonia selective metal-organic framework-derived Co-doped Fe/Fe2O3 catalysts for electrochemical nitrate reduction.

Ammonia (NH3) is an ideal carbon-free power source in the future sustainable hydrogen economy for growing energy demand. The electrochemical nitrate reduction reaction (NO3-RR) is a promising approach for nitrate removal and NH3 production at ambient conditions, but efficient electrocatalysts are lacking. Here, we present a metal-organic framework (MOF)-derived cobalt-doped Fe@Fe2O3 (Co-Fe@Fe2O3) NO3-RR catalyst for electrochemical energy production. This catalyst has a nitrate removal capacity of 100.8 mg N gcat-1 h-1 and an ammonium selectivity of 99.0 ± 0.1%, which was the highest among all reported research. In addition, NH3 was produced at a rate of 1,505.9 µg h-1 cm-2, and the maximum faradaic efficiency was 85.2 ± 0.6%. Experimental and computational results reveal that the high performance of Co-Fe@Fe2O3 results from cobalt doping, which tunes the Fe d-band center, enabling the adsorption energies for intermediates to be modulated and suppressing hydrogen production. Thus, this study provides a strategy in the design of electrocatalysts in electrochemical nitrate reduction.

Boosted ammonium production by single cobalt atom catalysts with high Faradic efficiencies.

Efficient n = O bond activation is crucial for the catalytic reduction of nitrogen compounds, which is highly affected by the construction of active centers. In this study, n = O bond activation was achieved by a single-atom catalyst (SAC) with phosphorus anchored on a Co active center to form intermediate N-species for further hydrogenation and reduction. Unique phosphorus-doped discontinuous active sites exhibit better n = O activation performance than conventional N-cooperated single-atom sites, with a high Faradic efficiency of 92.0% and a maximum ammonia yield rate of 433.3 µg NH4·h-1·cm-2. This approach of constructing environmental sites through heteroatom modification significantly improves atom efficiency and will guide the design of future functional SACs with wide-ranging applications.

Atomically dispersed Fe atoms anchored on S and N-codoped carbon for efficient electrochemical denitrification.

Nitrate, a widespread contaminant in natural water, is a threat to ecological safety and human health. Although direct nitrate removal by electrochemical methods is efficient, the development of low-cost electrocatalysts with high reactivity remains challenging. Herein, bifunctional single-atom catalysts (SACs) were prepared with Cu or Fe active centers on an N-doped or S, N-codoped carbon basal plane for N2 or NH4+ production. The maximum nitrate removal capacity was 7,822 mg N ⋅ g-1 Fe, which was the highest among previous studies. A high ammonia Faradic efficiency (78.4%) was achieved at a low potential (-0.57 versus reversible hydrogen electrode), and the nitrogen selectivity was 100% on S-modified Fe SACs. Theoretical and experimental investigations of the S-doping charge-transfer effect revealed that strong metal-support interactions were beneficial for anchoring single atoms and enhancing cyclability. S-doping altered the coordination environment of single-atom centers and created numerous defects with higher conductivity, which played a key role in improving the catalyst activity. Moreover, interactions between defects and single-atom sites improved the catalytic performance. Thus, these findings offer an avenue for high active SAC design.

Monodisperse amino-modified nanosized zero-valent iron for selective and recyclable removal of TNT: Synthesis, characterization, and removal mechanism.

Nitroaromatic explosives are major pollutants produced during wars that cause serious environmental and health problems. The removal of a typical nitroaromatic explosive, 2,4,6-trinitrotoluene (TNT), from aqueous solution, was conducted using a new recyclable magnetic nano-adsorbent (Fe@SiO2NH2). This adsorbent was prepared by grafting amino groups onto Fe@SiO2 particles with a well-defined core-shell structure and demonstrated monodispersity in solution. The removal performance of the nano-adsorbent towards TNT was found to be 2.57 and 4.92 times higher than that towards two analogous explosives, 2,4-dinitrotoluene (2,4-DNT) and 2-nitrotoluene (2-NT), respectively, under neutral conditions. The difference in the removal performance among the three compounds was further compared in terms of the effects of different conditions (pH value, ionic strength, humic acid concentration, adsorbent modification degree and dosage, etc.) and the electrostatic potential distributions of the three compounds. The most significant elevation is owing to modification of amino on Fe@SiO2 which made a 20.7% increase in adsorption efficiency of TNT. The experimental data were well fit by the pseudo-second-order kinetic model and the Freundlich adsorption isotherm model, indicating multilayer adsorption on a heterogeneous surface. The experimental results and theoretical considerations show that the interactions between Fe@SiO2NH2 NPs and TNT correspond to dipole-dipole and hydrophobic interactions. These interactions should be considered in the design of an adsorbent. Furthermore, the adaptability to aqueous environment and excellent regeneration capacity of Fe@SiO2NH2 NPs makes these remediation materials promising for applications.

