Sustainable ammonia synthesis: opportunities for electrocatalytic nitrate reduction

Journal of Energy Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Фев. 1, 2025

Язык: Английский

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Lattice Oxygen-Driven Co-Adsorption of Carbon Dioxide and Nitrate on Copper: A Pathway to Efficient Urea Electrosynthesis

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Фев. 10, 2025

The electrochemical coupling of CO2 and NO3– on copper-based catalysts presents a sustainable strategy for urea production while simultaneously addressing wastewater denitrification. However, the inefficient random adsorption copper surface limits interaction key carbon nitrogen intermediates, thereby impeding efficient C–N coupling. In this study, we demonstrate that residual lattice oxygen in oxide-derived nanosheets (OL-Cu) can effectively tune electron distribution, thus activating neighboring atoms generating electron-deficient (Cuδ+) sites. These Cuδ+ sites enhance stabilize *CO which enables directional at adjacent This mechanism shortens pathway achieves yield up to 298.67 mmol h–1 g–1 −0.7 V versus RHE, with an average Faradaic efficiency 31.71% high current density ∼95 mA cm–2. situ spectroscopic measurements confirmed formation tracked evolution intermediates (i.e., *CO, *NO, *OCNO, *NOCONO) during synthesis. Density functional theory calculations revealed promote coadsorption *NO3, as well *OCNO significantly improving kinetics. study underscores critical role facilitating selectivity.

Язык: Английский

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Self-Triggering a Locally Alkaline Microenvironment of Co₄Fe₆ for Highly Efficient Neutral Ammonia Electrosynthesis

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Фев. 28, 2025

Electrochemical nitrate reduction reaction (eNO3-RR) to ammonia (NH3) holds great promise for the green treatment of NO3- and ambient NH3 synthesis. Although Fe-based electrocatalysts have emerged as promising alternatives, their excellent eNO3-RR-to-NH3 activity is usually limited harsh alkaline electrolytes or alloying noble metals with Fe in sustainable neutral electrolytes. Herein, we demonstrate an unusual self-triggering localized alkalinity Co4Fe6 electrocatalyst efficient media, which breaks down conventional pH-dependent kinetics restrictions shows a 98.6% Faradaic efficiency (FE) 99.9% selectivity at -0.69 V vs RHE. The synergetic Co-Fe dual sites were demonstrated enable optimal free energies species balance water dissociation protonation adsorbed NO2-. Notably, can attain high current density 100 mA cm-2 FE surpassing 96% long-term stability over 500 h membrane electrode assembly (MEA) electrolyzer. This work provides insight into tailoring self-reinforced local-alkalinity on alloy thus avoids practical upcycling technology.

Язык: Английский

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Nanoflower‐Like CuPd/CuO Heterostructure for an Energy‐Output Electrocatalytic System Coupling Ammonia Electrosynthesis and Zinc‐Nitrate Battery

Advanced Functional Materials, Год журнала: 2025, Номер unknown

Опубликована: Март 18, 2025

Abstract Electrochemical nitrate reduction reaction (NO 3 RR) can effectively alleviate pollution and simultaneously realize ammonia electrosynthesis at room temperature. However, it remains a significant challenge for NO RR to achieve high Faradic efficiency in full concentration range. Herein, nanoflower‐like copper‐palladium alloy/CuO heterostructure (CuPd/CuO@NF) is successfully fabricated by the hydrothermal synthesis of CuO nanoflowers subsequent formation CuPd alloy. The as‐obtained CuPd/CuO@NF exhibits remarkable electrochemical performance − ‐N range from 20 1400 ppm, especially with conversion rate 97.8% NH selectivity 99.3% 94.2% yield 1.37 mmol h −1 cm −2 ppm. In‐situ Fourier transform infrared spectroscopy Raman spectra reveal that first catalyzes 2 , which rapidly reduced forming *NH, *NH OH intermediates. Density functional theory calculations suggest NHO route thermodynamically favorable. When applied zinc‐nitrate battery, demonstrates maximum power density 53.7 mW 99.9% 94.4%. This work offers valuable insights into design novel electrocatalysts batteries.

