RESUMEN

Excessive discharge of nitrogen-containing chemical products into the natural water environment leads to the serious environmental problem of nitrate-nitrogen pollution, threatening the ecological balance and human health. In this study, we propose an efficient denitrification electrochemical method utilizing iron-doped zeolite imidazolium framework derived defective nitrogen-doped carbon (d-FeNC) catalysts. The d-FeNC catalyst exhibited 97 % nitrate removal efficiency and 94 % total nitrogen (TN) removal, and the reaction rate constant was increased from 0.73 h-1 of the Fe-undoped electrocatalyst (d-NC) to 1.11 h-1. The successful synthesis of d-FeNC with carbon defect sites and encapsulated Fe was confirmed by in-depth characterization. In situ electron paramagnetic resonance (EPR) analysis in conjunction with cyclic voltammetry (CV) tests confirmed the carbon substrates with defect enhanced the trapping of atomic hydrogen (H*) on the catalyst surface. Density functional theory (DFT) calculations clarified the doping of Fe facilitated the adsorption of nitrate, resulting in contact of H* with nitrate on the catalyst surface. In the synergy of the defective state organic framework and metal Fe, H* and nitrate realized a collision process. The electrochemical denitrification system achieved an excellent nitrate removal capacity of 7587 mgN·g-1cat in high-concentration nitrate solution and showed excellent stability under various conditions. Overall, this study underscores the potential of defective iron-doped carbon catalysts for efficient electrocatalytic denitrification, providing a promising approach for sustainable wastewater treatment.

RESUMEN

Electrocatalytic denitrification is an attractive and effective method for complete elimination of nitrate (NO3-). However, its application is limited by the activity and stability of the electrocatalyst. In this work, a novel bimetallic electrode was synthesized, in which N-doped graphitized carbon sealed with Cu and Fe nanoparticles and immobilized them on nickel foam (CuFe NPs@NC/NF) without any chemical binder. The immobilized Cu-Fe nanoparticles not only facilitated the adsorption of the reactant but also enhanced the electron transfer between the cathode and NO3-, thus promoting the electrochemical reduction of NO3-. Therefore, the as-prepared electrode exhibited enhanced electrocatalytic activity for NO3- reduction. The composite electrode with the Cu/Fe molar ratio of 1:2 achieved the highest NO3- removal (79.4 %) and the lowest energy consumption (0.0023 kW h mg-1). Furthermore, the composite electrode had a robust NO3- removal capacity under various conditions. Benefitting from the electrochlorination on the anode, this electrochemical system achieved nitrogen (N2) selectivity of 94.0 %. Moreover, CuFe NPs@NC/NF exhibited good stability after 15 cycles, which should be attributed to the graphitized carbon layer. This study confirmed that CuFe NPs@NC/NF electrode is a promising and inexpensive electrode with long-term stability for electrocatalytic denitrification.

Asunto(s)

RESUMEN

The green and efficient removal of nitrate (NO3-) in groundwater is a primary concern nowadays, and membrane capacitive deionization (MCDI) is an emerging technology for the removal of nitrate (NO3-) from water. In this study, a novel electrochemical system for nitrate denitrification removal was established, wherein the economic non-noble metal copper was used as the electrode material to achieve harmless removal of nitrate in a single electrochemical cell. The effects of applied voltage, initial NO3- concentration, and co-existing matters on NO3- denitrification removal during electro-adsorption/reduction system were deeply investigated. The results showed that the NO3- denitrification removal increased with raised voltage and in proportion to the initial NO3- concentration within certain limits, wherein the removal rate reached a maximum of 53.3% in the single-solute solution of 200 mg L-1 NaNO3 at 1.8 V. Nevertheless, overhigh voltage or initial NO3- concentration would have a negative effect on nitrate removal, which was caused by multiple factors, including side reactions in the solution, fouling of activated carbon fiber and anion exchange membrane, and corrosion of copper electrode. The presence of NaCl also had a negative effect on the removal of nitrate, which was mainly caused by fouling of ACF/IEM and redox reaction on account of the chloride ions. This study provides a potential economical alternative for the NO3- denitrification removal to achieve a more environmentally friendly outcome.

Asunto(s)

RESUMEN

Nitrate is the leading cause of eutrophication worldwide and is one of the most challenging pollutants for restoration of polluted surface waters such as lakes, rivers and reservoirs. We report herein a new architecture of iron nanoparticles for high-efficiency denitrification by selective reduction of nitrate (NO3-) to dinitrogen (N2). The iron nanoparticles are doped with nitrogen (FeN) and encapsulated within a thin layer of nitride-carbon (NC). The nanoparticles have high pyrrolic N content (17.4 at.%) and large specific surface area (2040 m2/g). Laboratory experiments demonstrated high N2 selectivity (91%) and nitrate removal capacity (6004 mg N/g Fe) for treatment of nitrate-containing water. This iron-based nanomaterial overcomes shortcomings of conventional catalysts by eliminating the use of precious and toxic heavy metals (e.g., Pd, Pt, Cu, Ni) and minimizing the generation of undesirable byproducts (e.g., ammonia) from the reactions with nanoscale zero-valent iron (nZVI). The multiple electron transfers process from NO3- to N2 can be fine-tuned by adjusting the NC shell thickness. Superior electrocatalytic performance, low cost and minimal environmental impact of the iron-derived nanocatalyst offer promising prospects for water purification, waste treatment and environmental remediation.

RESUMEN

Electrocatalytic denitrification is considered as the most promising technology to transform nitrates to nitrogen gas in sewage so far. Although noble metal-based catalysts as a cathode material have reached decent removal capacity of nitrate, the high cost is the main hamper of electrocatalytic reduction. Therefore, the development of alternative catalysis toward highly effective denitrification is imperative yet still remains a significant challenge. Herein, a corchorifolius-like structure, where Fe nanoparticles are sealed in carbon microspheres (CL-Fe@C) with a rough surface, has been elaborately designed by self-assemble strategy. Impressively, the architectured CL-Fe@C microspheres are surrounded with a lot of small iron nanoparticles and contain the high iron content of ∼74%. As a result, an excellent removal capacity of 1816 mg N/g Fe and a high nitrogen selectivity of 98% under a very low nitrate concentration of 100 mg/L are achieved when using the CL-Fe@C microspheres as electrocatalytic denitrification. The present work not only explores high performance electrocatalysis for the denitrification but also promote new inspiration for the preparation of other iron-based functional materials for diverse applications.