Efficient electrocatalytic nitrate reduction via boosting oxygen vacancies of TiO2 nanotube array by highly dispersed trace Cu doping.

Nitrate pollution of water bodies is a serious global-scale environmental problem. The electrocatalytic nitrate reduction reaction (NO3RR) using Cu-based electrodes allows excellent nitrate removal; however, its long-term operation results in copper leaching, leading to health risks. This study proposes a strategy for efficient nitrate removal through the activation of oxygen vacancies on a highly dispersed Cu-doped TiO2 nanotube array (Cu/TNTA) cathode via electrodeposition. The mechanism underlying the activation of oxygen vacancies and enhancement in charge transfer at the cathode-pollutant interface upon trace (0.02 wt%) Cu doping is elucidated by electron paramagnetic resonance analysis, UV-visible diffuse reflection spectroscopy, and Raman spectroscopy. The Cu/TNTA-300 exhibits a nitrate removal rate of 84.3% at 12 h; the electrode activity did not decrease after 10 cycles, and no Cu2+ was detected in the solution. Electrochemical characterization and density functional theory calculations demonstrate that Cu doping promotes efficient charge transfer between nitrate and the electrode and reduces the energy barrier of the nitrate reduction reaction. This work provides a platform for novel design of cathodes for use in efficient and safe electrocatalytic nitrate reduction in environmental water bodies.

High efficient bio-denitrification of nitrate contaminated water with low ammonium and sulfate production by a sulfur/pyrite-based bioreactor.

Sulfur-based autotrophic denitrification (SAD) and pyrite-based autotrophic denitrification (PAD) are important technologies that address nitrate pollution, but high sulfate production and low denitrification efficiency, respectively, limit their application in engineering. A bio-denitrification reactor with sulfur and pyrite as filler materials was studied to remove NO3--N from nitrate contaminated water. At an influent NO3--N concentration of 50 mg/L, NO3--N removal efficiency of the sulfur/pyrite-based bioreactor was 99.2%, producing less NH4+-N and SO42- than the sulfur-based bioreactor, even after long-term operation. Denitrification performance was significantly related to environmental variable, especially dissolved oxygen. Proteobacteria and Epsilonbacteraeota were the predominant phyla in the sulfur/pyrite-based bioreactor, and fewer dissimilatory nitrate reductions to ammonia process-related bacteria were enriched compared to those in the sulfur-based bioreactor. Sulfur-pyrite bio-denitrification provides an efficient alternative method for treatment of nitrate contaminated water.

Efficient recovery of Cu(II) by LTA-zeolites with hierarchical pores and their resource utilization in electrochemical denitrification: Environmentally friendly design and reutilization of waste in water.

Water pollution seriously endangers human health and the environment. Here we prepared and tested mesoporous LTA zeolites for the adsorption of Cu(II) from aqueous media and the captured copper was further used for electrochemical nitrate reduction. The prepared hierarchically porous LTA exhibited a high capacity (341.5 mg g-1) for Cu(II) adsorption, following the pseudo-second-order kinetic and Freundlich adsorption isotherm models well. The Cu-LTA sample was characterised by various analytical methods, and Cu(I) species were identified as the active sites for nitrate electrochemical reduction. Based on the spectral characterization and reducibility, strong metal-support interaction was found between copper and LTA, which is beneficial to the dispersion of active sites and their contacts with nitrates. In total, 10.1 g-N-NO3 g-1-Cu was reduced over the Cu-LTA-modified cathode in a three-electrode system with high N2 selectivity (92.1 %). Compared to purely microporous zeolites, mesoporous LTA has a higher capacity for Cu(II) removal and nitrate reduction. The mesoporous structure allows easy access to the inner active sites with low diffusion resistance. The low Tafel slope and high current density confirm the high activity of the mesoporous Cu-LTA, making it a promising and efficient material for the removal and reuse of heavy metal ions.

Mechanism and optimization of electrochemical system for simultaneous removal of nitrate and ammonia.

In this study, an electrochemical system was established for simultaneous harmless removal of nitrate and ammonia multiple contamination in an undivided single cell. Cyclic voltammetry was used to investigate the electrochemical cathode and anode coupling redox mechanism and concurring evolution of nitrate and ammonia. The cyclic voltammograms showed the cathodic reduction of nitrate to ammonia and nitrite, the chloride ion conversion to hypochlorite and hypochlorous acid, and the oxidation of ammonia to nitrogen gas and nitrate. A circular transformation process was formed in the electrochemical system and the final product was harmless nitrogen gas. The multiple nitrogen pollutants in the original contaminated system were gradually removed with the reaction predominantly produced harmless nitrogen gas. Response surface methodology was used to build mathematical models for optimizing the operating conditions. The optimum time, NaCl concentration, and current density were 85.38 min, 0.24 g/L, and 45.13 mA/cm2, respectively. Under the optimum conditions, the nitrate and ammonia concentrations in the treated solution were 9.17 and 0.00 mg/L, respectively.