Core–Shell Engineering Boosted Active Hydrogen Generation in Cu_2–xS/MoS₂ Quantum Dots for Efficient Electrocatalytic Nitrate Reduction to Ammonia

ACS Sustainable Chemistry & Engineering, Год журнала: 2024, Номер 12(15), С. 5979 - 5990

Опубликована: Апрель 1, 2024

The electrochemical nitrate reduction reaction (NO3RR) emerges as a promising method for ammonia (NH3) production, which faces the dilemma of inhibiting hydrogen evolution (HER) and promoting active (Hads) supply hydrogenation nitrogen intermediates. Here, core–shell structure engineering strategy is developed Cu2–xS/MoS2, where strong Hads adsorption storage capacity can accelerate As result, an eminent NH3 yield 0.178 mmol h–1 cm–2 Faradaic efficiency 84.5% were achieved. A series tests demonstrate that tuning Cu2–xS/MoS2 interface improve activity conversion NO2–, while avoiding HER effectively retain Hads. density functional theory calculation further demonstrates has *H retention ability to promote NO3RR process. This work offers novel perspective on manipulation generation NO3RR.

Язык: Английский

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Engineering the Metal‐Support Interaction and Oxygen Vacancies on Ru@P‐Fe/Fe₃O₄ Nanorods for Synergetic Enhanced Electrocatalytic Nitrate‐to‐Ammonia Conversion

Advanced Functional Materials, Год журнала: 2024, Номер 34(36)

Опубликована: Апрель 2, 2024

Abstract Ruthenium (Ru) loaded catalysts show high activity and selectivity for ammonia (NH 3 ) synthesis via electrochemical reduction of nitrate (NO − ), but their practical application is still restricted by cost insufficient stability. Herein, a multi‐component electrocatalyst Ru nanoclusters on phosphorus‐doped/phosphate‐modified oxygen vacancy (O V )‐rich Fe/Fe O 4 composite nanorods (Ru@P‐Fe/Fe to synergistically promote electrocatalytic NO reaction RR)‐to‐NH performance strong metal‐support interaction (SMSI) reported. Impressively, the best Ru@P‐Fe/Fe catalyst exhibits outstanding RR activity, selectivity, durability in 0.1 M KNO + 0.5 KOH solution, with an NH yield rate 14.37 ± 0.21 mg NH3 h −1 cm −2 (1710.71 25 at −0.75 versus reversible hydrogen electrode (vs. RHE), Faradaic efficiency (FE) 97.2% −0.55 vs. RHE, superior stability over 50 h, suppressing most reported Fe‐based Ru‐based electrocatalysts. The characterizations theoretical calculations unveil that SMSI between P‐Fe/Fe can generation , tune electronic structure species, stabilize nanoclusters, thereby reducing energy barrier RR‐to‐NH inhibiting competitive evolution reaction, boosting FE,

Язык: Английский

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Boosting Electrochemical Ammonia Synthesis via NO_x Reduction over Sulfur‐Doped Copper Oxide Nanoneedle Arrays

Advanced Energy Materials, Год журнала: 2024, Номер 14(30)

Опубликована: Май 14, 2024

Abstract The electrochemical NO x reduction reactions, involving nitrate and nitrite reactions (NO 3 − RR 2 RR), have emerged as promising approaches for both removal, ammonium (NH ) synthesis under ambient conditions. However, the incorporation stabilization of sulfur dopants in catalysts efficient are rarely explored, leading to an unclear effect on mechanism. Herein, sulfur‐doped Cu O (S‐Cu O) nanoneedle arrays via situ treatment synthesized. S‐Cu catalyst possesses excellent durability selectivity NH over a wide range potentials RR, attaining maximum Faradaic efficiency 94% at −0.6 V RHE yield high 1.06 mmol h −1 cm −2 . In dopant can accelerate step from , contributing superior performance assembled Zn−NO battery device. Density functional theory (DFT) calculations reveal that presence enhance initial *NO adsorption, lower reaction barriers formation *NHO intermediate, activate H dissociation process. work sheds light role enhancing electrocatalytic provides unique perspective understanding

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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Manipulating d-band center of bimetallic Sn-alloy coupling with carbon nanofibers for high-performance electrocatalytic production of ammonia from nitrate

Chemical Engineering Journal, Год журнала: 2024, Номер 496, С. 154094 - 154094

Опубликована: Июль 17, 2024

Язык: Английский

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