Язык: Английский

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Boosting Active Hydrogen Generation via Ruthenium Single Atoms for Efficient Electrocatalytic Nitrate Reduction to Ammonia

Applied Catalysis B Environment and Energy, Год журнала: 2024, Номер unknown, С. 124943 - 124943

Опубликована: Дек. 1, 2024

Язык: Английский

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Engineering Nickel Dopants in Atomically Thin Molybdenum Disulfide for Highly Efficient Nitrate Reduction to Ammonia

Advanced Functional Materials, Год журнала: 2024, Номер unknown

Опубликована: Сен. 16, 2024

Abstract The electrocatalytic nitrate reduction reaction (NO 3 − RR) presents a promising pathway for achieving both ammonia (NH ) electrosynthesis and water pollutant removal simultaneously. Among various electrocatalysts explored, 2D materials have emerged as candidates due to their ability regulate electronic states active sites through doping. However, the impact of doping effects in on mechanism NO RR remains relatively unexplored. Here, Ni‐doped MoS 2 (Ni‐MoS nanosheets are investigated model system, demonstrating enhanced performance compared undoped counterparts. By controlling concentration, Ni‐MoS achieve remarkable faradic efficiency (FE) 92.3% NH at −0.3 V RHE with excellent stability. mechanistic studies reveal that elevation performances originates from generation more hydrogen acceleration nitrite facilitated by Ni Combining experimental observations theoretical calculations it is revealed appropriate level can enhance *NO adsorption strength, thereby facilitating subsequent steps. Together demonstration Zn−NO battery devices, work provides new insights into design regulation material catalysts efficient RR.

Язык: Английский

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FeIr Alloy Optimizes the Trade‐Off Between Nitrate Reduction and Active Hydrogen Generation for Efficient Electro‐Synthesis of Ammonia in Neutral Media

Advanced Functional Materials, Год журнала: 2025, Номер unknown

Опубликована: Фев. 10, 2025

Abstract Electrochemically promoted nitrate reduction reaction (NITRR) holds great potential for the “green” synthesis of ammonia (NH 3 ). However, NITRR in neutral media, though close to practical scenario, is often limited by an insufficient supply active hydrogen (*H) due sluggish water cleavage. In this work, it demonstrated that a bimetallic alloy FeIr can optimize trade‐off between and *H formation media. As result, exhibits excellent catalytic performance toward with Faradaic efficiency NH up 97.3% high yield rate 11.67 mg h −1 cm −2 at low working −0.6 V (versus reversible electrode (RHE)), surpassing monometallic catalysts as well majority Fe‐based state‐of‐the‐art. It also found displays remarkable electron rearrangement hetero‐atoms their significant orbital hybridization, which benefits not only but process. Moreover, coupling FeIr‐based methanol oxidation (MOR) results sustainable productions formate combined FE nearly 200% cell‐voltage 2 V. This work thus demonstrates promising strategy designing efficient NITRR.

Язык: Английский

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Incorporating Ordered Indium Sites into Rhodium for Ultra‐Low Potential Electrocatalytic Conversion of Ethylene Glycol to Glycolic Acid

Advanced Materials, Год журнала: 2025, Номер unknown

Опубликована: Март 3, 2025

Abstract The upcycling of polyethylene terephthalate (PET)‐derived ethylene glycol (EG) to glycolic acid (GA, a biodegradable polymer monomer) via electrocatalysis not only produces valuable chemicals but also mitigates plastic pollution. However, the current reports for electrooxidation EG‐to‐GA usually operate at reaction potentials >1.0 V vs reversible hydrogen electrode (RHE), much higher than theoretical potential (0.065 RHE), resulting in substantial energy wastage. Herein, body‐centered cubic RhIn intermetallic compounds (IMCs) anchored on carbon support (denoted as RhIn/C) are synthesized, which shows excellent performance with an onset 0.35 RHE, lower values reported literature. catalyst possesses satisfactory GA selectivity (85% 0.65 RHE). Experimental results combined density functional theory calculations demonstrate that IMCs enhance adsorption EG and OH − , facilitating generation reactive oxygen species thereby improving catalytic performance. RhIn/C exhibits electrocatalytic evolution reaction, ensuring it can be used bifunctional two‐electrode system coupled production. This work opens new avenues reducing consumption PET‐derived clean

Язык: Английский

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Intermetallic compounds for nitrogen electrochemistry

Green Energy & Environment, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Язык: Английский

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Balancing Hydrogen Evolution and Hydrogenation Reaction via Facet Engineering for Efficient Conversion of Nitrate to Ammonia in Actual Wastewater

Angewandte Chemie International Edition, Год журнала: 2025, Номер unknown

Опубликована: Март 11, 2025

Abstract Due to the competitive relationship between nitrate reduction reaction (NO 3 − RR) and hydrogen evolution (HER), conventional approach improve Faradaic efficiency is select a catalyst without HER activity. Nevertheless, such strategy not only limits application of catalysts in NO RR, but also causes insufficient source, thereby sacrificing ammonia yield rate. We believe that should be excluded from hydrogenation reduction. Herein, taking traditional water electrolysis material Co O 4 as model system, we reveal oxygen vacancies on crystal facet can greatly promote dissociation capture intermediate for successfully shifting pathway hydrogenation. Beyond development, construct hybrid reactor achieve an recovery rate 1216.8 g‐N m −2 d −1 nuclear industry wastewater with ultra‐high concentration. This study breaks through limitation which provides significant insight into designing mechanism.

Язык: Английский

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